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WO2001060788A1 - Procede de production de methionine - Google Patents

Procede de production de methionine Download PDF

Info

Publication number
WO2001060788A1
WO2001060788A1 PCT/EP2000/001528 EP0001528W WO0160788A1 WO 2001060788 A1 WO2001060788 A1 WO 2001060788A1 EP 0001528 W EP0001528 W EP 0001528W WO 0160788 A1 WO0160788 A1 WO 0160788A1
Authority
WO
WIPO (PCT)
Prior art keywords
methionine
ammonia
resin
alkali metal
ketone
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.)
Ceased
Application number
PCT/EP2000/001528
Other languages
English (en)
Inventor
Hervé Ponceblanc
Jean-Christophe Rossi
Georges Gros
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adisseo France SAS
Original Assignee
Rhone Poulenc Animal Nutrition SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Animal Nutrition SA filed Critical Rhone Poulenc Animal Nutrition SA
Priority to PCT/EP2000/001528 priority Critical patent/WO2001060788A1/fr
Priority to US09/782,416 priority patent/US6545179B2/en
Priority to AU2001240664A priority patent/AU2001240664B2/en
Priority to AU4066401A priority patent/AU4066401A/xx
Priority to DK01911708T priority patent/DK1263717T3/da
Priority to ES01911708T priority patent/ES2282237T3/es
Priority to PCT/EP2001/002261 priority patent/WO2001060790A1/fr
Priority to PT01911708T priority patent/PT1263717E/pt
Priority to RU2002124569/04A priority patent/RU2265593C2/ru
Priority to DE60127538T priority patent/DE60127538T2/de
Priority to AT01911708T priority patent/ATE358120T1/de
Priority to EP01911708A priority patent/EP1263717B1/fr
Priority to CNB018049214A priority patent/CN1227223C/zh
Priority to JP2001559842A priority patent/JP4815089B2/ja
Publication of WO2001060788A1 publication Critical patent/WO2001060788A1/fr
Priority to US10/218,862 priority patent/US6911557B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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

Definitions

  • the present invention relates to a process for the production of methionine and in particular to a process for the production of methionine wherein the methionine obtained in not contaminated with sodium salts.
  • a process for the production of methionine is disclosed in FR 2772026 where methionine amide is hydro lysed in the presence of sodium hydroxide.
  • the resulting product stream comprises the sodium salt of methionine. It is necessary to isolate the methionine.
  • This patent application discloses the use of a cation exchange resin wherein the product stream is contacted with the resin such that the sodium ion is exchanged with the resin, thus liberating the methionine.
  • the present invention provides a process for the production of methionine which comprises (a) a first step of contacting hydroxymethylthiobutyronitrile with ammonia or a solution of ammonia to produce a product comprising 2-amino methylthiobutyronitrile,
  • step (e) a fifth step of contacting the product stream of step (d) with an ion exchange resin, to carry out an exchange process of the alkali metal on the resin, and thereby liberating free methionine,
  • step (f) a sixth step of hydrolising the methionine amide in the presence of a catalyst comprising titanium to produce ammonium methioninate, and
  • the process of the present invention provides the advantage over the prior art processes in that it the process can be operated at a lower temperature and can treat a greater concentration of substrate.
  • the methionine salt is limited in quantity after the aminoamide synthesis and thus less resin is required and as compared to the process of FR 2772026.
  • the exchange step is carried out prior to the hydrolysis of the amide, the process can be carried out at a lower temperature and without dilution of the stream.
  • a further advantage of the present process is that methionine obtained at the end of the process, is obtained in solution without any mineral salt thus the process for recovering solid methionine is very simple compared to the known prior art processes where complicated separation processes must be used.
  • hydroxymethylthiobutyronitrile is contacted with ammonia or a solution of ammonium and water, to produce a mixture containing 2-amino methylthiobutyronitrile.
  • the molar amount of ammonia relative to hydroxymethylthiobutyronitrile is suitably from 3 to 10, preferably from 4 to 7.
  • the solution is suitably at a concentration greater that 25% by weight, preferably greater than 60% by weight.
  • the hydroxymethylthiobutyronitrile is contacted with pure ammonia.
  • This first step of the process is suitably carried out at a temperature of from 40 to 80°C, preferably from 70 to 75°C and under a pressure of fromlO to 30 bar, preferably from 15 to 25 bar.
  • the reaction may be carried out in a stirred or tubular reactor with, in particular, a plug flow reactor with a calorific exchange system.
  • the excess ammonia is removed from the reactor. This may be implemented by flash depressurisation or by entrainment with an inert gas such as nitrogen.
  • the temperature during this separation step is suitably below 60°C, preferably between 10 and 40°C.
  • the pressure can be atmospheric pressure or below atmospheric pressure. Preferably a pressure of from 0.1 to 0.5 xl 0 5 Pa is used.
  • the ammonia recovered from the reaction may then be condensed or recuperated by any other suitable process and mixed with additional ammonia and recycled into the reactor.
  • the 2-amino methylthiobutyronitrile produced in the first step of the process is then hydrated in the presence of a ketone and a catalytic amount of alkali metal hydroxide to produce methionine amide.
  • the ketone is suitably present in a concentration of from 0.1 to 1, preferably 0.2 to 0.5 equivalent of ketone.
  • the alkali metal hydroxide is suitably present in a catalytic concentration of from 0.05 to 0.5, preferably from 0.1 to 0.25 equivalent of alkali metal hydroxide.
  • the ketone is acetone.
  • the alkali metal hydroxide is potassium hydroxide or sodium hydroxide, especially sodium hydroxide.
  • the hydration reaction is suitably carried out at a temperature of from 10 to 40°C, preferably from 25 to 35°C.
  • the reaction is carried out under atmospheric pressure.
  • the reaction may be carried out in a stirred or in a tubular reactor or in a column packed with suitable packing material with a calorific exchange system.
  • By-products to this reaction include the alkali metal salt of methionine, residue aminomethylthiobutyronitrile, imidazolidinone (2,2-dimethyl-5(2-(methyl thio)ethyl)-4-imidazolidinone), aqueous ammonia, unreacted ketone and the alkali metal hydroxide.
  • the unreacted ketone and the aqueous ammonia in the product stream are then separated from the other components.
  • the product stream may be distilled or stripped or by any other suitable separation technique.
  • the ketone and the ammonia may be recycled back to the reactor.
  • the product stream devoid of the ketone and ammonia is then contacted with a resin wherein the alkali metal of the alkali metal methioninate salt is retained on the ion-exchange resin, thereby providing a solution containing methionine, free of alkali metal ions.
  • Suitable resins are sulphonic resins. Commercially available resins sold under the trade names Rohm & Haas IMAC
  • C16P and Fluka Amberlist 15 may be used.
  • carboxylic acid resins wherein the pK a of the acid is less than 6.2.
  • Suitable resins are resins such as those sold under the trade name Fluka Duolite C464 or Rohm & Haas IRC50. It is preferred to use a carboxylic acid resin.
  • the stream comprising the alkali metal methioninate salt is passed continuously over the resin.
  • the resin is suitably regenerated by displacing the metal ions.
  • the metal ions may be displaced by treatment in acidic medium for example with a strong inorganic acid, such as sulphuric acid or hydrochloric acid.
  • inorganic acid corresponding to 2 to 14 mol, preferably 3 to 6 mol of acid per kg of resin
  • the carboxylic acid resin may alternatively be regenerated by treating the resin with carbon dioxide in an aqueous medium under pressure of typically 10 to 25 bar. The regeneration is suitably carried out with a molar amount of acid corresponding to 2 to 14, preferably from 3 to 6 mol acid per kg of resin.
  • the eluate of the resin containing the alkali metal sulphate or chloride formed is itself free of methionine.
  • the inorganic salt may then be easily crystallised and separated.
  • the next step in the process of the present invention is the hydrolysis of the methionine amide to produce ammonium methioninate.
  • the stream comprising the amide is, of course, now substantially devoid of alkali metal salt.
  • the hydrolysis step is catalysed using a titanium based catalyst, for example TiO 2 .
  • a mixture of titanium and at least one other metal may be also used , for example Ti-W, Ti-Mo, Ti-Si-W, Ti-Nb, Ti-Nb-W, Ti-Nb-Mo, Ti-Zr, Ti-Al, Ti-Cr, Ti-Zn and Ti-V.
  • the catalyst is TiO 2
  • the catalyst may be used in the powdered form, suitably in a concentration of from 0.1 to 2g of catalyst per gram of aminoamide, preferably from 0.5 to 1.5g of catalyst per gram of aminoamide.
  • the catalyst may be used in the form of pellets.
  • the catalyst is in the form of pellets and used in a continuous process.
  • the catalysed hydrolysis of the methionine amide is suitably carried out at a temperature of from 50 to 150°C, preferably from 80 to 130°C, and under a pressure of from atmospheric pressure to 10 bar, preferably from 1 to 5 bar.
  • Water may be added to the process at any appropriate stage during the process.
  • water is added before or after step (e), namely before or after contact with the resin, or before hydrolysis of the aminoamide, namely before step (f), or before removal of ammonia, namely before step (g).
  • water is introduced into the reaction stream immediately before hydrolysis of the aminoamide. Where water is added, it is added in an amount so as to have a molar amount of free methionine after step (g) from 0.5 to 1.5, preferably from 0.7 to 1 mol/kg of free methionine.
  • the components of the product stream from the hydrolysis step are then separated by any suitable separation technique, for example a stripping process.
  • the liberated ammonia is withdrawn, leaving an aqueous solution comprising free methionine and minor amounts of unreacted aminoamide and imidazolinone.
  • This solution of course does not contain ammonia or alkali metal salt.
  • the final resulting product stream comprising free methionine in the liquid form may be used as is or optionally it may be further treated to recover solid methionine. This may be achieved by separating the methionine using any suitable separation method, for example by simple crystallisation after concentration or by atomisation after partial concentration, crystallisation and grinding, or by granulation after concentration.
  • the overall reaction can be represented by the scheme shown in Figure 1 wherein the compositions of the streams at each stage of the reaction are given in Table 1.
  • 2-hydroxymethylthiobutyronotrile is reacted with ammonia in reactor (A) to provide a mixture comprising 2-aminomethylthiobutyronotrile (composition 1).
  • the excess ammonia is separated from the product stream and passed to a recovery vessel (B) for recycling back to the reactor (A) after further treatment in the recovery block.
  • the treated stream (composition 2) is passed to tank (C).
  • Acetone, water and sodium hydroxide are fed into tank C and the resulting mixture passed to reactor (D).
  • the resulting product stream comprising methionine amide (composition 3) is distilled to separate the unreacted acetone and ammonia. Water is added to the resulting amide solution (composition 4) and the solution (composition 5) is then continuously contacted with the resin.
  • composition 6 Additional water added to the treated product which does not comprise sodium salts and the resulting stream (composition 6) are contacted with the titanium catalyst in reactor (E).
  • the product stream comprising ammonium methioninate (composition 7) is treated to liberate ammonia and isolate the free methionine by stripping in an ammonium stripper (F).
  • the liquid free methionine (composition 8) may be treated further to obtain solid methionine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé destiné à la production de méthionine qui consiste à (a) mettre en contact de l'hydroxyméthylthiobutyronitrile avec de l'ammoniac ou une solution d'ammoniaque afin d'obtenir un produit contenant du 2-amino méthylthiobutyronitrile, (b) à éliminer tout excès d'ammoniac ou de solution d'ammoniaque du produit, (c) à faire réagir le 2-amino méthylthiobutyronitrile avec une cétone et un hydroxyde de métal alcalin afin de produire un flux de produit contenant un amide de méthionine et un sel de métal alcalin de méthionine, (d) à éliminer toute cétone n'ayant pas réagi et l'excès d'ammoniac du flux de produit, (e) à mettre en contact le flux de produit traité à l'étape précédente avec une résine d'échange d'ions, afin de réaliser un procédé d'échange du métal alcalin sur la résine avec libération de méthionine libre, (f) à hydrolyser l'amide de méthionine en présence d'un catalyseur contenant du titane afin de produire du méthioninate d'ammonium, et (g) à libérer la méthionine à partir du méthioninate d'ammonium.
PCT/EP2000/001528 2000-02-15 2000-02-15 Procede de production de methionine Ceased WO2001060788A1 (fr)

Priority Applications (15)

Application Number Priority Date Filing Date Title
PCT/EP2000/001528 WO2001060788A1 (fr) 2000-02-15 2000-02-15 Procede de production de methionine
US09/782,416 US6545179B2 (en) 2000-02-15 2001-02-13 Process for the production of methionine
PT01911708T PT1263717E (pt) 2000-02-15 2001-02-14 Processo para a produção de metionina.
DE60127538T DE60127538T2 (de) 2000-02-15 2001-02-14 Verfahren zur herstellung von methionin
DK01911708T DK1263717T3 (da) 2000-02-15 2001-02-14 Fremgangsmåde til fremstilling af methionin
ES01911708T ES2282237T3 (es) 2000-02-15 2001-02-14 Procedimiento para la produccion de metionina.
PCT/EP2001/002261 WO2001060790A1 (fr) 2000-02-15 2001-02-14 Procede de production de methionine
AU2001240664A AU2001240664B2 (en) 2000-02-15 2001-02-14 Process for the production of methionine
RU2002124569/04A RU2265593C2 (ru) 2000-02-15 2001-02-14 Способ получения метионина
AU4066401A AU4066401A (en) 2000-02-15 2001-02-14 Process for the production of methionine
AT01911708T ATE358120T1 (de) 2000-02-15 2001-02-14 Verfahren zur herstellung von methionin
EP01911708A EP1263717B1 (fr) 2000-02-15 2001-02-14 Procede de production de methionine
CNB018049214A CN1227223C (zh) 2000-02-15 2001-02-14 制备甲硫氨酸的方法
JP2001559842A JP4815089B2 (ja) 2000-02-15 2001-02-14 メチオニンを製造する方法
US10/218,862 US6911557B2 (en) 2000-02-15 2002-08-14 Process for the production of methionine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2000/001528 WO2001060788A1 (fr) 2000-02-15 2000-02-15 Procede de production de methionine

Publications (1)

Publication Number Publication Date
WO2001060788A1 true WO2001060788A1 (fr) 2001-08-23

Family

ID=8163847

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/001528 Ceased WO2001060788A1 (fr) 2000-02-15 2000-02-15 Procede de production de methionine

Country Status (5)

Country Link
CN (1) CN1227223C (fr)
AT (1) ATE358120T1 (fr)
AU (1) AU4066401A (fr)
RU (1) RU2265593C2 (fr)
WO (1) WO2001060788A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103497133A (zh) * 2013-10-24 2014-01-08 重庆紫光化工股份有限公司 利用d,l-蛋氨酸生产的皂化液制备n-羟甲基-d,l-蛋氨酸微量元素螯合物的方法
ES2441667A1 (es) * 2012-12-04 2014-02-05 Sumitomo Chemical Company, Limited Método de producción de metionina
EP3689851A1 (fr) 2019-02-04 2020-08-05 Evonik Operations GmbH Production sans sel de méthionine à partir de nitrile de méthionine
WO2023144265A1 (fr) 2022-01-28 2023-08-03 Evonik Operations Gmbh Catalyseur granulaire pour l'hydrolyse d'aminonitriles et d'aminoamides en aminoacides ou dérivés de ceux-ci

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2919607B1 (fr) * 2007-07-31 2012-10-12 Adisseo Ireland Ltd Procede pour la conversion catalytique de 2-hydroxy-4- methylthiobutanenitrile (hmtbn) en 2-hydroxy-4- methylthiobutanamide (hmtbm).
DE102011081828A1 (de) * 2011-08-30 2013-02-28 Evonik Degussa Gmbh Verfahren zur Umsetzung von Methylmercaptopropionaldehyd aus Roh-Acrolein und Roh-Methylmercaptan
WO2013030068A2 (fr) * 2011-08-30 2013-03-07 Evonik Degussa Gmbh Procédé de production d'un sel de méthionine
CN103641757B (zh) * 2013-11-19 2016-03-30 重庆紫光化工股份有限公司 D,l-2-羟基-4-甲硫基丁酸钙的制备方法
CN113939498A (zh) * 2019-06-13 2022-01-14 赢创运营有限公司 制备甲硫氨酸的方法
CN112979515A (zh) * 2019-12-18 2021-06-18 重庆紫光化工股份有限公司 一种制备2-氨基-4-甲硫基丁酰胺的方法
CN112979514A (zh) * 2019-12-18 2021-06-18 重庆紫光化工股份有限公司 2-羟基-4-甲硫基丁腈制备d,l-蛋氨酸的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0393753A (ja) * 1989-09-04 1991-04-18 Sumitomo Chem Co Ltd α―アミノ酸の製造方法
FR2772026A1 (fr) * 1997-12-05 1999-06-11 Rhone Poulenc Nutrition Animal Procede de preparation de la methionine ou de l'hydroxyanalogue

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4235295A1 (de) * 1992-10-20 1994-04-21 Degussa Kontinuierlich durchführbares Verfahren zur Herstellung von Methionin oder Methioninderivaten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0393753A (ja) * 1989-09-04 1991-04-18 Sumitomo Chem Co Ltd α―アミノ酸の製造方法
FR2772026A1 (fr) * 1997-12-05 1999-06-11 Rhone Poulenc Nutrition Animal Procede de preparation de la methionine ou de l'hydroxyanalogue

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199122, Derwent World Patents Index; Class B05, AN 1991-159343, XP002148378 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2441667A1 (es) * 2012-12-04 2014-02-05 Sumitomo Chemical Company, Limited Método de producción de metionina
CN103497133A (zh) * 2013-10-24 2014-01-08 重庆紫光化工股份有限公司 利用d,l-蛋氨酸生产的皂化液制备n-羟甲基-d,l-蛋氨酸微量元素螯合物的方法
CN103497133B (zh) * 2013-10-24 2015-05-13 重庆紫光化工股份有限公司 利用d,l-蛋氨酸生产的皂化液制备n-羟甲基-d,l-蛋氨酸微量元素螯合物的方法
EP3689851A1 (fr) 2019-02-04 2020-08-05 Evonik Operations GmbH Production sans sel de méthionine à partir de nitrile de méthionine
WO2020161074A1 (fr) 2019-02-04 2020-08-13 Evonik Operations Gmbh Production sans sel de méthionine à partir de méthionine nitrile
CN113396142A (zh) * 2019-02-04 2021-09-14 赢创运营有限公司 由甲硫氨酸腈无盐生产甲硫氨酸
CN113396142B (zh) * 2019-02-04 2023-04-18 赢创运营有限公司 由甲硫氨酸腈无盐生产甲硫氨酸
WO2023144265A1 (fr) 2022-01-28 2023-08-03 Evonik Operations Gmbh Catalyseur granulaire pour l'hydrolyse d'aminonitriles et d'aminoamides en aminoacides ou dérivés de ceux-ci

Also Published As

Publication number Publication date
AU4066401A (en) 2001-08-27
RU2002124569A (ru) 2004-01-10
ATE358120T1 (de) 2007-04-15
CN1227223C (zh) 2005-11-16
RU2265593C2 (ru) 2005-12-10
CN1400966A (zh) 2003-03-05

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