WO2002008181A1 - Procede de production d'acide 2-hydroxy-4-methylthiobutanoique - Google Patents

Procede de production d'acide 2-hydroxy-4-methylthiobutanoique Download PDF

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Publication number
WO2002008181A1
WO2002008181A1 PCT/JP2001/005982 JP0105982W WO0208181A1 WO 2002008181 A1 WO2002008181 A1 WO 2002008181A1 JP 0105982 W JP0105982 W JP 0105982W WO 0208181 A1 WO0208181 A1 WO 0208181A1
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WO
WIPO (PCT)
Prior art keywords
hydroxy
water
aqueous layer
methylthiobutanoic acid
acid
Prior art date
Application number
PCT/JP2001/005982
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English (en)
Japanese (ja)
Inventor
Kenji Ikudome
Tetsuya Shiozaki
Takehiro Otani
Shogo Sudo
Original Assignee
Sumitomo Chemical Company, Limited
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 Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to AU2001269501A priority Critical patent/AU2001269501A1/en
Publication of WO2002008181A1 publication Critical patent/WO2002008181A1/fr

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    • 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 method for producing 2-hydroxy-4-methylthiobutanoic acid.
  • Japanese Patent Publication No. 5-18787 discloses a method using an organic solvent such as isobutyl methyl ketone.
  • a method for extracting and extracting —hydroxy — 4-methylthiobutanoic acid from a reaction solution is described.
  • this method increases the cost of raw materials and decreases the volumetric efficiency due to the use of organic solvents, and also requires the recovery and purification of organic solvents and the removal of organic solvents from final products and wastewater. Equipment and processes are required.
  • U.S. Pat.No. 4,912,257 discloses a method of neutralizing ammonium bisulfate in a reaction solution with ammonia to form ammonium sulfate, and separating the obtained solution into oil and water by a salting out effect. Has been described. However, this method is not sufficient in terms of oil-water separation properties and the extraction efficiency of 2-hydroxy-4-methylthiobutanoic acid.
  • An object of the present invention is to provide a method for producing 2-hydroxy-4-methylthiobutanoic acid, which solves the above-mentioned problems and allows 2-hydroxy-4-methylthiobutanoic acid to be efficiently removed from the reaction solution with good operability. It is in.
  • the present inventors have found that the above object can be achieved by employing a circulation system in a method for producing 2-hydroxy-4-methylthiobutanoic acid from 2-hydroxy-4-methylthiobutanenitrile using sulfuric acid. And found that the present invention was completed. That is, the present invention
  • reaction solution obtained in the step (B) is separated into an oil layer and an aqueous layer containing 2-hydroxy-4-methylthiobutanoic acid to obtain an oil layer and an aqueous layer.
  • 2-hydroxy-4-methylthiobutyronitrile is used as a raw material, and a hydration reaction is carried out in the presence of sulfuric acid to obtain a reaction solution containing 2-hydroxy-4-methylthiobutanamide.
  • a hydration reaction is carried out in the presence of sulfuric acid to obtain a reaction solution containing 2-hydroxy-4-methylthiobutanamide.
  • 2-Hydroxy-4-methylthiobutyronitrile is prepared, for example, by reacting acrolein with methyl mercaptan to obtain 3-methylthiopropionaldehyde, which is then reacted with hydrogen cyanide. can do.
  • the amount of sulfuric acid used in the 7-sum reaction may be about 0.5 mol or more, preferably about 0 mol, from the viewpoint of the reaction rate with respect to 1 mol of 2-hydroxy-4-methylthiobutane nitrile. It is at least 6 mol, and from the viewpoint of the separation of oil and water after hydrolysis, it can be at most about 1 mol, preferably at most 0.9 mol.
  • the amount of water used in the hydration reaction may be about 15 parts by weight or more, and preferably about 15 parts by weight, based on 100 parts by weight of 2-hydroxy-4-methylthiobutanenitrile, from the viewpoint of the reaction rate. It is not less than 25 parts by weight, and can be not more than about 70 parts by weight, preferably not more than about 50 parts by weight.
  • 2-hydroxy-4-methylthiobutanenitrile, sulfuric acid and water are supplied from the viewpoint of the reaction rate. It is preferable to supply methylthiobutanenitrile. At this time, water is supplied with 2-hydroxy-4-methylthiobutanenitrile.
  • the reaction temperature of the hydration reaction can be about 40 ° C. to about 70 ° C., and the reaction time can be about 1 hour to about 3 hours.
  • the hydration reaction can be carried out at around normal pressure, but may be carried out under increased or reduced pressure as necessary.
  • the reaction solution containing 2-hydroxy-4-methylthiobutanoic acid can be obtained by hydrolyzing 2-hydroxy-4-methylthiobutanamide in the reaction solution obtained in step (A) [Step (B) ]. By circulating and using a part of the aqueous layer separated in the step (B) described later in the step (B), the obtained reaction solution can be separated into oil and water with good liquid separation properties and high distribution efficiency.
  • the circulation amount of the aqueous layer was determined based on 1 mol of the sulfuric acid used in the hydration reaction (ie, added in step (A)) or when added to the carohydrate decomposition reaction (ie, sulfuric acid was added in step (B)).
  • ammonium sulfate and bisulfuric acid contained in the aqueous layer were used for 1 mol of the total amount of sulfuric acid used in the hydration reaction and the hydrolysis reaction (added in steps (A) and (B)).
  • the amount can be about 1.0 mol to about 2.0 mol, preferably about 1.2 mol to about 1.8 mol, in terms of the total amount of ammonium.
  • step (B) water may be added as needed.
  • the amount of water to be added was the sum of the amount of water contained in the reaction solution obtained in step (A) and the amount of water contained in the circulating aqueous layer used in the hydration reaction (step
  • sulfuric acid was added to 100 parts by weight of sulfuric acid (added in (A)) or during the hydrolysis reaction (in step (B)), it was used for the hydration reaction and hydrolysis reaction. It may be about 100 parts by weight to about 300 parts by weight, preferably about 200 parts by weight, based on 100 parts by weight of the sulfuric acid (added in steps (A) and (B)). Parts by weight to about 300 parts by weight.
  • sulfuric acid may be added as needed. In this case, the amount of sulfuric acid used in the hydration reaction (added in step (A)) may be reduced compared to when no sulfuric acid is added during the hydrolysis reaction (in step (B)).
  • the reaction solution obtained in the step (A) and the circulating aqueous layer are used from the viewpoint of operability.
  • an aqueous layer circulated therein and, if necessary, water or sulfuric acid may be gradually added.
  • the reaction temperature of the hydrolysis reaction can be from about 90 to about 130 ° C, and the reaction time can be from about 2 hours to about 6 hours. Further, the hydrolysis reaction can be carried out at around normal pressure, but may be carried out under increased or reduced pressure as necessary.
  • the reaction solution obtained in the step (B) is separated into an oil layer containing 2-hydroxy-14-methylthiobutanoic acid and an aqueous layer, and the 2-hydroxy-4-methylthiobutanoic acid can be taken out as an oil layer [Step ( C)].
  • oil-water separation may be performed as it is. It is preferable to separate oil and water after dissolving the compound. Further, even when no precipitate is present, liquid separation can be enhanced by heating.
  • the temperature during oil-water separation can be from about 30 ° C to about 110 ° C, preferably from about 70 to about 90 ° C.
  • the reaction solution obtained in the step (B) may be subjected to an operation such as concentration before the oil-water separation.
  • a part of the aqueous layer separated in the step (C) can be recycled to, for example, the step (B) as described above [Step (C ′)]. Since the aqueous layer usually contains ammonium bisulfate and ammonium bisulfate, ammonium sulfate may be recovered from the remaining aqueous layer that is not circulated after neutralizing the included ammonium bisulfate with ammonia. Alternatively, a trace amount of 2-hydroxy-4-methylthiobutanoic acid contained in the aqueous layer may be recovered by an appropriate method.
  • the oil layer separated in step (C) contains water, ammonium sulfate, ammonium bisulfate, etc.
  • step (C) in addition to 2-hydroxy-4-methylthiobutanoic acid depending on the conditions in steps (A) to (C). It may be.
  • the oil layer separated in step (C) must be separated.
  • the mixture is mixed with ammonia, and the ammonium bisulfate contained therein is neutralized into ammonium sulfate to precipitate insolubles [Step (D)]. [Step (E)].
  • the amount of ammonia used in the step (D) may be about equimolar to the amount of ammonium bisulfate contained in the oil layer separated in the step (C).
  • this ammonia is preferably in the form of ammonia gas or liquid ammonia from the viewpoint of reducing the water content in the obtained mixed solution, while it is preferably in the form of an aqueous ammonia solution from the viewpoint of operability. .
  • step (D ) Before removing insolubles from the mixture obtained in step (D), the mixture is concentrated to remove water [step (D ')], and more insolubles are precipitated. This is preferred because a final product having reduced moisture and ammonium sulfate content can be obtained.
  • the content of ammonium sulfate in the product is
  • the mixture In order to reduce the amount of water to 1% by weight or less, it is preferable to concentrate the mixture until the amount of water contained in the mixture is about 5% or less, preferably about 2% or less.
  • 2-hydroxy-4-methylthiobutanoic acid may adhere to the surface or may be contained in the inside.
  • at least a part of the insoluble matter is preferably recycled to the step (D) [Step (F)]. in this case, The insolubles may be washed with water to elute 2-hydroxy-4-methylthiobutanoic acid, and the resulting washing may be recycled to step (D).
  • the operability can be improved efficiently.
  • —Hydroxy 4-methylthiobutanoic acid can be extracted.
  • the amount of circulation of the water layer and other conditions may be performed in accordance with the case where circulation is performed in the step (B).
  • a part of the aqueous layer separated in the step (C) may be circulated to both the step (B) and the step (C).
  • 2-hydroxy-4-methylthiobutanoic acid As described above, according to the method for producing 2-hydroxy-4-methylthiobutanoic acid of the present invention, 2-hydroxy-4-methylthiobutanoic acid can be efficiently extracted with good operability.

Abstract

L'invention concerne un procédé de production d'acide 2-hydroxy-4-méthylthiobutanoique, consistant à hydrater du 2-hydroxy-4-méthylthiobutanenitrile en présence d'acide sulfurique, à hydrolyser le 2-hydroxy-4-méthylthiobutanamide contenu dans le mélange réactionnel, à séparer par la suite le mélange réactionnel obtenu en une couche d'huile renfermant de l'acide 2-hydroxy-4-méthylthiobutanoique et une couche aqueuse, et à faire circuler une partie de la couche aqueuse dans l'étape d'hydrolyse et/ou dans l'étape de séparation huile/eau. Ce procédé permet d'obtenir efficacement de l'acide 2-hydroxy-4-méthylthiobutanoique de façon satisfaisante sans utilisation d'un solvant organique.
PCT/JP2001/005982 2000-07-25 2001-07-09 Procede de production d'acide 2-hydroxy-4-methylthiobutanoique WO2002008181A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001269501A AU2001269501A1 (en) 2000-07-25 2001-07-09 Process for producing 2-hydroxy-4-methylthiobutanoic acid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-223436 2000-07-25
JP2000223436A JP4517474B2 (ja) 2000-07-25 2000-07-25 ２−ヒドロキシ−４−メチルチオブタン酸の製造方法

Publications (1)

Publication Number Publication Date
WO2002008181A1 true WO2002008181A1 (fr) 2002-01-31

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ID=18717527

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/005982 WO2002008181A1 (fr) 2000-07-25 2001-07-09 Procede de production d'acide 2-hydroxy-4-methylthiobutanoique

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JP (1) JP4517474B2 (fr)
AU (1) AU2001269501A1 (fr)
WO (1) WO2002008181A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7465827B2 (en) 2004-08-18 2008-12-16 Sumitomo Chemical Company, Limited Process for producing 2-hydroxy-4-methylthiobutyric acid

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4759828B2 (ja) * 2001-03-30 2011-08-31 住友化学株式会社 ２−ヒドロキシ−４−メチルチオブタン酸の製造方法
JP4948002B2 (ja) * 2006-03-10 2012-06-06 住友化学株式会社 ２−ヒドロキシ−４−メチルチオブタン酸の製造方法および製造装置
JP2007238552A (ja) * 2006-03-10 2007-09-20 Sumitomo Chemical Co Ltd ２−ヒドロキシ−４−メチルチオブタン酸の製造方法および製造装置
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).

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524077A (en) * 1983-11-14 1985-06-18 Monsanto Company Liquid 2-hydroxy-4-methylthiobutyric acid and process for the preparation thereof
WO1994028717A1 (fr) * 1993-06-09 1994-12-22 Novus International, Inc. Regeneration de l'acide sulfurique a partir de sous-produits du sulfate utilises dans la fabrication d'acide 2-hydroxy-4-(methylthio)butyrique
WO1996040630A1 (fr) * 1995-06-07 1996-12-19 Novus International, Inc. Procede d'hydrolyse en continu pour la preparation d'acide 2-hydroxy-4-methylthiobutanoique ou de sels de cet acide
WO2000002852A1 (fr) * 1998-07-10 2000-01-20 Aventis Animal Nutrition S.A. Procede de preparation de l'acide hydroxymethylthiobutyrique
WO2000046190A1 (fr) * 1999-02-03 2000-08-10 Sumitomo Chemical Company, Limited Procede de production de l'acide 2-hydroxy-4-methyl-thiobutanoique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3465194D1 (en) * 1983-11-14 1987-09-10 Monsanto Co Process for the preparation of liquid 2-hydroxy-methylthiobutyric acid
GB8333729D0 (en) * 1983-12-19 1984-01-25 Pfizer Ltd Fermentation process
PL180933B1 (pl) * 1994-07-11 2001-05-31 Degussa Sposób otrzymywania kwasu 2-hydroksy-4-metylotiomasłowego (MHA), kwas 2-hydroksy-4-metylotiomasłowy
DE19548538C2 (de) * 1995-12-23 1997-12-18 Degussa Verfahren zur Gewinnung von 2-Hydroxy-4-methylthiobuttersäure (MHA)
FR2780969B1 (fr) * 1998-07-10 2000-08-18 Rhone Poulenc Nutrition Animal Procede de separation de l'acide hydroxymethylthiobutyrique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524077A (en) * 1983-11-14 1985-06-18 Monsanto Company Liquid 2-hydroxy-4-methylthiobutyric acid and process for the preparation thereof
WO1994028717A1 (fr) * 1993-06-09 1994-12-22 Novus International, Inc. Regeneration de l'acide sulfurique a partir de sous-produits du sulfate utilises dans la fabrication d'acide 2-hydroxy-4-(methylthio)butyrique
WO1996040630A1 (fr) * 1995-06-07 1996-12-19 Novus International, Inc. Procede d'hydrolyse en continu pour la preparation d'acide 2-hydroxy-4-methylthiobutanoique ou de sels de cet acide
WO2000002852A1 (fr) * 1998-07-10 2000-01-20 Aventis Animal Nutrition S.A. Procede de preparation de l'acide hydroxymethylthiobutyrique
WO2000046190A1 (fr) * 1999-02-03 2000-08-10 Sumitomo Chemical Company, Limited Procede de production de l'acide 2-hydroxy-4-methyl-thiobutanoique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7465827B2 (en) 2004-08-18 2008-12-16 Sumitomo Chemical Company, Limited Process for producing 2-hydroxy-4-methylthiobutyric acid

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JP4517474B2 (ja) 2010-08-04
JP2002037769A (ja) 2002-02-06

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