WO2016047516A1 - メチオニンの製造方法 - Google Patents
メチオニンの製造方法 Download PDFInfo
- Publication number
- WO2016047516A1 WO2016047516A1 PCT/JP2015/076234 JP2015076234W WO2016047516A1 WO 2016047516 A1 WO2016047516 A1 WO 2016047516A1 JP 2015076234 W JP2015076234 W JP 2015076234W WO 2016047516 A1 WO2016047516 A1 WO 2016047516A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methylthio
- butanenitrile
- amino
- oxide
- methionine
- Prior art date
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 50
- 229930182817 methionine Natural products 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- MWLKEJXYXYRWIH-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanenitrile Chemical compound CSCCC(N)C#N MWLKEJXYXYRWIH-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 31
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 claims abstract description 7
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000004811 liquid chromatography Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 150000001785 cerium compounds Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 4
- -1 cerium oxide compound Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JPWPMBYFDCHLKL-UHFFFAOYSA-N 4-methylsulfanylbutanenitrile Chemical compound CSCCCC#N JPWPMBYFDCHLKL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- GSYTVXOARWSQSV-BYPYZUCNSA-N L-methioninamide Chemical compound CSCC[C@H](N)C(N)=O GSYTVXOARWSQSV-BYPYZUCNSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- QPLYDNXPENUGIY-WCCKRBBISA-N N[C@@H](CCSC)C(=O)N.NC(C#N)CCSC Chemical compound N[C@@H](CCSC)C(=O)N.NC(C#N)CCSC QPLYDNXPENUGIY-WCCKRBBISA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NDYYRETYXBJDGQ-UHFFFAOYSA-N [O-2].[Ce+3].[O-2].[Ce+3] Chemical compound [O-2].[Ce+3].[O-2].[Ce+3] NDYYRETYXBJDGQ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/14—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
Definitions
- the present invention relates to a method for producing methionine in one step using 2-amino-4- (methylthio) butanenitrile as a raw material.
- An object of the present invention is to provide a method for easily producing methionine from 2-amino-4- (methylthio) butanenitrile with a good yield.
- a method for producing methionine comprising a step of contacting 2-amino-4- (methylthio) butanenitrile with water in the presence of an oxide catalyst containing cerium.
- the oxide catalyst containing cerium is at least one selected from the group consisting of cerium oxide and an oxide solid solution containing cerium.
- the step is performed at 0 to 300 ° C. 4).
- the 2-amino-4- (methylthio) butanenitrile is 2-amino-4- (methylthio) butanenitrile prepared by contacting 2-hydroxy-4- (methylthio) butanenitrile with aqueous ammonia. 5.
- the above-mentioned 2-amino-4- (methylthio) butanenitrile is 2-amino-4- (methylthio) butanenitrile produced by contacting 3- (methylthio) propionaldehyde, hydrocyanic acid and aqueous ammonia. 5.
- methionine can be produced from 2-amino-4- (methylthio) butanenitrile in a good yield by a simple process.
- methionine can be produced by bringing 2-amino-4- (methylthio) butanenitrile into contact with water in the presence of an oxide catalyst containing cerium.
- oxide catalyst containing cerium examples include an oxide containing cerium (Ce), a composite oxide containing cerium, and an oxide solid solution containing cerium.
- Examples of the oxide containing cerium (Ce) include cerium oxide.
- Examples of cerium oxide include cerium oxide (III) (Ce 2 O 3 ), cerium oxide (IV) (CeO 2 ), a mixture thereof, or a cerium oxide compound having a mixed phase thereof. Of these, cerium (IV) oxide CeO 2 is preferred.
- oxide solid solutions containing cerium examples include CeO 2 —ZrO 2 (ceria-zirconia), CeO 2 —Y 2 O 3 , CeO 2 —La 2 O 3, etc., and there is no limitation on the components that solidify with cerium oxide.
- three or more kinds of metals may be included, and among these, ceria-zirconia is most preferable.
- cerium oxide and an oxide solid solution containing cerium are preferable, and cerium oxide is more preferable.
- the content of cerium is preferably 5 to 100% by weight, more preferably 30 to 100% by weight, still more preferably 70 to 100% by weight, and more preferably 95 to 100% as cerium oxide (CeO 2 ). Even more preferred is weight percent.
- An oxide catalyst containing cerium may be used as a mixture with other catalysts.
- Other catalysts are not particularly limited, and examples thereof include oxides such as zirconium oxide, magnesium oxide, zinc oxide, and titanium oxide, and clay minerals such as hydrotalcite, among which zirconium oxide is preferable.
- the oxide catalyst containing cerium may be used in combination of two or more catalysts having different compositions and physical properties (shape, particle diameter, etc.).
- the average particle diameter of the powdered catalyst is preferably 500 nm or less, more preferably 100 nm or less, and still more preferably 20 nm or less.
- the specific surface area of the catalyst measured by the BET method is preferably 10 to 2000 m 2 / g, more preferably 50 to 1000 m 2 / g, still more preferably 100 to 500 m 2 / g.
- a commercially available product may be used as the oxide containing cerium. For example, you may use what was prepared by methods, such as baking the precursor containing a cerium compound by atmosphere of oxidizing gas, such as air.
- examples of the precursor containing the cerium compound include cerium compounds and those obtained by impregnating a carrier with a cerium compound.
- cerium compounds include cerium halides, inorganic salts (eg, sulfates, nitrates, carbonates, phosphates), acetates, oxalates, hydroxides, and the like.
- the oxide catalyst containing cerium may be, for example, a catalyst in which an oxide containing cerium is supported on a carrier, or a catalyst in which another component is supported on an oxide containing cerium.
- the oxide catalyst containing cerium may be heat-treated with, for example, an oxidizing gas such as air, an inert gas such as nitrogen or argon, a reducing gas such as hydrogen, carbon dioxide, or steam.
- the treatment temperature is not particularly limited, but is preferably 200 to 900 ° C, more preferably 400 to 800 ° C.
- the oxide containing cerium and the oxide catalyst containing cerium may be processed into a molded product such as a pellet.
- the molded product is, for example, a powdered cerium compound or a mixture of the same compound and a solid carrier, or a support of both, and after adding water or the like to a paste, and then extruding to obtain a pellet or the like obtained It can be prepared by firing the molded product.
- the method for producing 2-amino-4- (methylthio) butanenitrile to be used is not necessarily limited. Usually, [Method A] 2-hydroxy-4- (methylthio) butanenitrile and aqueous ammonia are used. 2-amino-4- (methylthio) butanenitrile produced by contact is used, or [Method B] produced by contacting 3- (methylthio) propionaldehyde, hydrocyanic acid (hydrogen cyanide) and aqueous ammonia. 2-amino-4- (methylthio) butanenitrile is used.
- the theoretically required amount of water is 1 mol of 2-amino-4- (methylthio) butanenitrile. Two moles are usually used, but usually in excess of the theoretical amount.
- the amount of water necessary to dissolve 2-amino-4- (methylthio) butanenitrile is used. Specifically, it is 0.5 to 10 parts by weight of water, more preferably 2 to 5 parts by weight of water with respect to 1 part by weight of 2-amino-4- (methylthio) butanenitrile.
- water is usually used in a solvent amount, but if necessary, an organic solvent miscible or immiscible with water may be used.
- the solvent miscible with water include ether solvents such as 1,4-dioxane and tetrahydrofuran, N-methylpyrrolidinone, N-ethylpyrrolidinone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, acetone and the like.
- the amount of oxide containing cerium is usually 0.0010 to 5.0 moles, more preferably 0.010 to 3.0 moles as cerium with respect to 1 mole of 2-amino-4- (methylthio) butanenitrile. Mol, more preferably 0.020 to 1.50 mol.
- the step of bringing 2-amino-4- (methylthio) butanenitrile into contact with water is usually carried out at 0 to 300 ° C., preferably 40 to 150 ° C., more preferably 50 to 110 ° C.
- This step may be performed under pressure, and the pressure in that case is preferably 0.1 MPa to 2 MPa in absolute pressure, and more preferably the reaction is performed under pressure of 0.2 MPa to 0.5 MPa.
- the step may be performed by any of a continuous type, a semi-continuous type, and a batch type.
- the catalyst After completion of the reaction, the catalyst is filtered off from the reaction mass, and then by-product ammonia is removed by atmospheric pressure concentration or vacuum concentration to obtain a methionine aqueous solution. It can also be obtained.
- the obtained methionine solid can also be obtained as high-purity methionine by recrystallization.
- the catalyst whose activity has been reduced by the reaction may be separated from the reaction mass and regenerated before use.
- a cleaning or heat treatment method can be employed. Washing can be performed, for example, with water, acid, alkali, organic solvent, or the like.
- the heat treatment is usually performed in an atmosphere such as an oxidizing gas such as air, an inert gas such as nitrogen or argon, a reducing gas such as hydrogen, carbon dioxide, or steam.
- an atmosphere of the heat treatment it is preferable to carry out in an oxidizing gas atmosphere.
- the temperature of the heat treatment is preferably 200 to 800 ° C, more preferably 300 to 600 ° C.
- Ammonia is usually in the range of 1 to 10 moles per mole of 2-hydroxy-4- (methylthio) butanenitrile.
- the reaction temperature is usually in the range of 10 to 80 ° C.
- water is usually used, and 2-amino-4- (methylthio) butanenitrile is obtained as an aqueous solution after completion of the reaction.
- an aqueous solution containing 2-amino-4- (methylthio) butanenitrile is obtained by deammonia or partial concentration, and the obtained aqueous solution is used as a raw material in the methionine production method of the present invention. Can do.
- hydrocyanic acid is usually in the range of 1 to 2 mol
- ammonia is in the range of 1 to 10 mol.
- the reaction temperature is usually in the range of 10 to 80 ° C.
- water is usually used, and 2-amino-4- (methylthio) butanenitrile is obtained as an aqueous solution after completion of the reaction.
- an aqueous solution containing 2-amino-4- (methylthio) butanenitrile is obtained by deammonia or partial concentration, and the obtained aqueous solution is used as a raw material in the methionine production method of the present invention. Can do.
- Example 1 Preparation of 2-amino-4- (methylthio) butanenitrile from 2-hydroxy-4- (methylthio) butanenitrile 72.00 g of water in a 1 L three-necked flask equipped with a stirrer, thermometer and dropping funnel ( 4.000 mol) and 304.11 g (5.00 mol) of 28% aqueous ammonia were charged and heated to 45 ° C., then 142.52 g (1.00 mol) of 2-hydroxy-4- (methylthio) butanenitrile was added from a dropping funnel. ) Was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at 45 ° C.
- the amount of CeO 2 is 2-amino-4- (methylthio) the amount of CeO 2 per butanenitrile 1 mole To express.
- a tantalum reaction vessel equipped with a thermocouple and a stirrer 15.0 g of cerium oxide (87.15 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) and an aqueous 2-amino-4- (methylthio) butanenitrile solution obtained by the above method 45.0 g (68.69 mmol) was added, and the mixture was stirred at 100 ° C. for 1 hour. Then, when the reaction liquid obtained by removing cerium oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 93.2%.
- Example 2 Production of methionine (Amount of CeO 2 used: 0.58 mol) A two-necked flask equipped with a stirrer and a thermometer was charged with 0.7 g of cerium oxide (4.07 mmol; manufactured by Kanto Chemical Co., Inc.) and 4.7 g of water, and 2-amino-4 obtained by the method of Example 1 was used. -4.7 g (7.02 mmol) of a-(methylthio) butanenitrile aqueous solution was added, and the mixture was stirred at 75 ° C. for 2 hours. Then, when the reaction liquid obtained by removing cerium oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 95.2%.
- Example 3 Production of methionine (Amount of CeO 2 used: 2.04 mol) A 2-neck flask equipped with a stirrer and a thermometer was charged with 5.2 g (30.21 mmol; Wako Pure Chemical Industries, Ltd.) of cerium oxide and 9.6 g of water, and the 2-amino acid obtained by the method of Example 1 was used. 9.6 g (14.78 mmol) of -4- (methylthio) butanenitrile aqueous solution was added, and the mixture was stirred at 75 ° C. for 2 hours. Then, when the reaction liquid obtained by removing cerium oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 92.6%.
- Example 4 Production of methionine (used for recovering CeO 2) A 2-necked flask equipped with a stirrer and a thermometer was charged with 5.1 g (29.63 mmol) of cerium oxide recovered in Example 3 and 9.5 g of water, and 2-amino-obtained by the method of Example 1 was used. 9.5 g (14.22 mmol) of 4- (methylthio) butanenitrile aqueous solution was added, and the mixture was stirred at 75 ° C. for 2 hours. Then, when the reaction liquid obtained by removing cerium oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 97.0%.
- Example 5 Preparation of 2-amino-4- (methylthio) butanenitrile from 3- (methylthio) propionaldehyde
- 29.71 g (1.10 mmol) of hydrocyanic acid was added.
- 28.46 g (3.00 mmol) of 28% aqueous ammonia and 104.17 g (1.00 mol) of 3- (methylthio) propionaldehyde were stirred and stirred at 45 ° C. for 1 hour to obtain 314.3 g of a reaction mixture.
- the reaction mixture was analyzed by liquid chromatography. As a result, the content of 2-amino-4- (methylthio) butanenitrile was 39.6%.
- Example 6 Production of methionine (cerium oxide) A two-necked flask equipped with a stirrer and a thermometer was charged with 1.3 g of cerium oxide (specific surface area 159.6 m 2 / g, manufactured by Daiichi Rare Element Chemical Co., Ltd.) and 4.1 g of water, and the method of Example 5 Then, 4.1 g (12.5 mmol) of the 2-amino-4- (methylthio) butanenitrile aqueous solution obtained in the above was added, and the mixture was stirred at 75 ° C. for 2 hours. Then, when the reaction liquid obtained by removing cerium oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 94.4%.
- Example 7 Production of methionine (ceria-zirconia; 78 wt% CeO 2 -22 wt% ZrO 2 ) Instead of cerium oxide, a ceria-zirconia solid solution (78 wt% CeO 2 -22 wt% ZrO 2 , specific surface area 72.0 m 2 / g, manufactured by Daiichi Rare Chemicals Co., Ltd.) was used, and 2-amino-4- (methylthio) The same reaction as in Example 6 was carried out except that butanenitrile was changed to 12.7 mmol. The methionine reaction yield was 94.5%.
- Example 8 Production of methionine (ceria-zirconia; 40 wt% CeO 2 -60 wt% ZrO 2 ) Instead of cerium oxide, a ceria-zirconia solid solution (40 wt% CeO 2 -60 wt% ZrO 2 , specific surface area 54.1 m 2 / g, manufactured by Daiichi Rare Element Chemical Industries, Ltd.) was used, and 2-amino-4- (methylthio) The same reaction as in Example 6 was carried out except that butanenitrile was changed to 12.6 mmol. The methionine reaction yield was 92.5%.
- Example 9 Production of methionine (cerium oxide) Example 6 except that the amount of cerium oxide was 0.22 g (specific surface area 159.6 m 2 / g, manufactured by Daiichi Rare Element Chemical Co., Ltd.) and 2-amino-4- (methylthio) butanenitrile was 11.6 mmol. The same reaction was performed. The methionine reaction yield was 60.9%.
- Example 10 Production of methionine (combination of cerium oxide and zirconium oxide) Cerium oxide instead of cerium oxide 0.22 g (specific surface area 159.6m 2 / g, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) and zirconium oxide 0.22 g (specific surface area 97.3m 2 / g, manufactured by Daiichi Kigenso Kagaku
- the same reaction as in Example 6 was performed except that 2-amino-4- (methylthio) butanenitrile was changed to 12.8 mmol.
- the methionine reaction yield was 80.0%.
- Example 11 Production of methionine (combination of cerium oxide and zirconium oxide) Instead of the cerium oxide cerium oxide 0.22 g (specific surface area 159.6m 2 / g, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) and zirconium oxide 0.66 g (specific surface area 97.3m 2 / g, manufactured by Daiichi Kigenso Kagaku The same reaction as in Example 6 was performed except that 2-amino-4- (methylthio) butanenitrile was changed to 12.8 mmol. The methionine reaction yield was 88.6%.
- Example 12 Production of methionine (use of air calcined cerium oxide) Cerium oxide (specific surface area: 159.6 m 2 / g, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) was calcined in a muffle furnace at 700 ° C. for 10 hours in the air. The same reaction as in Example 6 was carried out except that 0.22 g of air-calcined cerium oxide was used instead of uncalcined cerium oxide, and 2-amino-4- (methylthio) butanenitrile was changed to 13.0 mmol. It was. The methionine reaction yield was 67.7%.
- Example 13 Production of methionine (use of nitrogen-treated cerium oxide) Cerium oxide (specific surface area: 159.6 m 2 / g, manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.) was held in a tubular furnace at 700 ° C. for 10 hours under nitrogen supply to perform nitrogen treatment. The same reaction as in Example 6 was performed, except that 0.22 g of nitrogen-treated cerium oxide was used instead of untreated cerium oxide, and 2-amino-4- (methylthio) butanenitrile was changed to 13.0 mmol. . The methionine reaction yield was 74.1%.
- Comparative Example Comparison with zinc oxide A two-necked flask equipped with a stirrer and a thermometer was charged with 2.0 g (24.57 mmol) of zinc oxide (particle size: 20 nm; manufactured by Kanto Chemical Co., Inc.) and 5.0 g of water, and carried out. 5.0 g (14.08 mmol) of the 2-amino-4- (methylthio) butanenitrile aqueous solution obtained in Example 1 was added, and the mixture was stirred at 65 ° C. for 4 hours. Then, when the reaction liquid obtained by removing zinc oxide with a membrane filter was analyzed by liquid chromatography, the reaction yield of methionine was 17.0%.
- methionine can be obtained in good yield from 2-amino-4- (methylthio) butanenitrile without complicated steps.
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Abstract
Description
金属亜鉛または亜鉛の酸化物の存在下に、α-アミノニトリルと水とを反応させてアミノ酸を直接得る方法(特許文献2参照)も知られているが、メチオニンの収率は、必ずしも満足のいくものではない。
1.セリウムを含む酸化物触媒の存在下、2-アミノ-4-(メチルチオ)ブタンニトリルと水とを接触させる工程を包含するメチオニンの製造方法。
2.前記セリウムを含む酸化物触媒が、酸化セリウムおよびセリウムを含む酸化物固溶体からなる群から選ばれる少なくとも1つである前項1に記載の製造方法。
3.前記工程が、0~300℃で実施される前項1または2のいずれかに記載の製造方法。
4.アンモニアの存在下に、2-アミノ-4-(メチルチオ)ブタンニトリルと水を接触させる前項1~3のいずれかに記載の製造方法。
5.前記の2-アミノ-4-(メチルチオ)ブタンニトリルが、2-ヒドロキシ-4-(メチルチオ)ブタンニトリルとアンモニア水とを接触させて製造した2-アミノ-4-(メチルチオ)ブタンニトリルである、前項1~4のいずれかに記載の製造方法。
6.前記の2-アミノ-4-(メチルチオ)ブタンニトリルが、3-(メチルチオ)プロピオンアルデヒドと青酸とアンモニア水とを接触させて製造した2-アミノ-4-(メチルチオ)ブタンニトリルである、前項1~4いずれかに記載の製造方法。
反応により活性が低下した触媒は、反応マスから分離し、再生した後、使用してもよい。再生の方法として、洗浄や熱処理の方法をとることができる。洗浄は、例えば、水、酸、アルカリ、有機溶媒等により行うことができる。熱処理は、空気等の酸化性ガス、窒素、アルゴン等の不活性ガス、水素等の還元性ガス、二酸化炭素、またはスチームなどの雰囲気で通常、実施する。熱処理の雰囲気としては、酸化性ガス雰囲気下で実施することが好ましい。熱処理の温度は、200~800℃が好ましく、300~600℃がより好ましい。これらの洗浄や熱処理の方法を組み合わせてもよい。
2-ヒドロキシ-4-(メチルチオ)ブタンニトリル1モルに対して、アンモニアは、通常、1~10モルの範囲である。反応温度は、通常、10~80℃の範囲である。溶媒としては、通常、水を使用し、反応終了後、2-アミノ-4-(メチルチオ)ブタンニトリルは水溶液として得られる。必要ならば、脱アンモニアや部分濃縮を行って2-アミノ-4-(メチルチオ)ブタンニトリルを含有する水溶液を得て、得られたた水溶液を本発明のメチオニン製造方法において、原料として使用することができる。
3-(メチルチオ)プロピオンアルデヒド1モルに対して、青酸は、通常、1~2モルの範囲、アンモニアは1~10モルの範囲である。反応温度は、通常、10~80℃の範囲である。溶媒としては、通常、水を使用し、反応終了後、2-アミノ-4-(メチルチオ)ブタンニトリルは水溶液として得られる。必要ならば、脱アンモニアや部分濃縮をして2-アミノ-4-(メチルチオ)ブタンニトリルを含有する水溶液を得て、得られた水溶液を、本発明のメチオニン製造方法において、原料として使用することができる。
攪拌機、温度計及び滴下ロートを備えた1Lの三口フラスコに水72.00g(4.00mol)及び28%アンモニア水304.11g(5.00mol)を仕込み、45℃に加温した状態で、滴下漏斗より2-ヒドロキシ-4-(メチルチオ)ブタンニトリル142.52g(1.00mol)を20分かけて滴下した。滴下終了後、45℃で1時間攪拌し、2-アミノ-4-(メチルチオ)ブタンニトリルを反応収率88.0%で得た。得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液は精製することなく、次工程の原料として用いた。
熱電対及び攪拌機を備えたタンタル製反応容器に、酸化セリウム15.0g(87.15mmol;和光純薬工業社製)及び前記の方法で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液45.0g(68.69mmol)を加え、100℃で1時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は93.2%であった。
撹拌機及び温度計を備えた二口フラスコに、酸化セリウム0.7g(4.07mmol;関東化学社製)及び水4.7gを仕込み、実施例1の方法で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液4.7g(7.02mmol)を加え、75℃で2時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は95.2%であった。
撹拌機及び温度計を備えた二口フラスコに、酸化セリウム5.2g(30.21mmol;和光純薬工業社製)及び水9.6gを仕込み、実施例1の方法で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液9.6g(14.78mmol)を加え、75℃で2時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は92.6%であった。
撹拌機及び温度計を備えた二口フラスコに、実施例3で回収した酸化セリウム5.1g(29.63mmol)及び水9.5gを仕込み、実施例1の方法で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液9.5g(14.22mmol)を加え、75℃で2時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は97.0%であった。
撹拌機及び温度計を備えた500mLの3口フラスコに、青酸29.71g(1.10mmol)、28%アンモニア水182.46g(3.00mmol)及び3-(メチルチオ)プロピオンアルデヒド104.17g(1.00mol)を仕込み、45℃で1時間撹拌し、314.3gの反応混合物を得た。その後、反応混合物を液体クロマトグラフィーで分析したところ、2-アミノ-4-(メチルチオ)ブタンニトリルの含量は39.6%であった。
前記の方法で調製した反応混合物20.03gに2時間1.15L/分の窒素をバブリングして、アンモニアを除去した。その結果、アンモニア含量は、8.84%から0.07%に低下し、反応液は16.55gに濃縮され、2-アミノ-4-(メチルチオ)ブタンニトリルの含量は41.8%となった。
撹拌機及び温度計を備えた二口フラスコに、酸化セリウム1.38g(8.02mmol;比表面積159.6m2/g、第一稀元素化学工業社製)及び水5gを仕込み、脱アンモニア処理した該2-アミノ-4-(メチルチオ)ブタンニトリル水溶液5g(16.0mmol)を加え、75℃で2時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は80.0%であった。
撹拌機及び温度計を備えた二口フラスコに、酸化セリウム1.3g(比表面積159.6m2/g、第一稀元素化学工業社製)及び水4.1gを仕込み、実施例5の方法で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液4.1g(12.5mmol)を加え、75℃で2時間撹拌した。その後、メンブレンフィルターで酸化セリウムを除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は94.4%であった。
酸化セリウムに代えて、セリア‐ジルコニア固溶体(78wt%CeO2-22wt%ZrO2、比表面積72.0m2/g、第一稀元素化学工業社製)とし、2-アミノ-4-(メチルチオ)ブタンニトリルを12.7mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、94.5%であった。
酸化セリウムに代えて、セリア‐ジルコニア固溶体(40wt%CeO2-60wt%ZrO2、比表面積54.1m2/g、第一稀元素化学工業社製)とし、2-アミノ-4-(メチルチオ)ブタンニトリルを12.6mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、92.5%であった。
酸化セリウム量を0.22g(比表面積159.6m2/g、第一稀元素化学工業社製)、2-アミノ-4-(メチルチオ)ブタンニトリルを11.6mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、60.9%であった。
酸化セリウムに代えて酸化セリウム0.22g(比表面積159.6m2/g、第一稀元素化学工業社製)および酸化ジルコニウム0.22g(比表面積97.3m2/g、第一稀元素化学工業社製)を併用し、2-アミノ-4-(メチルチオ)ブタンニトリルを12.8mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、80.0%であった。
酸化セリウムに代えて酸化セリウム0.22g(比表面積159.6m2/g、第一稀元素化学工業社製)および酸化ジルコニウム0.66g(比表面積97.3m2/g、第一稀元素化学工業社製)を併用し、2-アミノ-4-(メチルチオ)ブタンニトリルを12.8mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、88.6%であった。
酸化セリウム(比表面積159.6m2/g、第一稀元素化学工業社製)を、マッフル炉にて、大気中、700℃で、10h保持し、焼成を行った。焼成していない酸化セリウムに代えて、空気焼成した酸化セリウム0.22gを用い、2-アミノ-4-(メチルチオ)ブタンニトリルを13.0mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、67.7%であった。
酸化セリウム(比表面積159.6m2/g、第一稀元素化学工業社製)を、管状炉にて、窒素供給下、700℃で、10h保持し、窒素処理を行った。処理していない酸化セリウムに代えて窒素処理した酸化セリウム0.22gを用い、2-アミノ-4-(メチルチオ)ブタンニトリルを13.0mmolとした以外は、実施例6と同様の反応を行った。メチオニン反応収率は、74.1%であった。
撹拌機及び温度計を備えた二口フラスコに、酸化亜鉛(粒径20nm;関東化学社製)2.0g(24.57mmol)及び水5.0gを仕込み、実施例1で得られた2-アミノ-4-(メチルチオ)ブタンニトリル水溶液5.0g(14.08mmol)を加え、65℃で4時間撹拌した。その後、メンブレンフィルターで酸化亜鉛を除去し得られた反応液を液体クロマトグラフィーで分析したところ、メチオニンの反応収率は17.0%であった。
一方、酸化亜鉛2.0gに代えて、酸化セリウム(粒径15-30nm;関東化学社製)2.0gを使用して、同様に行ったところ、メチオニンの反応収率は82.0%であった。
Claims (6)
- セリウムを含む酸化物触媒の存在下、2-アミノ-4-(メチルチオ)ブタンニトリルと水とを接触させる工程を包含するメチオニンの製造方法。
- 前記セリウムを含む酸化物触媒が、酸化セリウムおよびセリウムを含む酸化物固溶体からなる群から選ばれる少なくとも1つである請求項1に記載の製造方法
- 前記工程が、0~300℃で実施される請求項1または2のいずれかに記載の製造方法。
- アンモニアの存在下に、2-アミノ-4-(メチルチオ)ブタンニトリルと水を接触させる請求項1~3のいずれかに記載の製造方法。
- 前記の2-アミノ-4-(メチルチオ)ブタンニトリルが、2-ヒドロキシ-4-(メチルチオ)ブタンニトリルとアンモニア水とを接触させて製造した2-アミノ-4-(メチルチオ)ブタンニトリルである、請求項1~4のいずれかに記載の製造方法。
- 前記の2-アミノ-4-(メチルチオ)ブタンニトリルが、3-(メチルチオ)プロピオンアルデヒドと青酸とアンモニア水とを接触させて製造した2-アミノ-4-(メチルチオ)ブタンニトリルである、請求項1~4いずれかに記載の製造方法。
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- 2015-09-16 JP JP2016550128A patent/JP6493410B2/ja active Active
- 2015-09-16 ES ES15845276T patent/ES2864754T3/es active Active
- 2015-09-16 EP EP15845276.3A patent/EP3199519B1/en active Active
- 2015-09-16 CN CN201580051133.4A patent/CN107108487B/zh active Active
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WO2018021010A1 (ja) * | 2016-07-28 | 2018-02-01 | 昭和電工株式会社 | グリシンの製造方法 |
CN109415299A (zh) * | 2016-07-28 | 2019-03-01 | 昭和电工株式会社 | 甘氨酸的制造方法 |
JPWO2018021010A1 (ja) * | 2016-07-28 | 2019-05-09 | 昭和電工株式会社 | グリシンの製造方法 |
US20190161434A1 (en) * | 2016-07-28 | 2019-05-30 | Showa Denko K.K. | METHOD FOR PRODUCING alpha-AMINO ACID |
US10774037B2 (en) * | 2016-07-28 | 2020-09-15 | Showa Denko K.K. | Method for producing alpha-amino acid |
CN109415299B (zh) * | 2016-07-28 | 2021-10-08 | 昭和电工株式会社 | 甘氨酸的制造方法 |
US11319278B2 (en) | 2016-07-28 | 2022-05-03 | Showa Denko K.K. | Method for producing glycine |
JP2020502221A (ja) * | 2016-12-21 | 2020-01-23 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | メチオニンの製造方法 |
EP3453701A1 (en) | 2017-09-08 | 2019-03-13 | Sumitomo Chemical Company, Limited | Method for producing methionine and/or 2-hydroxy-4-(methylthio)butanoic acid |
JP2019048774A (ja) * | 2017-09-08 | 2019-03-28 | 住友化学株式会社 | メチオニン及び/又は2−ヒドロキシ−4−(メチルチオ)ブタン酸の製造方法 |
US10501409B2 (en) | 2017-09-08 | 2019-12-10 | Sumitomo Chemical Company, Limited | Method for producing methionine and/or 2-hydroxy-4-(methylthio) butanoic acid |
JP7425074B2 (ja) | 2019-02-04 | 2024-01-30 | エボニック オペレーションズ ゲーエムベーハー | メチオニンの製造方法 |
Also Published As
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JP6493410B2 (ja) | 2019-04-03 |
US20170275247A1 (en) | 2017-09-28 |
EP3199519A4 (en) | 2018-05-23 |
EP3199519B1 (en) | 2021-02-17 |
EP3199519A1 (en) | 2017-08-02 |
JPWO2016047516A1 (ja) | 2017-07-13 |
ES2864754T3 (es) | 2021-10-14 |
ES2864754T8 (es) | 2022-01-07 |
CN107108487B (zh) | 2019-11-26 |
CN107108487A (zh) | 2017-08-29 |
SG11201701863VA (en) | 2017-04-27 |
US10029980B2 (en) | 2018-07-24 |
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