CN114213293A - Preparation method of methionine - Google Patents
Preparation method of methionine Download PDFInfo
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- CN114213293A CN114213293A CN202111589146.0A CN202111589146A CN114213293A CN 114213293 A CN114213293 A CN 114213293A CN 202111589146 A CN202111589146 A CN 202111589146A CN 114213293 A CN114213293 A CN 114213293A
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- CN
- China
- Prior art keywords
- methionine
- catalyst
- solid
- methylthiobutyronitrile
- amino
- Prior art date
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- 229930182817 methionine Natural products 0.000 title claims abstract description 81
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 52
- GSYTVXOARWSQSV-BYPYZUCNSA-N L-methioninamide Chemical compound CSCC[C@H](N)C(N)=O GSYTVXOARWSQSV-BYPYZUCNSA-N 0.000 claims abstract description 49
- MWLKEJXYXYRWIH-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanenitrile Chemical compound CSCCC(N)C#N MWLKEJXYXYRWIH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 33
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 28
- 239000000413 hydrolysate Substances 0.000 claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 239000011973 solid acid Substances 0.000 claims abstract description 16
- 238000007112 amidation reaction Methods 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000012452 mother liquor Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000003930 superacid Substances 0.000 claims description 9
- 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 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 10
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 27
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 27
- 239000002245 particle Substances 0.000 description 19
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000009615 deamination Effects 0.000 description 9
- 238000006481 deamination reaction Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- -1 methionine alkali salt Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 5
- 229940091173 hydantoin Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SWMDCXYSYSMCJM-UHFFFAOYSA-N 2-aminopentanethioic s-acid Chemical compound CCCC(N)C(S)=O SWMDCXYSYSMCJM-UHFFFAOYSA-N 0.000 description 1
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 description 1
- DNOUKPGPAUUCPC-UHFFFAOYSA-N 2-methylsulfanylpropanal Chemical compound CSC(C)C=O DNOUKPGPAUUCPC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 238000009825 accumulation Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GKBFFPJHOLVCHW-WCCKRBBISA-N azanium;(2s)-2-amino-4-methylsulfanylbutanoate Chemical compound [NH4+].CSCC[C@H](N)C([O-])=O GKBFFPJHOLVCHW-WCCKRBBISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical industry and discloses a preparation method of methionine, which comprises the step of enabling CeO2Procedure for contacting a solid catalyst with an aqueous stream of 2-amino-4-methylthiobutyronitrile, the CeO2The solid catalyst is a rod-shaped crystal form, the diameter of the crystal is 10-80nm, and the length of the crystal is 100-500 nm. Furthermore, the process of the invention gives priority to CeO2The catalytic step is only placed in the amidation reaction process of hydrolyzing 2-amino-4-methylthiobutyronitrile into methionine amide, then the methionine amide hydrolysate is hydrolyzed by using solid acid to prepare the methionine hydrolysate, and finally the crystal is acidified by using carbon dioxideIn this way, methionine is removed. The rod-shaped cerium dioxide catalyst used in the invention has higher catalyst activity and better anti-pollution capacity, the production process can not generate low-value byproduct salt, the cycle life of the cerium dioxide catalyst is longer, the once crystallization rate of methionine is high, the yield is stable, the industrial applicability is realized, and the industrial popularization and application of methionine can be realized.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing methionine by catalyzing 2-amino-4-methylthiobutyronitrile with rod-shaped cerium dioxide, which has industrial applicability.
Background
The chemical synthesis of methionine (MET, 2-amino-4-methylthiobutyric acid) mainly comprises the steps of synthesizing 2-hydroxy-4-methylthiobutyronitrile (cyanohydrin for short) by using methylthiopropanal and hydrocyanic acid, synthesizing a hydantoin intermediate by using the cyanohydrin, carbon dioxide and ammonia, hydrolyzing the hydantoin intermediate by using inorganic base to obtain methionine alkali salt, and acidifying the methionine alkali salt to obtain methionine; or the methyl-thiopropionaldehyde directly reacts with sodium cyanide, carbon dioxide, ammonia and other components to synthesize a hydantoin intermediate, and the hydantoin intermediate is subjected to alkaline hydrolysis and acidification to prepare the methionine. Although the above processes are mature and have high yield, a large amount of unnecessary by-product salts such as sodium sulfate, sodium chloride and the like can be generated no matter what alkali salt is adopted to hydrolyze hydantoin, and the product and the by-product salts are difficult to separate.
Chinese patent 201580051133.4 discloses a method for preparing methionine by contacting 2-amino-4-methylthiobutyronitrile with water in the presence of a cerium-containing oxide catalyst. In particular, the cerium-containing oxide catalyst used in the process is selected from cerium (Ce) oxide2O3) Cerium oxide (CeO)2) Cerium oxide compounds and cerium-containing oxide solid solutions selected from the group consisting of ceria-zirconia (CeO), mixtures thereof or mixtures thereof2-ZrO2) Cerium oxideYttrium oxide (CeO)2-Y2O3) Ceria-lanthana (CeO)2-La2O3) And the like. The method comprises the steps of contacting 2-amino-4-methylthiobutyronitrile with water in the presence of a cerium-containing oxide catalyst, obtaining a reaction feed liquid mainly containing methionine ammonium salt after the reaction is finished, concentrating to obtain a methionine aqueous solution or a methionine solid, recycling or regenerating the separated catalyst, and generating no large amount of byproduct salt. However, there are disadvantages that, firstly, the yield of methionine prepared by the patented method is unstable, and it can be seen from the examples that the yield varies over a wide range; the cerium oxide catalyst used is preferably 20 to 30nm (specific surface area 100 m)2More than g), but in practical application, the catalyst is difficult to be separated from a reaction system efficiently, the catalytic efficiency is obviously reduced when the catalyst is circularly catalyzed for 3 to 5 times, the appearance is changed from similar white or light yellow to brown, and the long-term circular catalysis is difficult to realize; and thirdly, the reaction feed liquid with the main component of methionine ammonium salt is subjected to deamination treatment by adopting modes of normal pressure concentration, reduced pressure concentration and the like to obtain methionine, the deamination treatment mode is long in time consumption and difficult to deaminate thoroughly, some unnecessary side reactions of original impurities and methionine in the system can be caused to deepen the color of the system and the methionine is difficult to take out completely, the impurities and the methionine still having a part can enter the system along with the crystallization mother liquid through circulation, and if the reaction feed liquid returns to the catalysis stage, the performance reduction and the separation difficulty of the catalyst can be further aggravated.
In summary, the prior art has the following main problems: in the traditional production, a large amount of unnecessary by-product salt is generated, and the methionine product and the by-product salt are difficult to separate; the process for preparing methionine by catalyzing 2-amino-4-methylthiobutyronitrile by using cerium oxide has the problems of overlong reaction time, unstable yield, difficulty in thorough deamination and incapability of realizing long-term circulating catalysis of a catalyst; in addition, cerium oxide has various crystal forms such as spherical, octahedral, rod-shaped and square, exposed active surfaces of different crystal forms are different, the crystal forms have important influence on the performance of a cerium oxide catalyst, the existing process directly selects a cerium oxide particle catalyst with a smaller particle size and a larger surface area in order to more obviously utilize the catalytic activity of the cerium oxide, so that the application defect of the cerium oxide particle catalyst is aggravated, the small particle type or small ball type catalyst with the above size is more easily adsorbed and coated by polymers, side reactants, pigment impurities and the like to cause activity reduction, a certain polymerization and flocculation effect is formed after pollution, the high-efficiency separation is difficult, and the water content of a filter cake of the catalyst is up to 30-50 w%.
Disclosure of Invention
In view of the above, the invention provides a method for preparing methionine, the methionine prepared by the method has higher extraction rate, the cerium dioxide catalyst can be recycled for a longer period, and the process has industrial applicability.
The method comprises reacting CeO2Procedure for contacting a solid catalyst with an aqueous stream of 2-amino-4-methylthiobutyronitrile, the CeO2The solid catalyst is a rod-shaped crystal form, the diameter of the crystal is 10-80nm, and the length of the crystal is 100-500 nm.
Preferably, the CeO2The rod-shaped crystals of the solid catalyst have a diameter of 20 to 60nm, more preferably 30 to 50 nm.
Preferably, the CeO2The rod-shaped crystal length of the solid catalyst is 100-400nm, and more preferably 100-300 nm.
Preferably, the CeO2The surface area of the rod-shaped crystals of the solid catalyst is 20-100cm2G, more preferably 30 to 80cm2/g。
Preferably, the 2-amino-4-methylthiobutyronitrile aqueous stream is prepared by mixing 2-amino-4-methylthiobutyronitrile with a water replenishing stream, wherein the content of the 2-amino-4-methylthiobutyronitrile is 3-70 w%.
Preferably, the 2-amino-4-methylthiobutyronitrile content of the aqueous 2-amino-4-methylthiobutyronitrile stream is between 5 and 50% w, more preferably between 10 and 30% w
Preferably, the 2-amino-4-methylthiobutyronitrile is prepared by reacting 2-hydroxy-4-methylthiobutyronitrile with ammonia.
Preferably, the preparation method specifically comprises the following steps:
(1) subjecting the CeO2Solid catalyst and 2-amino-4Contacting the-methylthio butyronitrile aqueous liquid flow, and carrying out amidation reaction to obtain a methionine amide reaction system;
(2) performing incomplete separation treatment on the methionine amide reaction system to respectively obtain methionine amide hydrolysis liquid and a catalyst system;
(3) and contacting the methionine amide hydrolysate with solid acid, and performing hydrolysis reaction to obtain the methionine hydrolysate.
In the context of the present invention, the methionine amide reaction system refers to the CeO2The solid catalyst is contacted with 2-amino-4-methylthiobutyronitrile for amidation reaction to obtain the catalyst containing water and CeO2Solid catalyst, methionine amide.
Further, the methionine amide reaction system also comprises methionine ammonium salt and/or methionine.
The methionine amide hydrolysis liquid refers to the separation of CeO from a methionine amide reaction system2The reactant solution obtained after the solid catalyst and comprising water and the amidation reaction of methionine amide.
Further, the methionine amide hydrolysis solution also comprises methionine ammonium salt and/or methionine.
The catalyst system refers to the solution which is remained after the methionine amide hydrolysis liquid is separated from the methionine amide reaction system and contains the components consistent with the components of the methionine amide hydrolysis liquid and the CeO2Solid-liquid mixing system of solid catalyst.
Preferably, in the methionine amide reaction system, the mass percent of the 2-amino-4-methylthiobutyronitrile is less than or equal to 0.05 percent.
Preferably, in the step (2), the incomplete separation treatment mode is one or more of standing sedimentation, decantation, centrifugation, pressure filtration and membrane filtration.
Preferably, the incomplete separation treatment mode is standing decantation and membrane filtration.
Preferably, the filtering membrane is one or more of an ultrafiltration membrane, a microfiltration membrane and a ceramic membrane.
Preferably, the catalyst body obtained in the step (2)Is recovered and/or utilized in the step (1), and the catalyst system comprises a solution with the same components as the methionine amide hydrolysate and the CeO2A solid catalyst, the solution being such as to cover at least the CeO when the catalyst system is at rest2A solid layer of solid catalyst; or the solution can ensure the CeO2The solid catalyst can realize full flow under the action of certain external force.
Preferably, the solid acid is one or more of oxide solid acid, sulfide solid acid, metal salt solid acid, zeolite molecular sieve solid acid, heteropolyacid solid acid, acidic cation exchange resin, immobilized liquid acid and solid super acid, the acidic ion exchange resin is one or more of ion exchange resins with functional groups of sulfonic acid group, carboxyl group, phosphoric acid group and phenolic group, and the solid super acid is one or more of SO42-/Fe2O3, SO42-/TiO2, SO42-/ZrO2, WO3/ZrO2 and MoO3/ZrO 2.
Preferably, in step (3), the hydrolysis reaction temperature is 60 to 300 ℃, more preferably 80 to 200 ℃, more preferably 90 to 160 ℃,
preferably, the method also comprises the step of carrying out deamination treatment on the methionine amide reaction system obtained in the step (1) and/or the methionine amide hydrolysate obtained in the step (2) and/or the methionine hydrolysate prepared in the step (3).
Preferably, the deamination treatment mode is one or more of steam stripping, flash evaporation and distillation.
Preferably, the method further comprises step (4): and (4) introducing carbon dioxide into the methionine hydrolysate prepared in the step (3) to carry out acidification reaction to prepare a crystallization system, and separating the crystallization system to obtain methionine solid and crystallization mother liquor containing ammonium bicarbonate.
Preferably, the crystallization mother liquor is subjected to a decomposition treatment, carbon dioxide and ammonia obtained by the decomposition are recovered, and a decomposition residual liquid is used for a water replenishing liquid flow and/or is utilized in the step (4).
The invention has the beneficial effects that:
1. compared with the common spherical and amorphous cerium dioxide catalyst, the rod-shaped cerium dioxide catalyst used in the invention has higher activity, and compared with the cerium oxide catalyst with the particle size of 20-50nm adopted in the prior art, the rod-shaped cerium oxide catalyst has larger particles, is easier to settle and separate from hydrolysate, and has better pollution resistance as proved by experiments.
2. Based on the problems of easy pollution and inactivation, difficult effective separation and the like of long-time contact reaction liquid faced by the conventional cerium oxide catalysis, the process of the invention preferentially considers that the step of cerium oxide catalysis is only placed in the amidation reaction process of hydrolyzing 2-amino-4-methylthiobutyronitrile into methionine amide, thereby effectively shortening the time length and the process flow of the hydrolysis reaction of cerium oxide; in addition, the cerium oxide catalyst is recycled and/or utilized without completely filtering methionine amide hydrolysate, and compared with the role that a cerium oxide catalyst solid layer serves as a filter element in a complete solid-liquid separation mode, the process disclosed by the invention can effectively avoid the condition that a large amount of polymers, impurity pigments and the like in a reaction system wrap the adsorption catalyst, so that the cycle life of expensive cerium dioxide is longer.
3. Compared with the prior method for obtaining methionine by deamination by using a reduced pressure distillation or concentration mode, the method for obtaining methionine by using the methionine hydrolysate has the advantages that the methionine is taken out by using a carbon dioxide acidification mode, the crystallization time is short, the methionine taking rate is high (the primary crystallization rate can reach 85.71%), the crystallization mother liquor can be used for recovering carbon dioxide and ammonia by decomposition, and the decomposition residual liquor can be further recycled. In addition, by adopting the crystallization mode, the generation and accumulation speed of the collected impurities in the methionine crystallization mother liquor is slower, and the healthy circulation of the mother liquor is facilitated, so that the catalyst can be used for a longer time.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art can make insubstantial modifications and adaptations to the embodiments described above without departing from the scope of the present invention.
Example 1 (Ammonification, cyanohydrin: Ammonia, 1:5)
Transferring 151.76g of cyanohydrin (86.4 w%, 1mol) into a 316L high-pressure kettle made of a zirconium material 1L, adding 340g of ammonia water (25 w%, 5mol), sealing the reaction kettle, starting heating and stirring, heating to 50 ℃, keeping the pressure at 0.4MPa, carrying out heat preservation reaction for 45min, detecting the conversion rate of the cyanohydrin in a reaction liquid by HPLC (high performance liquid chromatography) to reach 99.5%, cooling the system to normal temperature, and obtaining the 2-amino-4-methylthiobutyronitrile material for the subsequent catalytic preparation of methionine.
Example 2
369.3g of 2-amino-4-methylthiobutyronitrile (35.2 w%) prepared by the method of example 1 and 200g of a stream of water were placed in a 316L autoclave containing zirconium, and 172g of cerium oxide (rod-shaped cerium oxide, particle size 10nm, length 100nm, surface area 86.3 m) as catalyst A were added2(1.0 eq); stirred at 80 ℃ for 1h, filtered to remove catalyst A, and the reaction mixture was analyzed by HPLC, whereby the conversion of 2-amino-4-methylthiobutyronitrile to methionine and its ammonium salt was 99.9%. The catalyst A was reused for catalyzing 2-amino-4-methylthiobutyronitrile to prepare methionine, and the change of conversion rate after 15 cycles was analyzed and recorded as shown in Table 1.
Example 3
The procedure is as in example 2, the catalyst being replaced by catalyst B (cerium oxide in the form of a rod, particle size 30nm, length 200nm, surface area 45 m)2In terms of/g). The recycled catalyst B is circularly catalyzed for 15 times, and the change of the conversion rate in the circulating process is analyzed and recorded as shown in Table 1.
Example 4
The procedure is as in example 2, the catalyst being replaced by catalyst C (spherical cerium oxide, particle size 30nm, surface area 110 m)2In terms of/g). The recycled catalyst C was catalyzed for 5 cycles, and the change of conversion rate in the cyclic process was analyzed and recorded as shown in Table 1.
Example 5
The operation was carried out as in example 2, replacing the catalyst by catalyst D (spherical cerium oxide, particle size 200nm, surface area 23 m)2In terms of/g). The catalyst D was used for 5 cycles, and the change of conversion rate during the cycle was analyzed and recorded as shown in Table 1.
Example 6
The operation was carried out as in example 2, replacing the catalyst with catalyst E (spherical cerium oxide, particle size 1 μm, surface area 10 m)2In terms of/g). The recycled catalyst E is circularly catalyzed for 5 times, and the change of the conversion rate in the circulating process is analyzed and recordedTable 1.
Example 7
The procedure is as in example 2, the catalyst being replaced by catalyst F (cerium oxide square, particle size 30nm, surface area 110 m)2In terms of/g). The recycled catalyst F is circularly catalyzed for 10 times, and the change of the conversion rate in the circulating process is analyzed and recorded as shown in Table 1.
Example 8
The procedure is as in example 2, the catalyst is replaced by catalyst G (amorphous cerium oxide, particle size 20nm, surface area 139 m)2In terms of/g). The recycled catalyst G was used for 10 times of cyclic catalysis, and the change of the conversion rate in the cyclic process was analyzed and recorded as shown in Table 1.
Example 9
The procedure is as in example 2, the catalyst is replaced by catalyst H (spheroidal, octahedral mixed ceria, particle size 30nm, surface area 110 m)2In terms of/g). The catalyst H is recycled for 10 times of catalysis, and the change of the conversion rate in the recycling process is analyzed and recorded in the table 1.
Example 10 (one step catalysis, incomplete isolation, ion exchange resin, 95 ℃ C.)
419.4g of 2-amino-4-methylthiobutyronitrile (31 w%) prepared as in example 1 and 200g of a water-make stream were introduced into a 316L zirconium autoclave, to which 172g of catalyst A (rod-shaped cerium oxide, particle size 10nm, length 100nm, surface area 86.3 m) were added2(1.0eq), stirring for 30min at 60 ℃ for amidation reaction, detecting the conversion rate of 2-amino-4-methylthiobutyronitrile in the reaction liquid by HPLC (high performance liquid chromatography) to be 99.7 percent, standing and layering the obtained methionine amide reaction system, and then decanting the supernatant to obtain the methionine amide hydrolysis liquid A and a catalyst system with the lower layer immersed in the solution component. And (3) further filtering the methionine amide hydrolysate A by using a microfiltration membrane to obtain methionine amide hydrolysate B, and carrying out contact reaction on the methionine amide hydrolysate B and acidic sulfonic ion-exchange resin (polystyrene sulfonic) at 95 ℃ for 1h to obtain the methionine hydrolysate.
The above reaction steps were repeated and the catalyst system was reused in the reaction, recycled for 30 times, and the results were analyzed and reported in table 1.
Example 11 (one step catalysis, incomplete isolation, solid super acid, 140 ℃ C.)
Will be prepared by the method of example 1469.3g of 2-amino-4-methylthiobutyronitrile (27.7 w%) and 220g of a water-make stream were introduced into a 316L autoclave for zirconium, to which 172g of catalyst B (rod-shaped cerium oxide, particle size 30nm, length 200nm, surface area 45 m) were added2(1.0eq), sealing the reaction kettle, stirring for 30min at 70 ℃ for amidation reaction, detecting the conversion rate of 2-amino-4-methylthiobutyronitrile in the reaction liquid by HPLC (high performance liquid chromatography) to be 99.5%, standing and layering the obtained methionine amide reaction system, and then decanting the supernatant to obtain 517g of methionine amide hydrolysate (the content of methionine amide and ammonium methionine is 21.5%) and a catalyst system with the lower layer immersed in the solution component. Mixing the methionine amide hydrolysate with SO4 2-/Fe2O3Contacting and reacting the solid super acid at 140 ℃ for 50min to obtain 511g of methionine hydrolysate (the methionine content is 21.6%) with the yield of 98.6%;
the reaction steps are repeated, the catalyst system D is reused in the reaction, the reaction is recycled for 30 times, and the analysis results are recorded in Table 1.
TABLE 1 comparison of the conversion of 2-amino-4-methylthiobutyronitrile with different catalysts
Note: in examples 10 and 11, the cerium dioxide catalyst is unchanged compared with the catalysts in examples 2 and 3, but is different from the catalysts in examples 2 and 3 in that 2-amino-4-methylthiobutyronitrile is directly hydrolyzed into methionine hydrolysate, and is separated and recycled after only participating in the reaction system of hydrolyzing 2-amino-4-methylthiobutyronitrile into methionine amide.
Example 12 (one step catalysis, 0.6eq, deamination, solid acid hydrolysis)
462.6g of 2-amino-4-methylthiobutyronitrile (28.1 w%) prepared by the process of example 1 and 200g of a water-make stream were introduced into a 316L zirconium autoclave, to which 103.2g of catalyst B (cerium oxide in the form of rods, particle size 30nm, length 200nm, surface area 45 m) were added2(0.6 eq)/g), sealing the reaction kettle, stirring and reacting at 80 ℃ for 40min for amidation reaction, and detecting the conversion rate of 2-amino-4-methylthiobutyronitrile in the reaction liquid by HPLC (high performance liquid chromatography) to be 99.5% (0.04% of 2-amino-4-methylthiobutyronitrile residue)) Standing and layering the obtained methionine amide reaction system, decanting the supernatant to obtain 496.5g of methionine amide hydrolysate, steam stripping to remove free ammonia (free ammonia is less than 0.5%) in the methionine amide hydrolysate, deaminating, and loading with SO in a tubular reactor4 2-/ZrO2The solid super acid is contacted and reacted for 35min at the temperature of 80-160 ℃ in a step heating way to obtain 456g of methionine hydrolysate (the content of methionine is 24.5 percent), the methionine hydrolysate is transferred into a jacket crystallization kettle, carbon dioxide is introduced to acidify and crystallize for 60min, the pH value is reduced to 7.26, solid-liquid separation is carried out to obtain a methionine solid filter cake, the filter cake is washed by pure water for 2 times, the temperature is 105 ℃, and the methionine product is dried to obtain 95.76g, the purity is 99.5 percent, and the crystal extraction rate of the methionine is 85.71 percent at one time.
Example 13 (vacuum distillation crystallization)
487g of methionine hydrolysate (containing 22.95% methionine) prepared by the method of example 12 is subjected to reduced pressure distillation crystallization at 100 ℃ (-0.5-0.6 Mpa) for 2 hours, and then methionine solid and crystallization mother liquor are obtained through separation, the methionine solid is dried to obtain 72.73g, the purity is 98.6%, and the primary crystallization rate of methionine is 65.08%.
Example 14 (distillation + carbon dioxide acidification)
The 2-amino-4-methylthiobutyronitrile stream prepared as described in example 1 was introduced with a water-replenishing stream into a 316L zirconium autoclave, and catalyst B (rod-shaped cerium oxide, particle size 30nm, length 200nm, surface area 45 m) was added2(0.6eq), sealing the reaction kettle, stirring and reacting at 80 ℃ for 40min to carry out amidation reaction, detecting the conversion rate of 2-amino-4-methylthiobutyronitrile in the reaction liquid by HPLC (high performance liquid chromatography), standing and layering the obtained methionine amide reaction system to obtain supernatant to obtain methionine amide hydrolysis liquid, removing free ammonia in the methionine amide hydrolysis liquid by reduced pressure distillation, carrying out contact reaction with solid super acid loaded in a tubular reactor at 80-160 ℃ in step temperature rise after deamination to obtain methionine amide hydrolysis liquid, carrying out reduced pressure distillation at 90 ℃ for (-0.04-0.06 MPa) deamination for 1h, carrying out solid-liquid separation to obtain methionine product 1 and primary crystallization mother liquid, transferring the primary crystallization mother liquid into a jacket crystallization kettle, introducing carbon dioxide to acidify the secondary crystallization for 40min, solid-liquid separation to obtain secondary crystallized methionine solid filter cake, filter cake andthe methionine product 1 is combined and washed with pure water for 2 times, the methionine solid obtained after drying and washing at 105 ℃ is combined with 139.68g of methionine product with the purity of 99.2 percent and the yield of 93 percent, and the washing water is combined with the crystallization mother liquor for standby.
Example 15 (decomposition and recycle of mother solution for crystallization)
361g of the mother liquid (17.5% ammonium bicarbonate, 4.44% methionine) crystallized in example 12 was sent to a small size decomposing tower to decompose and recover carbon dioxide and ammonia at 180 ℃ to obtain 334g of decomposed raffinate at the bottom, which was analyzed to have 4.78% methionine, 1.13% ammonium radical and 73.8% ammonium bicarbonate removal rate.
Further, the decomposed residual liquid can be concentrated continuously, and carbon dioxide is introduced for acidification to recover methionine again, and the methionine can also be recycled to the crystallization step or used as water supplement of 2-amino-4-methylthiobutyronitrile.
Example 16 (5-time recycle, color)
Sending the 2-amino-4-methylthiobutyronitrile material prepared by the method of example 1 and the residual electrolyte recycled moisturizing material flow obtained by the method of example 15 into a 316L zirconium material autoclave, adding a catalyst K (rod-shaped cerium dioxide with the particle size of 50nm, the length of 300nm and the surface area of 32m2/g) (0.8eq), sealing the autoclave, stirring and reacting at 60 ℃ for 65min for amidation, detecting the conversion rate of 2-amino-4-methylthiobutyronitrile in the reaction liquid by HPLC (high performance liquid chromatography), standing and layering the obtained methionine reaction system, decanting the supernatant to obtain methionine amide hydrolysate, carrying out contact reaction with solid superacid loaded in a tubular reactor at the temperature of 80-160 ℃ after removing free ammonia in the methionine amide hydrolysate by reduced pressure distillation, obtaining methionine hydrolysate, transferring the methionine hydrolysate to a jacket crystallization kettle, introducing carbon dioxide to acidify and crystallize for 60min, carrying out solid-liquid separation to obtain a methionine solid filter cake and crystallization mother liquor, washing the filter cake with pure water for 2 times, drying at 105 ℃ to obtain a methionine product with the purity of 99.2%, and feeding the crystallization mother liquor into a decomposition tower to decompose to obtain secondary decomposition residual liquid. The decomposed solution was applied for 5 times to obtain a five-time decomposed residual solution, and the colorimetric degree was set to 8 using a gardner colorimetric tube.
Example 17 (5-time recycle, color impurity)
Methionine was prepared and a crystallization mother liquor was obtained by the same method as in example 13, the crystallization mother liquor was returned to the water supply and used for loop 5 times to obtain a crystallization mother liquor used for loop 5 times, and the colorimetric index was No. 12 using a gardner cuvette.
It can be seen from the above examples 12 and 13 that different crystallization methods applied to the methionine hydrolysate can affect the purity and the crystal yield of the final product, and the purity and the crystal yield of the methionine obtained by the process of the present invention are higher; from the color comparison between example 16 and example 17, it can be seen that the impurities are generated and accumulated more slowly in the production process of the present invention, which is more favorable for the healthy circulation of the mother liquor, so that the catalyst can be used for a longer time.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A method for producing methionine, characterized by comprising subjecting CeO2Procedure for contacting a solid catalyst with an aqueous stream of 2-amino-4-methylthiobutyronitrile, the CeO2The solid catalyst is a rod-shaped crystal form, the diameter of the crystal is 10-80nm, and the length of the crystal is 100-500 nm.
2. The process according to claim 1, wherein the aqueous stream of 2-amino-4-methylthiobutyronitrile is prepared by mixing 2-amino-4-methylthiobutyronitrile with a water make-up stream, wherein the content of 2-amino-4-methylthiobutyronitrile is 3 to 70 w%.
3. The method according to claim 1, characterized in that it comprises in particular the steps of:
(1) subjecting the CeO2Contacting a solid catalyst with 2-amino-4-methylthiobutyronitrile aqueous liquid flow, and carrying out amidation reaction to obtain a methionine amide reaction system;
(2) performing incomplete separation treatment on the methionine amide reaction system to respectively obtain methionine amide hydrolysis liquid and a catalyst system;
(3) and contacting the methionine amide hydrolysate with solid acid, and performing hydrolysis reaction to obtain the methionine hydrolysate.
4. The method according to claim 3, wherein the mass percent of the 2-amino-4-methylthiobutyronitrile in the methionine amide reaction system is less than or equal to 0.05%.
5. The method according to claim 3, characterized in that the catalyst system obtained in step (2) comprising the solution corresponding to the methionine amide hydrolysate component and the CeO is recovered and/or utilized in step (1)2A solid catalyst, the solution being such as to cover at least the CeO when the catalyst system is at rest2A solid layer of solid catalyst; or the solution can ensure the CeO2The solid catalyst can realize full flow under the action of certain external force.
6. The method according to claim 3, wherein the solid acid is one or more of an oxide solid acid, a sulfide solid acid, a metal salt solid acid, a zeolite molecular sieve solid acid, a heteropoly acid solid acid, an acidic cation exchange resin, an immobilized liquid acid and a solid super acid, the acidic ion exchange resin is one or more of an ion exchange resin with a functional group of sulfonic acid group, carboxyl group, phosphoric acid group and phenol group, and the solid super acid is SO4 2-/Fe2O3、SO4 2-/TiO2、SO4 2-/ZrO2、WO3/ZrO2、MoO3/ZrO2One or more of (a).
7. The method according to claim 3, wherein in the step (3), the hydrolysis reaction temperature is 60 to 300 ℃.
8. The method according to claim 3, further comprising a step of deaminating the methionine amide reaction system obtained in the step (1) and/or the methionine amide hydrolysis solution obtained in the step (2) and/or the methionine hydrolysis solution obtained in the step (3).
9. The method according to any one of claims 3 to 8, further comprising the step (4): and (4) introducing carbon dioxide into the methionine hydrolysate prepared in the step (3) to carry out acidification reaction to prepare a crystallization system, and separating the crystallization system to obtain methionine solid and crystallization mother liquor containing ammonium bicarbonate.
10. The process according to claim 9, wherein the crystallization mother liquor is subjected to a decomposition treatment, carbon dioxide and ammonia obtained by the decomposition are recovered, and a decomposition raffinate is used for a water-replenishing liquid stream and/or is used in step (4).
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