Process for converting a hydroxycarboxylic acid, or salts thereof, to an unsaturated carboxylic acid and/or its esters

• US 20090076297A1
• Filed: 09/09/2008
• Published: 03/19/2009
• Est. Priority Date: 09/17/2007
• Status: Active Grant

• Current Assignee: Rohm and Haas Company (Dow, Inc.)
• Original Assignee: Rohm and Haas Company (Dow, Inc.)
• Inventors: Silvano, Mark Anthony, Zolotorofe, Donald L., Bogan, Leonard Edward JR.
• Granted Patent: US 7,754,916 B2
• Time in Patent Office: Days
• US Class Current: 560/212
• CPC Class Codes: C07C 51/02 from salts of carboxylic acids
• CPC Class Codes: C07C 51/377 by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups C07C51/36 - C07C51/373 take precedence
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C07C 59/01 Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
• CPC Class Codes: C07C 59/08 Lactic acid
• CPC Class Codes: C07C 59/10 Polyhydroxy carboxylic acids

Abstract

A process for converting a salt of a hydroxycarboxylic acid to an unsaturated carboxylic acid, or esters thereof. The process involves converting an ammonium salt of a hydroxycarboxylic acid in aqueous solution to a corresponding hydroxycarboxylic acid and ammonium cation in aqueous solution; and separating the ammonium cation from the aqueous solution, leaving the hydroxycarboxylic acid in aqueous solution. The converting and separating steps may be accomplished by employing a hydrophobic acid or an acid ion exchange resin, each of which must have an acid dissociation constant, i.e., pK_a, at least 0.5 less that that of the salt of the hydroxycarboxylic acid. Where a hydrophobic acid is used, it must be immiscible in water, and its salt must also be immiscible in water, and the resulting multi-phase solution comprises an aqueous phase comprising the corresponding hydroxycarboxylic acid, as well as a non-aqueous phase comprising a neutralized acid. Alternatively, where the ion exchange resin is used, the aqueous solution of the ammonium salt of a hydroxycarboxylic acid is contacted with the resin, thereby converting the salt to a hydroxycarboxylic acid and capturing the ammonium cations on the resin. In either case, the aqueous solution is treated, such as by heating, to separate and recover the hydroxycarboxylic acid. The non-aqueous phase or resin is treated to separate and recover ammonia useful for preparing additional ammonium salt of a hydroxycarboxylic acid.

Claims

1. A process for preparing an unsaturated carboxylic acid, and esters thereof, from an ammonium salt of a hydroxycarboxylic acid, said process comprising:

a) providing an aqueous solution comprising the ammonium salt of a hydroxycarboxylic acid;

b) converting the ammonium salt of a hydroxycarboxylic acid to a corresponding hydroxycarboxylic acid and ammonium cation in aqueous solution; and

c) separating the ammonium cation from the aqueous solution, leaving the hydroxycarboxylic acid in aqueous solution;

wherein said converting and separating steps b) and c) are accomplished by a technique selected from the group consisting of;

(1) adding a solution comprising a hydrophobic acid and, optionally, an organic solvent, to the aqueous solution, wherein the hydrophobic acid comprises a proton and a conjugate base, is immiscible in water, is capable of forming an ammonium salt which is also immiscible in water, and has an acid dissociation constant (pK_a) which is at least 0.5 less than the acid dissociation constant of the hydroxycarboxylic acid, to form a multi-phase solution which comprises an aqueous phase comprising the hydroxycarboxylic acid, which comprises the carboxylic anion and the proton, and a non-aqueous phase comprising a neutralized acid, which comprises the ammonium cation and the conjugate base of the hydrophobic acid, and

(2) contacting the aqueous solution comprising the ammonium salt of hydroxycarboxylic acid with an acid ion exchange resin having an acid dissociation constant (pK_a) which is at least 0.5 less than the acid dissociation constant of the hydroxycarboxylic acid, to form an aqueous solution comprising the corresponding hydroxycarboxylic acid and a non-aqueous ammonium cation-containing exchange resin.

2. The process of claim 1, wherein said hydroxycarboxylic acid is selected from the group consisting of an α

-hydroxycarboxylic acid, a β

-hydroxycarboxylic acid, and an α

-β

-dihydroxycarboxylic acid.

3. The process of claim 2, wherein said hydroxycarboxylic acid is selected from the group consisting of:

lactic acid, citric acid, 3-hydroxypropionic acid, 3-hydroxy-2-methylpropionic acid, 3-hydroxybutanoic acid, 3-hydroxy-2-methylbutanoic acid, 3-hydroxy-2-methylpentanoic acid, 3-hydroxy-3-methylbutanoic acid, 2,3-dimethyl-3-hydroxybutanoic acid, 3-hydroxy-3-phenylpropionic acid, and combinations thereof.

4. The process of claim 3, wherein said beta-hydroxycarboxylic acid is beta-hydroxypropionic acid.

5. The process of claim 1, wherein said unsaturated carboxylic acid, and esters thereof is selected from the group consisting of:

acrylic acid, methacrylic acid, and esters thereof.

6. The process of claim 1, further comprising the step of:

(d) further treating the hydroxycarboxylic acid by a process selected from the group consisting of;

dehydration to form the desired unsaturated carboxylic acid product and esterification to form the desired ester of an unsaturated carboxylic acid product.

7. The process of claim 6, wherein dehydration of said hydroxycarboxylic acid occurs in the presence of a dehydration catalyst.

8. The process of claim 6, wherein the esterification of said hydroxycarboxylic acid occurs in the presence of an esterification catalyst.

9. The process of claim 6, further comprising the step of separating the unsaturated carboxylic acid product from the aqueous solution.

10. The process of claim 1, further comprising the steps of:

further treating the ammonium cations to form and separate ammonia; and

recovering and recycling the ammonia to an upstream process step in which quantities of an ammonium salt of a hydroxycarboxylic acid are formed in an aqueous solution of a hydroxycarboxylic acid.

11. The process of claim 10, wherein technique (1) is applied to form the multi-phase solution which comprises a non-aqueous phase comprising a neutralized acid and, optionally, an organic solvent, and the neutralized acid comprises the ammonium cation and the conjugate base of the hydrophobic acid, and wherein the non-aqueous phase comprising the neutralized acid, is treated by heating to form and separate ammonia from the non-aqueous phase;

and the ammonia is recovered and recycled to another process step in which additional quantities of an ammonium salt of a hydroxycarboxylic acid are formed in aqueous solution.

12. The process of claim 10, wherein technique (2) is applied to form an aqueous solution comprising the corresponding hydroxycarboxylic acid and a cation-containing ion exchange resin which comprises the ammonium cations, and the ammonium cations are treated by:

washing the ammonium cation-containing ion exchange resin with a washing acid, having an acid dissociation constant (pK_a) which is at least 0.5 less than the acid dissociation constant of the resin, to separate and recover an ammonium salt, comprising the ammonium cation and the conjugate base of the washing acid;

heating the ammonium salt to regenerate ammonia and the washing acid;

recycling the ammonia to an upstream process step in which quantities of an ammonium salt of a hydroxycarboxylic acid are produced; and

recycling the washing acid for washing the additional quantities of ammonia-containing resin and recovering the ammonia.

13. The process of claim 1, wherein the aqueous solution comprises at least 0.1% by weight of the salt of a hydroxycarboxylic acid, based on the total weight of the aqueous solution and salt of a hydroxycarboxylic acid.