Method for obtaining 2-hydroxy-4-methylthiobutyric acid (MHA) which is stable in storage

• US 6,008,409 A
• Filed: 12/29/1997
• Issued: 12/28/1999
• Est. Priority Date: 12/27/1996
• Status: Expired due to Term

• Current Assignee: Evonik Degussa GmbH (Rag-Stiftung)
• Original Assignee: Degussa AG (Rag-Stiftung)
• Inventors: Ronneburg, Axel, Hasselbach, Hans-Joachim, Hasseberg, Hans-Albrechl, Huthmacher, Klaus, Heinzel, Harald, Hafner, Volker
• Primary Examiner(s): Killos, Paul J.
• Application Number:
  US08/999,000
• Time in Patent Office: 729 Days
• Field of Search: 562/581, 560/152
• US Class Current: 562/581
• CPC Class Codes: A23K 20/105 Aliphatic or alicyclic compounds
• CPC Class Codes: C07C 319/26 Separation; Purification; Stabilisation; Use of additives
• CPC Class Codes: C07C 319/28 Separation; Purification
• CPC Class Codes: C07C 323/52 the carbon skeleton being acyclic and saturated

Abstract

A method for obtaining 2-hydroxy-4-methylthiobutyric acid (methionine-hydroxy analog, MHA) in primarily free form which is stable in storage by distilling a product solution containing MHA and by producing MHA product mixtures with improved storage stability from such a distillate. The distillate can be produced directly starting from MHA raw products from any MHA production process, which can optionally also contain solvent or water. The starting material may also be a commercial MHA product.

Claims

1. A method for obtaining 2-hydroxy-4-methylthiobutyric acid (MHA) which is stable in storage, comprising:

distilling a highly-concentrated liquid MHA containing >

95% by weight monomeric and oligomeric components of MHA for an average residence time of the MHA between 1 and 1×

10⁴ s, under reduced pressure of between 1×

10^-3 and 5×

10⁴ Pa, at a temperature in a range between 40° and

200°

C., at which the monomeric MHA is converted into a gaseous state for a time period which is sufficiently short that formation of significant by-product components is avoided.

2. The method according to claim 1, comprising obtaining the highly-concentrated liquid MHA as an educt by previous evaporation of any non-highly-concentrated MHA.

3. The method according to claim 2, comprising obtaining MHA as product having a stability in storage greater by a factor of 1.3 to about 2.5 than a stability in storage of the educt used with comparable water content, wherein the stability in storage is determined by comparing the MHA dimer and oligomer content of the product or educt with comparable water content which is adjusted in the equilibrium state.

4. The method according to claim 1, comprising obtaining the MHA as a solid, at least partially crystalline product.

5. The method according to claim 1, comprising obtaining an MHA product having an iodine color index in a range between 0 and <

20.

6. The method according to claim 1, wherein apparatus in which the average residence time of the MHA in the distillation is between 1 and 1×

10⁴ s comprises short-path distillation units.

7. The method according to claim 1, comprising obtaining MHA which is essentially free of MHA oligomers.

8. The method according to claim 1, comprising obtaining MHA with an oligomer content of less than 5% by weight at an exit of an evaporator.

9. The method according to claim 1, comprising obtaining bottom products in the MHA distillation which comprise MHA monomers, dimers and oligomers that are fed to a regeneration stage wherein the dimer and oligomer content is reduced by a hydrolysis step to values of ≦

30 molar %, preferably ≦

20 molar %, and especially ≦

10 molar % relative to MHA total.

10. The method according to claim 9, comprising adding at least one member selected from the group consisting of mineral acids, mineral acid salts, MHA and acidic ion exchangers in the hydrolysis step.

11. The method according to claim 10, comprising adding at least one member selected from the group consisting of the mineral acids H₂ SO₄, HCl, H₃ PO₄ and ammonium salts thereof.

12. The method according to claim 10, comprising carrying out hydrolysis of the bottom products of the MHA distillation simultaneously with hydrolysis of MHA amide.