CN116374974A - Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process - Google Patents
Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process Download PDFInfo
- Publication number
- CN116374974A CN116374974A CN202310219170.8A CN202310219170A CN116374974A CN 116374974 A CN116374974 A CN 116374974A CN 202310219170 A CN202310219170 A CN 202310219170A CN 116374974 A CN116374974 A CN 116374974A
- Authority
- CN
- China
- Prior art keywords
- methionine
- mother liquor
- crystallization mother
- potassium
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229930182817 methionine Natural products 0.000 title claims abstract description 184
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 183
- 239000012452 mother liquor Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000002425 crystallisation Methods 0.000 title claims abstract description 64
- 230000008025 crystallization Effects 0.000 title claims abstract description 64
- 230000008569 process Effects 0.000 title claims abstract description 44
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 title claims abstract description 39
- 239000012043 crude product Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 41
- 230000007062 hydrolysis Effects 0.000 claims abstract description 35
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 230000009615 deamination Effects 0.000 claims abstract description 16
- 238000006481 deamination reaction Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 230000020477 pH reduction Effects 0.000 claims abstract description 9
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005261 decarburization Methods 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 41
- 239000000920 calcium hydroxide Substances 0.000 claims description 40
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 40
- -1 amine compounds Chemical class 0.000 claims description 35
- 229940091173 hydantoin Drugs 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- 239000011575 calcium Substances 0.000 claims description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 25
- 229960005069 calcium Drugs 0.000 claims description 25
- 229910052791 calcium Inorganic materials 0.000 claims description 25
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000292 calcium oxide Substances 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 229910001414 potassium ion Inorganic materials 0.000 claims description 19
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 235000011181 potassium carbonates Nutrition 0.000 claims description 14
- 108010016626 Dipeptides Proteins 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 11
- 235000011151 potassium sulphates Nutrition 0.000 claims description 11
- 239000001506 calcium phosphate Substances 0.000 claims description 10
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 9
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 9
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 9
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 claims description 8
- DEWDMTSMCKXBNP-BYPYZUCNSA-N N-carbamoyl-L-methionine Chemical compound CSCC[C@@H](C(O)=O)NC(N)=O DEWDMTSMCKXBNP-BYPYZUCNSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 8
- 239000011736 potassium bicarbonate Substances 0.000 claims description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 8
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 7
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 7
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 7
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 7
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 7
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 claims description 6
- CDWZRHFHYAOGGK-WCCKRBBISA-M potassium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [K+].CSCC[C@H](N)C([O-])=O CDWZRHFHYAOGGK-WCCKRBBISA-M 0.000 claims description 5
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- XABQZBXNJZOZMS-UHFFFAOYSA-N O=C1CNC(=O)N1.CSCCC1NC(=O)NC1=O Chemical compound O=C1CNC(=O)N1.CSCCC1NC(=O)NC1=O XABQZBXNJZOZMS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000413 hydrolysate Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 12
- 150000001450 anions Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 229960004452 methionine Drugs 0.000 description 146
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 60
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 38
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 229910000019 calcium carbonate Inorganic materials 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- QHMWJBZUZWPWFB-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;potassium Chemical compound [K].CSCC[C@H](N)C(O)=O QHMWJBZUZWPWFB-WCCKRBBISA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- GSYTVXOARWSQSV-BYPYZUCNSA-N L-methioninamide Chemical compound CSCC[C@H](N)C(N)=O GSYTVXOARWSQSV-BYPYZUCNSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 235000011837 pasties Nutrition 0.000 description 5
- 229910001950 potassium oxide Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229960001714 calcium phosphate Drugs 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IREPZTZSVPKCAR-WCCKRBBISA-M sodium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [Na+].CSCC[C@H](N)C([O-])=O IREPZTZSVPKCAR-WCCKRBBISA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002741 methionine derivatives Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CNMFGFBWPBBGKX-SCGRZTRASA-L zinc;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [Zn+2].CSCC[C@H](N)C([O-])=O.CSCC[C@H](N)C([O-])=O CNMFGFBWPBBGKX-SCGRZTRASA-L 0.000 description 2
- KFSJYZYQSZKRRQ-BYPYZUCNSA-N (2s)-2-(hydroxyamino)-4-methylsulfanylbutanoic acid Chemical compound CSCC[C@H](NO)C(O)=O KFSJYZYQSZKRRQ-BYPYZUCNSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XBSLKMQADAAKGP-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;phosphane Chemical compound P.OC(=O)CC(O)(C(O)=O)CC(O)=O XBSLKMQADAAKGP-UHFFFAOYSA-N 0.000 description 1
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- OFNJDDJDXNMTHZ-UHFFFAOYSA-L calcium;2-aminoacetate Chemical compound [Ca+2].NCC([O-])=O.NCC([O-])=O OFNJDDJDXNMTHZ-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CDWZRHFHYAOGGK-UHFFFAOYSA-M potassium;2-amino-4-methylsulfanylbutanoate Chemical compound [K+].CSCCC(N)C([O-])=O CDWZRHFHYAOGGK-UHFFFAOYSA-M 0.000 description 1
- GYJIUFKWWIHWRF-UHFFFAOYSA-M potassium;2-hydroxypentanethioate Chemical compound [K+].CCCC(O)C([O-])=S GYJIUFKWWIHWRF-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/12—Formation of amino and carboxyl groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical industry, in particular to a recycling method of methionine crude product crystallization mother liquor in a methionine potassium salt process, which comprises the steps of reacting the methionine crude product crystallization mother liquor with a hydrolysis agent at the temperature of 140-170 ℃ and the pressure of 0.30-1.5 MPa for 15-60 min to obtain hydrolysis liquid; deamination treatment is carried out on the hydrolysate, filtrate and insoluble matters are respectively obtained after deamination and filtration, and the obtained insoluble matters are added into phosphoric acid aqueous solution for neutralization reaction to prepare calcium phosphate salt compounds; the crude methionine crystallization mother liquor is the crystallization mother liquor after acidification of methionine potassium salt process carbon dioxide, and is obtained after decarburization treatment. According to the method, nitrogen-containing organic matters in the methionine crude crystallization mother liquor are converted into methionine, divalent anion impurities in the mother liquor are effectively removed, the circulating mother liquor is purified, the alkalinity of the circulating mother liquor is increased, the utilization rate of raw materials is improved, and waste is avoided.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for recycling methionine crude product crystallization mother liquor in a methionine potassium salt process.
Background
In the industrial chemical synthesis production process of D, L-methionine, hydantoin as an intermediate of methionine is required to be hydrolyzed in the presence of strong alkaline substances such as sodium hydroxide, potassium carbonate and the like to generate aqueous solution of methionine salt, and the aqueous solution of methionine salt is acidified and separated to obtain methionine product and methionine crystallization mother liquor. Therefore, the solid methionine production process mainly comprises a sodium methionine salt process and a potassium methionine salt process, wherein the sodium methionine salt process mainly adopts sodium hydroxide to hydrolyze hydantoin, then sulfuric acid is used for acidification, solid methionine is obtained and sodium sulfate is a byproduct, the potassium methionine salt process adopts potassium hydroxide or potassium carbonate to hydrolyze hydantoin, and carbon dioxide is used for acidification, so that methionine is obtained, and potassium bicarbonate mother liquor containing methionine is recycled to alkali for hydantoin hydrolysis step after decarburization. When the potassium salt is used as the hydrolysis agent, based on the process setting of physical properties, potassium ions are recycled in the hydantoin hydrolysis, methionine saponification liquid and methionine mother liquor, so that the operation of additionally separating inorganic salt is avoided, the problems of difficult separation and difficult treatment of byproduct salt in the methionine production process are solved, and the method has the advantages of cleaning, energy saving, low production cost and the like.
However, due to the existence of side reactions in the reaction process, such as slight excess hydrogen cyanide during the synthesis of cyanohydrin, residual hydrogen cyanide in the cyanohydrin product is hydrolyzed and converted into formate and cyanide is polymerized into macromolecular pigment in the subsequent reaction process, and cyanohydrin is polymerized and decomposed into sulfur-containing impurities and cyanohydrin is partially hydrolyzed and converted into potassium salt of 2-hydroxy-4-methylthiobutanoic acid (MHA), and cyanide is polymerized into macromolecular pigment; the condensation of potassium methionine and hydantoin under alkaline conditions is carried out to form methionine dipeptide and methionine tripeptide, two molecules of methionine can be dehydrated and converted into methionine diketopiperazine under high temperature conditions, 5- (beta-methylthioethyl) -hydantoin is incompletely hydrolyzed to obtain intermediates such as hydantoin acid salt (N-carbamoylmethionine salt), methionine amide and the like, and the front-end raw material cyanohydrin needs to be sulfated to pH=2-3 due to stable storage, which means that 1 kg of 98% sulfuric acid is needed to be added to 1 ton of cyanohydrin, so that sulfate impurities contained in the front-end raw material cyanohydrin are brought into mother liquor at the rear end, and besides the organic impurities, inorganic impurities are potassium sulfate, various impurities are continuously accumulated in the system along with the circulation of the mother liquor, and finally, the crystallization yield and quality of methionine are directly influenced.
Among the above derived impurities, except for the methionine dipeptide, methionine tripeptide, methionine diketopiperazine and hydantoin incomplete hydrolysis products, the elimination of part of the impurities can be regenerated by the mother liquor at high temperature and high pressure, but the elimination is based on the fact that only part of methionine derived impurities can be eliminated by potassium carbonate hydrolysis in the mother liquor circulation at present, which is probably because the alkaline strength of potassium carbonate is not as strong as potassium hydroxide and the hydrolysis capacity thereof is not as strong as potassium hydroxide. Other impurities are accumulated in a single direction basically, and the catalyst and the stabilizer used in the synthesis and storage process of the 3-methylthiopropanal and the cyanohydrin are also expected to accumulate in a single direction in the system, which is also supported by analysis results. Therefore, a part of methionine crystallization mother liquor is required to be extracted from process consideration and is not recycled, the potassium salt lost with the extracted mother liquor is fed into the system through fresh potassium salt, long-term stability in the process is realized by partially updating the recycled mother liquor, but more dissolved methionine and potassium salt are still unavoidable in the extracted crystallization mother liquor, the methionine and potassium salt in the methionine crystallization mother liquor are necessarily required to be directly or indirectly recycled from economic and environmental protection considerations, and the recycling cost and the benefit of recycling products are determined to be positively or negatively beneficial in the whole methionine production process. In the methionine potassium salt production process, after impurities are accumulated to influence the circulation of the mother liquor, part of the mother liquor is extracted for incineration treatment, organic matters such as potassium methionine, potassium methionine dipeptide, diketopiperazine, hydantoin and hydantoin in the incineration treatment mother liquor are converted into carbon dioxide, nitrogen oxides, sulfur dioxide and moisture at more than 1000 ℃, incineration tail gas is discharged after desulfurization and denitration, even under the condition of insufficient incineration, highly toxic substances such as hydrogen cyanide are generated, residual solids after incineration are mainly potassium carbonate containing potassium sulfate impurities and then sulfuric acid is added for neutralization, and a potassium sulfate product is produced, so that although the methionine potassium salt process is not like the methionine sodium salt process, a large amount of inorganic salts and a salt-containing mother liquor which are difficult to treat, the byproduct of the potassium sulfate is unavoidable, the yield of the potassium sulfate is dependent on the amount of impurities after hydrolysis of hydantoin and the amount of methionine dipeptide, methionine tripeptide, diketopiperazine, hydantoin, 2-hydroxy-4-methylthio potassium butyrate, hydantoin, methionine amide, 5- (beta-methylthioethyl) -hydantoin are converted into residual amounts or the residual amounts of the mother liquor after hydrolysis is recycled, and the alkaline is reduced in order to achieve the strength of the hydrolysis of the mother liquor, and the alkaline is recycled, and the alkaline is a key to be used for the alkaline treatment is reduced.
Patent CN109485589 discloses a method for preparing methionine zinc chelate by methionine mother liquor containing potassium carbonate or potassium bicarbonate, wherein the methionine mother liquor is treated and concentrated by bipolar membrane electrodialysis to have a molar ratio of methionine to potassium ion of 1:0.8-1.1, the methionine desalination mother liquor obtained in an acid chamber reacts with zinc salt with molar equivalent of 0.5 methionine at 70-90 ℃ for 30-90 min, then the temperature is reduced and separated to prepare the methionine zinc chelate, and the recovered potassium hydroxide dilute alkali obtained in an alkali chamber is recycled for methionine production. The method has the problems that the bipolar membrane is used for treating methionine mother liquor containing potassium carbonate or potassium bicarbonate, carbon dioxide gas can be generated in the ion migration process, and the generation of the carbon dioxide gas can reduce the migration efficiency of ions in an acid chamber and an alkali chamber in the bipolar membrane, so that the current efficiency of the bipolar membrane is influenced, the service life of the bipolar membrane is also influenced by the carbon dioxide gas, the membrane replacement frequency is increased, and the production cost is greatly increased.
Patent CN106748932 discloses a method for post-treatment of mother liquor comprising the steps of filtration, acidification, gas-liquid separation, methionine separation, regeneration of saturated acidification column and the like. Filtering the extracted mother liquor through a microporous membrane to remove methionine and macromolecular polymers of intermediate, acidifying the filtrate through acidic resin, adsorbing metal cations in the filtrate, stripping and separating carbon dioxide to obtain a mixed solution with main components of methionine and potassium formate, and carrying out electrodialysis separation to obtain methionine concentrate and potassium formate concentrate, wherein the methionine concentrate and the potassium formate concentrate enter recycling and biochemical treatment respectively. And finally, acidifying and regenerating the ion exchange resin to obtain a potassium sulfate byproduct. Compared with a direct incineration mode, the method can recycle methionine in the extracted mother liquor, but the value of the obtained methionine is much smaller than the input of high-value equipment such as continuous chromatography, electrodialysis and the like, so that the comprehensive economic benefit is almost negative after treatment, and the production of potassium sulfate and salt-containing wastewater thereof is unavoidable, and the biochemical treatment difficulty of the wastewater is relatively high. Therefore, the method has little industrial value.
Based on the prior art, research on how to solve the recovery and reuse of the extracted crystallization mother liquor in the methionine production process and avoid the waste of the effective nitrogenous organic impurities in the recovered crystallization mother liquor has important significance.
Disclosure of Invention
Therefore, the invention aims to provide a recycling method of methionine crude crystallization mother liquor in a methionine potassium salt process, which converts nitrogen-containing organic matters in the methionine crude crystallization mother liquor into methionine, effectively removes divalent anion impurities in the mother liquor, purifies circulating mother liquor, increases the alkalinity of the circulating mother liquor, improves the utilization rate of raw materials and avoids waste.
The invention solves the technical problems by the following technical means:
the invention provides a recycling method of methionine crude product crystallization mother liquor in a methionine potassium salt process, which comprises the following steps:
reacting the methionine crude product crystallization mother liquor with a hydrolysis agent for 15-60 min at the temperature of 140-170 ℃ and the pressure of 0.30-1.5 MPa to obtain hydrolysis liquid;
deamination treatment is carried out on the hydrolysate, filtrate and insoluble matters are respectively obtained after deamination and filtration, and the obtained insoluble matters are added into phosphoric acid aqueous solution for neutralization reaction to prepare calcium phosphate salt compounds;
the methionine crude product crystallization mother liquor is the crystallization mother liquor after acidification of methionine potassium salt process carbon dioxide, and is obtained after decarburization treatment.
In some embodiments, the methionine crude crystallization mother liquor contains the following nitrogen-containing organic amine compounds in percentage by mass: methionine 5.0-6.5%, methionamide 0.01-0.5%, methionine dipeptide 0.05-0.8%, 2, 5-beta-methylthioethyl diketopiperazine 0.05-1.0%, methionine tripeptide 0.01-0.1%, hydantoin acid (N-carbamoylmethionine) 0.05-0.5%, 5- (beta-methylthioethyl) -hydantoin (hydantoin) 0.1-1.0%;
the organic acid salt also comprises the following organic acid salts in percentage by mass: 0.5 to 2.0 percent of formate radical and 0.01 to 0.8 percent of 2-hydroxy-4-methylthio butyric acid.
In some embodiments, the methionine crude crystallization mother liquor further comprises potassium sulfate, potassium carbonate and potassium bicarbonate, wherein the total potassium ions in the methionine crude crystallization mother liquor are 9.0-11.6%, sulfate radicals are 0.1-5.0%, and carbonate radicals are 4.0-7.5%.
In some embodiments, the hydrolyzer is calcium oxide or calcium hydroxide, the mass percentage of the calcium oxide is more than or equal to 87%, wherein the magnesium oxide content is less than or equal to 4%, the silicon dioxide content is less than or equal to 4%, the aluminum oxide content is less than or equal to 0.9%, the sulfur trioxide content is less than or equal to 0.7%, and the ferric oxide is less than or equal to 0.3%, and the calcium hydroxide is obtained by filtering calcium oxide hydration slurry through a 20-40 mesh sieve.
In some embodiments, the calcium in the hydrolyzer and the dianion in the crude crystallization mother liquor of methionine are 1.0-1.2:1.0, and the dianion comprises carbonate and sulfate.
In some embodiments, the organic amine compound in the hydrolysate is only methionine.
In some embodiments, the deamination treatment is terminated with an ammonia content of less than 30 ppm.
In some embodiments, the phosphoric acid is wet-process phosphoric acid, wherein phosphorus pentoxide in the phosphoric acid is 50-61.6 g/L, the fluorine ion content is less than 1000mg/kg, and the arsenic content is less than 10mg/kg.
In some embodiments, the calcium phosphate salt is one of calcium hydrogen phosphate, calcium dihydrogen phosphate, and dicalcium phosphate, which is a complex of calcium hydrogen phosphate and calcium dihydrogen phosphate.
In some embodiments, the filtrate obtained by filtration after deamination is completely recycled to the 5- (β -methylthioethyl) -hydantoin hydrolysis step.
The invention has the following beneficial effects:
(1) According to the invention, calcium oxide or calcium hydroxide hydrolyzer is used for hydrolyzing the methionine potassium salt process methionine crude product crystallization mother liquor, impurities such as nitrogen-containing organic amine compounds and the like can be effectively converted into methionine potassium products, the separation and purification of water-soluble methionine potassium, potassium hydroxide and potassium formate and generated inorganic calcium salts (calcium sulfate and calcium carbonate) and residual calcium hydroxide are simple, and sediment removed through simple filtration after hydrolysis is finished, so that divalent anion impurities (sulfate radical and carbonate radical) are prevented from accumulating in the mother liquor, no salt-containing wastewater is generated, and the environment-friendly clean production process is truly realized.
(2) According to the invention, calcium oxide or calcium hydroxide is used for hydrolyzing the methionine potassium salt process methionine crude product crystallization mother liquor, so that potassium carbonate in the mother liquor to be recycled can be completely converted into potassium hydroxide, the alkaline strength of the recycled mother liquor is increased, the recycled mother liquor is beneficial to hydrolyzing hydantoin, and the added calcium oxide or calcium hydroxide is finally converted into a mixed solid of calcium sulfate, calcium carbonate and calcium hydroxide which are easy to remove by a simple filtering mode, wherein the solid contains rich calcium ions, and the comprehensive utilization of metal ions of a hydrolyzer is used for producing valuable feed-grade calcium phosphate compounds, so that waste residues are avoided.
(2) The invention can effectively hydrolyze peptide bonds and amide bonds and organic amine impurities such as hydantoin acid, hydantoin acid amide and the like, and almost 100% of the organic amine impurities are effectively converted into calcium glycinate, so that the yield of glycine is improved, the yield can be improved by 1% -20%, the discharge of glycine mother liquor is reduced, and the loss rate of glycine is reduced; especially, calcium oxide or calcium hydroxide is used as a hydrolyzer, sulfate radicals and carbonate radicals accumulated in the mother liquor can be effectively removed, and the removal rate of the sulfate radicals and the carbonate radicals in the mother liquor can reach more than 99 percent.
(3) According to the method, the calcium oxide or calcium hydroxide is used for hydrolyzing impurities in the methionine crude product crystallization mother liquor, so that the impurities in the mother liquor can be effectively removed, the influence of the impurities on the cyclic utilization of the mother liquor and the influence of the methionine quality are eliminated, the methionine yield is increased, the cyclic frequency of the methionine crystallization mother liquor is increased, the mother liquor discharge capacity is reduced, the generation of potassium sulfate byproducts is reduced or avoided, the fuel natural gas and sulfuric acid are saved, the salt-containing wastewater is not generated, and the method has good environmental benefit and economic benefit.
(4) Compared with the traditional wet-process phosphoric acid production feed-grade calcium phosphate process, the method comprehensively utilizes the hydrolyzer calcium ions of the methionine crude product crystallization mother liquor of the methionine potassium salt process, has low production cost, fully recovers the hydrolyzer calcium ions, not only increases the yield of methionine in the crystallization mother liquor, but also combines the feed-grade calcium phosphate, and the organic nitrogen in the methionine crude product crystallization mother liquor of the methionine potassium salt process truly plays a role in comprehensive utilization, so that wastes are converted into high-value methionine and feed-grade calcium phosphate.
Drawings
FIG. 1 is a schematic flow chart of a production process of D, L-methionine potassium salt in the embodiment of the invention;
FIG. 2 shows impurities in crude methionine crystallization mother liquor of methionine potassium salt process;
FIG. 3 shows the mechanism of organic impurity generation in the crude methionine crystallization mother liquor of methionine potassium salt process.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The raw materials, equipment or instruments used are conventional products commercially available without identifying the manufacturer.
Referring to fig. 1, the crude methionine crystallization mother liquor in the present application is a crystallization mother liquor after acidification of carbon dioxide in a production process of methionine potassium salt, and is obtained after decarbonizing treatment, and the synthesis method of the mother liquor is as follows:
under the hydrolysis of potassium carbonate, the reaction temperature of the aqueous solution containing 5- (beta-methylthioethyl) -hydantoin is 170-180 ℃, the reaction pressure is 1.0-2.0 MPa, the reaction time is 20-40 min, potassium methionine saponification liquid containing potassium carbonate is obtained, after deamination, carbon dioxide is introduced into the saponification liquid for acidification and neutralization, the pH is controlled at 7.0-8.6, the precipitated crude methionine is filtered, and a small amount of water is used for washing, and the washing water and filtrate are combined into a potassium bicarbonate aqueous solution mainly containing methionine; and (3) carrying out decarburization treatment on the potassium bicarbonate aqueous solution containing methionine at a decarburization temperature of 100-120 ℃ to obtain a potassium carbonate aqueous solution mainly containing potassium methionine, wherein the aqueous solution is a crude product crystallization mother liquor of methionine in the potassium methionine salt process.
Referring to fig. 2, the above-mentioned methionine crude product crystallization mother liquor contains water as main components, and organic matters and inorganic matters, wherein the organic matters include nitrogen-containing organic amine compounds and organic acid salts, and the nitrogen-containing organic amine compounds include (w/w): methionine 5.0-6.5%, methionamide 0.01-0.5%, methionine dipeptide 0.05-0.8%, 2, 5-beta-methylthioethyl diketopiperazine 0.05-1.0%, methionine tripeptide 0.01-0.1%, hydantoin (N-carbamoylmethionine) 0.05-0.5%, 5- (beta-methylthioethyl) -hydantoin (hydantoin) 0.1-1.0%, organic acid salts mainly potassium formate and potassium 2-hydroxy-4-methylthiobutyrate, wherein formate (w/w) 0.5-2.0%, 2-hydroxy-4-methylthiobutyrate (hydroxy methionine) (w/w) 0.01-0.8%, inorganics including potassium sulfate, potassium carbonate and potassium bicarbonate, wherein total potassium ions (w/w) 9.0-11.6%, sulfate (w/w) 0.1% -5.0%, and carbonate 4.0-7.5%. The mechanism of the generation of the organic impurities is shown in FIG. 3.
The recycling method of the methionine crude product crystallization mother liquor comprises the following steps:
the methionine crude product crystallization mother liquor reacts with a hydrolysis agent for 15 min-60 min at the temperature of 140-170 ℃ and the pressure of 0.30-1.5 MPa, so as to obtain hydrolysis liquid. Wherein the hydrolysis agent is calcium oxide or calcium hydroxide, the mass percentage of the calcium oxide is more than or equal to 87%, the magnesium oxide content is less than or equal to 4%, the silicon dioxide content is less than or equal to 4%, the aluminum oxide content is less than or equal to 0.9%, the sulfur trioxide is less than or equal to 0.7%, the ferric oxide is less than or equal to 0.3%, the calcium hydroxide is obtained by filtering calcium oxide and hydrated slurry through a 20-40 mesh sieve, the mass ratio of the specific calcium oxide to water is 1:2-5, the calcium hydroxide is prepared, and the preferred mass ratio of the calcium oxide to the water is 1:3 in examples 1-6. The ratio of calcium in the hydrolytic agent to divalent anions (including carbonate and sulfate) in the methionine crude crystallization mother liquor is 1.0-1.2:1.0.
Deamination treatment is carried out on the hydrolysate, ammonia content is lower than 30ppm as a deamination end point, filtrate and insoluble matters are respectively obtained after deamination, and the obtained insoluble matters are added into phosphoric acid aqueous solution for neutralization reaction to prepare the calcium phosphate salt compound. Wherein the phosphoric acid is wet-process phosphoric acid, namely phosphoric acid crude acid is obtained by extracting phosphorite with sulfuric acid, and 50-61.6 g/L of phosphorus pentoxide is obtained by purifying the crude acid by removing sulfuric acid, defluorination, dearsenation and the like, wherein the content of fluorine ions is less than 1000mg/kg, and the content of arsenic is less than 10mg/kg; the pH of the reaction of phosphoric acid and insoluble matter is controlled to be 3.0-7.0, wherein, when the pH is 3.0-4.0, the calcium biphosphate product is obtained, and the chemical formula of the calcium biphosphate product is Ca (H) 2 PO 4 ) 2 ·H 2 O, when pH is 3.5-5.0, the product of dicalcium phosphate is obtained, and the chemical formula is Ca (H) 2 PO4)·2H 2 O·CaHPO 4 ·2H 2 O, and calcium hydrophosphate product is obtained when the pH value is 5.5-7.0, and the chemical formula of the calcium hydrophosphate product is CaHPO 4 ·2H 2 O. The filtrate obtained by filtering after deamination is a mixed water solution of potassium methionine, potassium hydroxide and potassium formate, wherein the total methionine (including hydroxy methionine) (w/w) is 7.0-12.0%, the formate (w/w) is 0.3-2.0%, the hydroxyl (w/w) is 2.0-4.0%, and the potassium ion (w/w) is 7.0-14.0%. The filtrate is completely recycled to the (hydantoin) hydrolysis step, and potassium ions and organic matters (the sum of methionine, 5- (beta-methylthioethyl) -hydantoin) are fed in the mole during the hydrolysisThe ratio is 2.0-3.0:1.
In order to better understand the recycling method of the present application, the following examples were performed:
example 1
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): 10.5% of total potassium ions; an organic amine compound, methionine 5.5%, methionine dipeptide 0.5%, methionine tripeptide 0.05%, 2, 5-diketopiperazine 1.0%, methionine amide 0.5%, N-carbamoylmethionine 0.1%, 5- (. Beta. -methylthioethyl) -hydantoin 0.5%; an organic acid salt compound, formate 0.5%, 2-hydroxy-4-Methylthiobutyrate (MHA) 0.1%; adding 2.5% of sulfate radical and 5.5% of carbonate radical and 90.92g of calcium oxide powder with the mass percentage content of 87% into a high-pressure reaction kettle with a zirconium lining, wherein the feeding mole ratio of calcium to divalent anions (sulfate radical and carbonate radical) is 1.2:1, heating to 140 ℃, hermetically stirring and reacting for 50 minutes, the pressure in the reaction kettle is 0.60MPa, after the hydrolysis reaction is finished, decompressing to normal pressure, transferring the materials into a flask, then steaming ammonia water under the conditions of negative pressure and temperature of 80-90 ℃ until the content of free ammonia in the mother liquor is lower than 30ppm, simultaneously recovering ammonia to obtain a mixed aqueous solution of methionine potassium and potassium hydroxide with white precipitates of calcium hydroxide, calcium carbonate and calcium sulfate, analyzing the hydrolysis liquid organic amine to be methionine, filtering white insoluble matters (calcium hydroxide, calcium sulfate and calcium carbonate) in the reaction liquid, and washing with a small amount of water to obtain 200.0g of off-white pasty solid, wherein the content of calcium is 28.25%; the wash water was combined with the filtrate to obtain 1100.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 7.53% by mass, potassium ion was 9.55% by mass, formate was 0.38% by mass, hydroxyl group was 3.20% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
200g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 190.60g of phosphoric acid (wherein phosphorus pentoxide is 50.0 g/L) at 50 ℃ to acidify to pH 6.5, the mixture is stirred for 30min at 75 ℃ in a heat preservation mode, a large amount of white precipitate is generated in the reaction system, the mixture is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 274.27g of calcium hydrophosphate product which is white powder is obtained, the total phosphorus content is 17.0% after analysis, the phosphorus citrate soluble phosphorus content is 14.5%, the calcium content is 20.6%, and the product quality meets the feed grade standard.
Example 2
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): total potassium ion 11.6%; an organic amine compound, methionine 6.5%, methionine dipeptide 0.8%, methionine tripeptide 0.5%, 2, 5-diketopiperazine 0.5%, methionine amide 0.05%, N-carbamoylmethionine 0.5%, 5- (. Beta. -methylthioethyl) -hydantoin 1.0%; an organic acid salt compound, 2.0% formate, 0.8% 2-hydroxy-4-Methylthiobutyrate (MHA); adding calcium oxide powder with the mass percentage of 87% of sulfate radical 0.2%, 7.0% of carbonate radical and 76.47g into a high-pressure reaction kettle made of lining zirconium material, wherein the feeding mole ratio of calcium to divalent anions (sulfate radical and carbonate radical) is 1.0:1, heating to 170 ℃, sealing and stirring for reaction for 20 minutes, wherein the pressure in the reaction kettle is 1.5MPa, after the hydrolysis reaction is finished, decompressing to normal pressure, transferring the materials into a flask, then steaming ammonia water under the conditions of negative pressure and temperature of 80-90 ℃ until the free ammonia content in the mother liquor is lower than 30ppm, simultaneously recovering ammonia to obtain a mixed aqueous solution of methionine potassium and potassium hydroxide with white precipitate calcium hydroxide, calcium carbonate and calcium sulfate, analyzing the hydrolysis liquid organic amine to be methionine, detecting no other organic amine compounds, filtering white insoluble matters (calcium hydroxide, calcium sulfate and calcium carbonate) in the reaction liquid, and washing with a small amount of water to obtain 155.0g of off-white pasty solid, wherein the calcium content is 30.65%; the wash water was combined with the filtrate to give 1028.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 10.27% by mass, potassium ion was 11.28% by mass, formate was 1.5% by mass, hydroxyl group was 3.18% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
155.0g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 138.27g of phosphoric acid (61.0 g/L of phosphorus pentoxide) at 60 ℃ to acidify to pH 7.0, a large amount of bubbles are generated, the mixture is stirred at 80 ℃ for 30min, a large amount of white precipitate is generated in the reaction system, the reaction system is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 231.80g of calcium hydrophosphate product is obtained, the calcium hydrophosphate product is white powder, the total phosphorus content is 17.5 percent, the citrate soluble phosphorus content is 14.6 percent, the calcium content is 20.5 percent after analysis, and the product quality meets the feed grade standard.
Example 3
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): total potassium ion 11.6%; an organic amine compound, methionine 6.5%, methionine dipeptide 0.8%, methionine tripeptide 0.5%, 2, 5-diketopiperazine 0.5%, methionine amide 0.05%, N-carbamoylmethionine 0.5%, 5- (. Beta. -methylthioethyl) -hydantoin 1.0%; an organic acid salt compound, 2.0% formate, 0.8% 2-hydroxy-4-Methylthiobutyrate (MHA); adding calcium oxide powder with the mass percentage of 87% of sulfate radical 0.2%, 7.0% of carbonate radical and 76.47g into a high-pressure reaction kettle made of lining zirconium material, wherein the feeding mole ratio of calcium to divalent anions (sulfate radical and carbonate radical) is 1.0:1, heating to 170 ℃, sealing and stirring for reaction for 20 minutes, wherein the pressure in the reaction kettle is 1.5MPa, after the hydrolysis reaction is finished, decompressing to normal pressure, transferring the materials into a flask, then steaming ammonia water under the conditions of negative pressure and temperature of 80-90 ℃ until the free ammonia content in the mother liquor is lower than 30ppm, simultaneously recovering ammonia to obtain a mixed aqueous solution of methionine potassium and potassium hydroxide with white precipitate calcium hydroxide, calcium carbonate and calcium sulfate, analyzing the hydrolysis liquid organic amine to be methionine, detecting no other organic amine compounds, filtering white insoluble matters (calcium hydroxide, calcium sulfate and calcium carbonate) in the reaction liquid, and washing with a small amount of water to obtain 155.0g of off-white pasty solid, wherein the calcium content is 30.65%; the wash water was combined with the filtrate to give 1028.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 10.27% by mass, potassium ion was 11.28% by mass, formate was 1.5% by mass, hydroxyl group was 3.18% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
155.0g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 70.0g of phosphoric acid (61.0 g/L of phosphorus pentoxide) at 60 ℃ to acidify to pH 3.5, a large amount of bubbles are generated, the mixture is stirred at 80 ℃ for 60min, the white precipitate generated by the reaction system is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 352.0g of calcium dihydrogen phosphate product is obtained, the calcium dihydrogen phosphate product is white powder, the total phosphorus content is 22.5 percent, the water-soluble phosphorus content is 21.0 percent, the calcium content is 13.5 percent after analysis, and the product quality meets the feed grade standard.
Example 4
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): total potassium ion 11.6%; an organic amine compound, methionine 6.5%, methionine dipeptide 0.8%, methionine tripeptide 0.5%, 2, 5-diketopiperazine 0.5%, methionine amide 0.05%, N-carbamoylmethionine 0.5%, 5- (. Beta. -methylthioethyl) -hydantoin 1.0%; an organic acid salt compound, 2.0% formate, 0.8% 2-hydroxy-4-Methylthiobutyrate (MHA); adding calcium oxide powder with the mass percentage of 87% of sulfate radical 0.2%, 7.0% of carbonate radical and 76.47g into a high-pressure reaction kettle made of lining zirconium material, wherein the feeding mole ratio of calcium to divalent anions (sulfate radical and carbonate radical) is 1.0:1, heating to 170 ℃, sealing and stirring for reaction for 20 minutes, wherein the pressure in the reaction kettle is 1.5MPa, after the hydrolysis reaction is finished, decompressing to normal pressure, transferring the materials into a flask, then steaming ammonia water under the conditions of negative pressure and temperature of 80-90 ℃ until the free ammonia content in the mother liquor is lower than 30ppm, simultaneously recovering ammonia to obtain a mixed aqueous solution of methionine potassium and potassium hydroxide with white precipitate calcium hydroxide, calcium carbonate and calcium sulfate, analyzing the hydrolysis liquid organic amine to be methionine, detecting no other organic amine compounds, filtering white insoluble matters (calcium hydroxide, calcium sulfate and calcium carbonate) in the reaction liquid, and washing with a small amount of water to obtain 155.0g of off-white pasty solid, wherein the calcium content is 30.65%; the wash water was combined with the filtrate to give 1028.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 10.27% by mass, potassium ion was 11.28% by mass, formate was 1.5% by mass, hydroxyl group was 3.18% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
155.0g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 100.0g of phosphoric acid (wherein phosphorus pentoxide is 61.0 g/L) at 60 ℃ to acidify to pH 4.5, a large amount of bubbles are generated, the mixture is stirred at 80 ℃ for 60min, the white precipitate generated by the reaction system is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 339.43g of dicalcium phosphate product is obtained, the white powder is white powder, the total phosphorus content is 21.5%, the citrate soluble phosphorus content is 18.6%, the water soluble phosphorus content is 11.0%, the calcium content is 14.0%, and the product quality meets the feed grade standard after analysis.
Example 5
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): 10.0% of total potassium ions; an organic amine compound, methionine 5.0%, methionine dipeptide 0.8%, methionine tripeptide 0.1%, 2, 5-diketopiperazine 1.0%, methionine amide 0.5%, N-carbamoylmethionine 0.5%, 5- (. Beta. -methylthioethyl) -hydantoin 1.0%; an organic acid salt compound, formate 0.5%, 2-hydroxy-4-Methylthiobutyrate (MHA) 0.01%; adding 0.1% of sulfate radical, 7.5% of carbonate radical and 116.58g of 96% calcium hydroxide powder into a high-pressure reaction kettle made of lining zirconium material, wherein the molar ratio of calcium to divalent anions (sulfate radical and carbonate radical) is 1.2:1, heating to 170 ℃, hermetically stirring and reacting for 15 minutes, the pressure in the reaction kettle is 1.5MPa, after the hydrolysis reaction is finished, decompressing to normal pressure, transferring the materials into a flask, then steaming ammonia water under negative pressure at the temperature of 80-90 ℃ until the free ammonia content in the mother liquor is lower than 30ppm, simultaneously recovering ammonia to obtain a mixed aqueous solution of methionine potassium and potassium hydroxide with white precipitate calcium hydroxide, calcium carbonate and calcium sulfate, analyzing the hydrolysis liquid organic amine to be methionine, filtering white insoluble matters (calcium hydroxide, calcium sulfate and calcium carbonate) in the reaction liquid, washing with a small amount of water to obtain 175.0g of off-white pasty solid, wherein the calcium content is 34.57%; the wash water was combined with the filtrate to give 985.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 8.99% by mass, potassium ion was 10.15% by mass, formate was 0.45% by mass, hydroxyl ion was 3.23% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
175.0g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 97.52g of phosphoric acid (wherein phosphorus pentoxide is 55.0 g/L) at 60 ℃ to acidify to pH 3.3, a large amount of bubbles are generated, the mixture is stirred at 80 ℃ for 60min, the white precipitate generated by the reaction system is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 438.41g of calcium dihydrogen phosphate product is obtained, the calcium dihydrogen phosphate product is white powder, the total phosphorus content is 23.0 percent, the water-soluble phosphorus content is 21.0 percent, the calcium content is 13.8 percent, and the product quality meets the feed grade standard after analysis.
Example 6
1000.0g of methionine crude product crystallization mother liquor obtained by methionine potassium salt process, wherein the analysis result (w/w): 10.0% of total potassium ions; an organic amine compound, methionine 5.0%, methionine dipeptide 0.8%, methionine tripeptide 0.1%, 2, 5-diketopiperazine 1.0%, methionine amide 0.5%, N-carbamoylmethionine 0.5%, 5- (. Beta. -methylthioethyl) -hydantoin 1.0%; an organic acid salt compound, formate 0.5%, 2-hydroxy-4-Methylthiobutyrate (MHA) 0.01%; divalent anion compound, sulfate 0.1%, carbonate 7.5%, the above mother liquor was mixed with calcium hydroxide emulsion after filtration after oxidation of calcified slurry (this emulsion was prepared as follows: 97.36g of 87% calcium oxide, wherein the content of magnesium oxide is 3.5%, the content of silicon dioxide is 2.5%, the content of aluminum oxide is 0.8%, the content of sulfate radical (calculated as sulfur trioxide) is 0.6%, the content of ferric oxide is 0.25%, 200g of water is added and fully stirred, then the mixture is filtered by a 40-mesh screen, the obtained emulsion is calcium hydroxide emulsion 294.86 g), the mixture is added into a high-pressure reaction kettle made of lining zirconium material, the molar ratio of calcium to divalent anions (sulfate radical and carbonate) is 1.2:1, then the mixture is heated to 170 ℃ and hermetically stirred for 15 minutes, the pressure in the reaction kettle is 1.5MPa, the pressure is relieved to normal pressure after the hydrolysis reaction, the mixture is transferred into a flask, then the mixture is steamed under the conditions of negative pressure and 80-90 ℃ until the content of free ammonia in the mother liquor is lower than 30ppm, ammonia is recovered, the mixture of methionine and potassium hydroxide with white precipitated calcium hydroxide, calcium carbonate and calcium hydroxide, the mixture solution of potassium hydroxide and ammonia hydroxide is only recovered, the organic amine of the hydrolysate is not detected, the white calcium hydroxide and calcium hydroxide solution is not detected, and the white calcium hydroxide is not washed by 180.37.0% of calcium hydroxide, and calcium hydroxide powder is obtained, wherein the white calcium hydroxide powder is not washed by a small amount of calcium hydroxide powder (37.37%; the wash water was combined with the filtrate to obtain 1200.0g of potassium hydroxide aqueous solution containing potassium methionine, wherein methionine (including MHA) was 7.38% by mass, potassium ion was 8.33% by mass, formate was 0.37% by mass, hydroxyl ion was 2.70% by mass, sulfate and carbonate dianion were not detected, and the filtrate was completely recycled to the 5- (. Beta. -methylthioethyl) -hydantoin hydrolysis step.
180.0g of the obtained white insoluble substances (calcium hydroxide, calcium sulfate and calcium carbonate) are added with 125.0g of phosphoric acid (wherein phosphorus pentoxide is 55.0 g/L) at 80 ℃ to acidify to pH 4.5, a large amount of bubbles are generated, the mixture is stirred at 80 ℃ for 60min, the white precipitate generated by the reaction system is cooled to room temperature after the reaction is finished, the white precipitate is filtered and directly dried to constant weight, 417.24g of dicalcium phosphate product is obtained, the white powder is white powder, the total phosphorus content is 21.8 percent, the citrate soluble phosphorus content is 18.5 percent, the water soluble phosphorus content is 11.0 percent, the calcium content is 14.5 percent, and the product quality meets the feed grade standard.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (10)
1. The method for recycling the methionine crude product crystallization mother liquor in the methionine potassium salt process is characterized by comprising the following steps of:
reacting the methionine crude product crystallization mother liquor with a hydrolysis agent for 15-60 min at the temperature of 140-170 ℃ and the pressure of 0.30-1.5 MPa to obtain hydrolysis liquid;
deamination treatment is carried out on the hydrolysate, filtrate and insoluble matters are respectively obtained after deamination and filtration, and the obtained insoluble matters are added into phosphoric acid aqueous solution for neutralization reaction to prepare calcium phosphate salt compounds;
the methionine crude product crystallization mother liquor is the crystallization mother liquor after acidification of methionine potassium salt process carbon dioxide, and is obtained after decarburization treatment.
2. The method for recycling crude crystallization mother liquor of methionine in the methionine potassium salt process according to claim 1, wherein the crude crystallization mother liquor of methionine contains the following nitrogen-containing organic amine compounds in percentage by mass: methionine 5.0-6.5%, methionamide 0.01-0.5%, methionine dipeptide 0.05-0.8%, 2, 5-beta-methylthioethyl diketopiperazine 0.05-1.0%, methionine tripeptide 0.01-0.1%, hydantoin acid (N-carbamoylmethionine) 0.05-0.5%, 5- (beta-methylthioethyl) -hydantoin (hydantoin) 0.1-1.0%;
the organic acid salt also comprises the following organic acid salts in percentage by mass: 0.5 to 2.0 percent of formate radical and 0.01 to 0.8 percent of 2-hydroxy-4-methylthio butyric acid.
3. The method for recycling crude crystallization mother liquor of methionine in the methionine potassium salt process according to claim 2, wherein the crude crystallization mother liquor of methionine further comprises potassium sulfate, potassium carbonate and potassium bicarbonate, wherein total potassium ions in the crude crystallization mother liquor of methionine are 9.0-11.6%, sulfate radicals are 0.1-5.0% and carbonate radicals are 4.0-7.5%.
4. The method for recycling the methionine crude product crystallization mother liquor in the methionine potassium salt process according to claim 1, wherein the hydrolysis agent is calcium oxide or calcium hydroxide, the mass percent of the calcium oxide is more than or equal to 87%, the magnesium oxide content is less than or equal to 4%, the silicon dioxide content is less than or equal to 4%, the aluminum oxide content is less than or equal to 0.9%, the sulfur trioxide content is less than or equal to 0.7%, and the ferric oxide content is less than or equal to 0.3%.
5. The method for recycling crude methionine crystallization mother liquor in methionine potassium salt process according to claim 4, wherein calcium in the hydrolyzer and dianion in crude methionine crystallization mother liquor are 1.0-1.2:1.0, and the dianion comprises carbonate and sulfate.
6. The method for recycling a crude crystallization mother liquor of methionine in a potassium methionine salt process according to claim 1, wherein the organic amine compound in the hydrolysate is methionine only.
7. The method for recycling a crude crystallization mother liquor of methionine in a potassium methionine salt process according to claim 1, wherein the deamination treatment takes ammonia content of less than 30ppm as a deamination end point.
8. The method for recycling the crude crystallization mother liquor of methionine in the methionine potassium salt process according to claim 1, wherein the phosphoric acid is wet phosphoric acid, wherein the phosphorus pentoxide in the phosphoric acid is 50-61.6 g/L, the fluorine ion content is less than 1000mg/kg, and the arsenic content is less than 10mg/kg.
9. The method for recycling crude crystallization mother liquor of methionine in methionine potassium salt process according to claim 8, wherein the calcium phosphate salt is one of calcium hydrogen phosphate, calcium dihydrogen phosphate and dicalcium phosphate, and the dicalcium phosphate is a complex of calcium hydrogen phosphate and dicalcium phosphate.
10. The method for recycling a crude crystallization mother liquor of methionine in a methionine potassium salt process according to any one of claims 1-9, wherein the filtrate obtained by filtering after deamination is completely recycled to the 5- (β -methylthioethyl) -hydantoin hydrolysis step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310219170.8A CN116374974A (en) | 2023-03-08 | 2023-03-08 | Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310219170.8A CN116374974A (en) | 2023-03-08 | 2023-03-08 | Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116374974A true CN116374974A (en) | 2023-07-04 |
Family
ID=86963911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310219170.8A Pending CN116374974A (en) | 2023-03-08 | 2023-03-08 | Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116374974A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1166543A (en) * | 1966-08-11 | 1969-10-08 | Sumitomo Chemical Co | Process for the Production of DL-Methionine Composition |
| CN105037230A (en) * | 2015-07-14 | 2015-11-11 | 重庆紫光化工股份有限公司 | Method for hydrolyzing 5-(2- methylthioethyl)-hydantoin |
| CN107344715A (en) * | 2017-07-13 | 2017-11-14 | 贵州川恒化工股份有限公司 | The production method of feed-level calcium biphosphate |
| CN109485589A (en) * | 2018-11-09 | 2019-03-19 | 禄丰天宝磷化工有限公司 | A method of the methionine mother liquor containing potassium carbonate or saleratus prepares zinc methionine chelate |
| CN109678768A (en) * | 2019-02-14 | 2019-04-26 | 禄丰天宝磷化工有限公司 | A method of methionine metal chelate is produced using methionine crystalline mother solution |
| CN112679401A (en) * | 2020-12-30 | 2021-04-20 | 天宝动物营养科技股份有限公司 | Potassium carbonate full-circulation process for preparing D, L-methionine |
-
2023
- 2023-03-08 CN CN202310219170.8A patent/CN116374974A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1166543A (en) * | 1966-08-11 | 1969-10-08 | Sumitomo Chemical Co | Process for the Production of DL-Methionine Composition |
| CN105037230A (en) * | 2015-07-14 | 2015-11-11 | 重庆紫光化工股份有限公司 | Method for hydrolyzing 5-(2- methylthioethyl)-hydantoin |
| CN107344715A (en) * | 2017-07-13 | 2017-11-14 | 贵州川恒化工股份有限公司 | The production method of feed-level calcium biphosphate |
| CN109485589A (en) * | 2018-11-09 | 2019-03-19 | 禄丰天宝磷化工有限公司 | A method of the methionine mother liquor containing potassium carbonate or saleratus prepares zinc methionine chelate |
| CN109678768A (en) * | 2019-02-14 | 2019-04-26 | 禄丰天宝磷化工有限公司 | A method of methionine metal chelate is produced using methionine crystalline mother solution |
| CN112679401A (en) * | 2020-12-30 | 2021-04-20 | 天宝动物营养科技股份有限公司 | Potassium carbonate full-circulation process for preparing D, L-methionine |
Non-Patent Citations (1)
| Title |
|---|
| 舒万艮: "《有色金属精细化工产品生产与应用》", 31 December 1995, 中南工业大学出版社, pages: 361 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108026037B (en) | Circulating method for producing taurine | |
| CN108658821B (en) | Clean production method of D, L-methionine and product thereof | |
| CN112679401B (en) | Potassium carbonate full-circulation process for preparing D, L-methionine | |
| CN109734637B (en) | Methionine crystallization mother liquor treatment method | |
| CN115947486B (en) | Desulfurization waste liquid recycling treatment process and system | |
| CN103922926A (en) | Process for purifying residual solid waste generated after alkali peeling wastewater treatment | |
| CN110590034A (en) | Process treatment method for lithium iron wastewater of lithium battery anode material | |
| CN109678768B (en) | Method for producing methionine metal chelate by using methionine crystallization mother liquor | |
| CN111606335B (en) | Clean comprehensive utilization method of potassium salt-containing mother liquor | |
| CN108892302B (en) | Comprehensive treatment method for prochloraz production wastewater | |
| CN116535338B (en) | Potassium salt recycling process in production process of D, L-methionine | |
| CN116374974A (en) | Recycling method of methionine crude product crystallization mother liquor in methionine potassium salt process | |
| CN109485589B (en) | Method for preparing zinc methionine chelate from methionine mother liquor containing potassium carbonate or potassium bicarbonate | |
| CN112225380B (en) | Resource intensive phosphorus-containing wastewater treatment method | |
| CN112707850B (en) | Preparation method of oligomer hydroxy methionine metal chelate | |
| CN114539082A (en) | Environment-friendly preparation and purification method of betaine hydrochloride | |
| CN113105376A (en) | Clean preparation method of high-purity methionine hydroxy analogue calcium salt | |
| US3009954A (en) | Process for the production of sarcosine and related alkylamino-acetic acids | |
| CN111892222A (en) | Ammonium sulfate wastewater recycling method | |
| CN116217420A (en) | Method for regenerating glycine by directly producing glycine crystallization mother liquor by hydantoin method | |
| CN116217421A (en) | Method for recovering glycine and co-producing feed-grade calcium hydrophosphate from glycine crude crystallization mother liquor | |
| CN112811647B (en) | Method for treating waste liquid in DL-methionine production | |
| CN104974054A (en) | Method and apparatus for preparing iminodiacetic acid by using iminodiacetonitrile to produce mother liquor | |
| CN109879747A (en) | A kind of method of carbide slag production calcium formate | |
| RU2821134C1 (en) | Method of producing purified calcium nitrate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |