Process for preparing carboxylic acids and derivatives thereof

• US 7,186,856 B2
• Filed: 05/07/2002
• Issued: 03/06/2007
• Est. Priority Date: 05/07/2001
• Status: Expired due to Fees

• Current Assignee: Cargill Incorporated
• Original Assignee: Cargill Incorporated
• Inventors: Abraham, Timothy W., Tsobanakis, Paraskevas, Malsam, Jeffrey, Meng, Xiangsheng
• Primary Examiner(s): Wilson; James O.
• Assistant Examiner(s): Tucker; Zachary C.
• Application Number:
  US10/476,711
• Publication Number:
  US 20040210087A1
• Time in Patent Office: 1,764 Days
• Field of Search: None
• US Class Current: 560/179
• CPC Class Codes: C07C 51/02 from salts of carboxylic acids
• CPC Class Codes: C07C 59/01 Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
• CPC Class Codes: C07C 59/06 Glycolic acid
• CPC Class Codes: C07C 59/08 Lactic acid
• CPC Class Codes: C07C 59/255 Tartaric acid
• CPC Class Codes: C07C 59/265 Citric acid
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/40 Succinic acid esters
• CPC Class Codes: C07C 69/675 of saturated hydroxy-carboxylic acids
• CPC Class Codes: C07C 69/68 Lactic acid esters

Abstract

Processes for preparing carboxylic acids and derivatives thereof in which an ammonium salt of the carboxylic acid is heated in the presence of an organic reagent to split the salt and form the acid or, where the organic reagent is an esterifying agent, the corresponding ester. Both the acid and the ester may be dehydrated to form unsaturated counterparts.

Claims

1. A process for preparing a carboxylic acid, comprising:

providing an aqueous mixture including an ammonium salt of a carboxylic acid;

adding an organic amine that is immiscible in water to the aqueous mixture; and

heating the ammonium salt of a carboxylic acid in the presence of the organic amine to split said salt and form a reaction product comprising said carboxylic acid and said organic amine.

2. A process according to claim 1 wherein said carboxylic acid comprises a hydroxy-functional carboxylic acid.

3. A process according to claim 2 wherein said hydroxy-functional carboxylic acid is selected from the group consisting of alpha hydroxy-functional carboxylic acids, beta hydroxy-functional carboxylic acids, gamma hydroxy-functional carboxylic acids, epsilon hydroxy-functional carboxylic acids, and combinations thereof.

4. A process according to claim 2 wherein said hydroxy-functional carboxylic acid comprises an alpha-hydroxy carboxylic acid.

5. A process according to claim 4 wherein said alpha-hydroxy carboxylic acid is selected from the group consisting of lactic acid, malic acid, tartaric acid, glycolic acid, and combinations thereof.

6. A process according to claim 2 wherein said hydroxy-functional carboxylic acid comprises a beta-hydroxy carboxylic acid.

7. A process according to claim 6 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxypropionic acid.

8. A process according to claim 6 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxybutyric acid.

9. A process according to claim 6 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxyisobutyric acid.

10. A process according to claim 2 wherein said hydroxy-functional carboxylic acid comprises citric acid.

11. A process according to claim 1 wherein said carboxylic acid comprises a mono-carboxylic acid.

12. A process according to claim 1 wherein said carboxylic acid comprises a poly-carboxylic acid.

13. A process according to claim 1 wherein said organic amine has a boiling point greater than 100°

C. when measured at a pressure of 1 atmosphere.

14. A process according to claim 1 wherein said organic amine has a boiling point greater than 175°

C. when measured at a pressure of 1 atmosphere.

15. A process according to claim 1 wherein said organic amine comprises an alkyl amine.

16. A process according to claim 15 wherein said alkyl amine comprises a trialkyl amine.

17. A process according to claim 16 wherein each alkyl group of said trialkyl amine, independently, is a branched or straight chain alkyl group having between 8 and 14 carbon atoms, inclusive.

18. A process according to claim 1 wherein the total number of carbon atoms in said organic amine is at least 18.

19. A process according to claim 1 wherein said organic amine is selected from the group consisting of trioctyl amine, tridecyl amine, tridodecyl amine, and combinations thereof.

20. A process according to claim 1 comprising heating said salt in the presence of said organic amine and an alkyl alcohol having between 8 and 26 carbon atoms, inclusive.

21. A process according to claim 1 further comprising separating said carboxylic acid from said organic amine.

22. A process according to claim 2 further comprising dehydrating said hydroxy-functional carboxylic acid to form an unsaturated carboxylic acid.

23. A process according to claim 22 comprising esterifying said unsaturated carboxylic acid to form an unsaturated carboxylic acid ester.

24. A process according to claim 1 wherein said ammonium salt is heated in the absence of an acidifying agent other than the carboxylic acid of the ammonium salt to split said salt and form said reaction product.

25. A process according to claim 1 further comprising hydrogenating the carboxylic acid group.

26. A process according to claim 2, further comprising dehydrating the carboxylic acid in the reaction product comprising the carboxylic acid and the organic amine.

27. A process according to claim 1, wherein the aqueous mixture comprises a fermentation broth.

28. A process according to claim 1, wherein the aqueous mixture including an ammonium salt of a carboxylic acid is produced by adding a neutralizing component to a fermentation broth.

29. A process according to claim 28, wherein the neutralizing component comprises ammonia.

30. A process according to claim 1,further comprising hydrogenating said carboxylic acid group.

31. A process according to claim 28, wherein the neutralizing component comprises trimethylamine, triethylamine, dibutylamine, or mixtures thereof.

32. A process according to claim 1, wherein the process is conducted in the absence of an acidifying agent other than the carboxylic acid of the ammonium salt.

33. A process for preparing a carboxylic acid, comprising

providing an aqueous mixture including an ammonium salt of a carboxylic acid;

adding an organic solvent having a boiling point of at least 175°

C. when measured at a pressure of 1 atmosphere to the aqueous mixture; and

heating an ammonium salt of a carboxylic acid in the presence of the organic solvent to split said salt and form a reaction product comprising said carboxylic acid and said organic solvent.

34. A process according to claim 33 wherein said organic solvent is selected from the group consisting of alcohols, amides, ethers, ketones, phosphorus esters, phosphinc oxides, phosphine sulfides, alkyl sulfides, and combinations thereof.

35. A process according to claim 33 wherein said organic solvent comprises an alcohol.

36. A process according to claim 35 wherein said alcohol comprises an alcohol having between 8 and 26 carbon atoms, inclusive.

37. A process according to claim 33 wherein said carboxylic acid comprises a hydroxy-functional carboxylic acid.

38. A process according to claim 37 wherein said hydroxy-functional carboxylic acid is selected from the group consisting of alpha hydroxy-functional carboxylic acids, beta hydroxy-functional carboxylic acids, gamma hydroxy-functional carboxylic acids, epsilon hydroxy-functional carboxylic acids, and combinations thereof.

39. A process according to claim 37 wherein said hydroxy-functional carboxylic acid comprises an alpha-hydroxy carboxylic acid.

40. A process according to claim 39 wherein said alpha-hydroxy carboxylic acid is selected from the group consisting of lactic acid, malic acid, tartaric acid, glycolic acid, and combinations thereof.

41. A process according to claim 37 wherein said hydroxy-functional carboxylic acid comprises a beta-hydroxy carboxylic acid.

42. A process according to claim 41 wherein said hydroxy-functional carboxylic acid comprises a beta-hydroxy carboxylic acid.

43. A process according to claim 41 wherein said beta-hydroxy carboxylic acid comprises 3-hybroxybutyric acid.

44. A process according to claim 41 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxyisobutyric acid.

45. A process according to claim 37 wherein said hydroxy-functional carboxylic acid comprises citric acid.

46. A process according to claim 33 wherein said carboxylic acid comprises a mono-carboxylic acid.

47. A process according to claim 33 wherein said carboxylic acid comprises a poly-carboxylic acid.

48. A process according to claim 33 further comprising separating said carboxylic acid from said organic solvent.

49. A process according to claim 37 further comprising dehydrating said carboxylic acid to form an unsaturated carboxylic acid.

50. A process according to claim 49 further comprising esterifying said unsaturated carboxylic acid to form an unsaturated carboxylic acid ester.

51. A process according to claim 33 wherein said ammonium salt is heated in the absence of an acidifying agent other than the carboxylic acid of the ammonium salt to split said salt and form said reaction product.

52. A process according to claim 33 further comprising hydrogenating the carboxylic acid group.

53. A process according to claim 33, wherein the process is conducted in the absence of an acidifying agent other than the carboxylic acid of the ammonium salt.

54. A process according to claim 33, wherein the aqueous mixture including an ammonium salt of a carboxylic acid is produced by adding a neutralizing component to a fermentation broth.

55. A process according to claim 54, wherein the neutralizing component comprises ammonia.

56. A process according to claim 54, wherein the neutralizing component comprises a monoamine or diamine having a boiling point no greater than 175°

C.

57. A process according to claim 54, wherein the neutralizing component comprises trimethylamine, triethylamine, dibutylamine, or mixtures thereof.

58. A process according to claim 37, further comprising dehydrating the carboxylic acid in the reaction product comprising the carboxylic acid and the organic solvent.

59. A process for preparing a beta-hydroxy carboxylic acid ester, comprising heating an ammonium salt of a beta-haydroxy carboxylic acid and an esterifying agent int he absence of an acidifying agent other than the carboxylic acid of the ammonium salt to split said salt and form an ester comprising the reaction product of said carboxylic acid and said esterifying agent.

60. A process according to claim 59, wherein said beta-hydroxy carboxylic acid comprises 3-hybroxybutyric acid.

61. A process according to claim 59, wherein said beta-hydroxy carboxylic acid comprises 3-hydroxybutyric acid.

62. A process according to claim 59, wherein said beta-hydroxy carboxylic acid comprises 3-hydroxyisobutyric acid.

63. A process according to claim 59 wherein said esterifying agent has a boiling point greater than 100°

C. when measured at a pressure of 1 atmosphere.

64. A process according to claim 59 wherein said esterifying agent has a boiling point greater than 175°

C. when measured at a pressure of 1 atmosphere.

65. A process according to claim 59 wherein said esterifying agent comprises an alcohol.

66. A process according to claim 65 wherein said alcohol comprises an alkyl alcohol.

67. A process according to claim 66 wherein said alkyl group of said alkyl alcohol is a branched or straight chain alkyl group having between 8 and 26 carbon atoms, inclusive.

68. A process according to claim 65 wherein said alcohol is selected from the group consisting of octanol, decanol, dodecanol, and combinations thereof.

69. A process according to claim 59 further comprising dehydrating said ester to form an unsaturated ester.

70. A process according to claim 59, wherein the aqueous mixture including an ammonium salt of a carboxylic acid is produced by adding a neutralizing component to a fermentation broth.

71. A process according to claim 59 further comprising hydrolyzing said ester to form the corresponding carboxylic acid.

72. A process according to claim 70, wherein the neutralizing component comprises ammonia.

73. A process according to claim 70, wherein the neutralizing component comprises an amine having a boiling point no greater than 175°

C.

74. A process according to claim 59 further comprising hydrogenating an ester group to produce a hydroxy-functional compound.

75. A process for preparing a carboxylic acid ester, comprising:

providing an aqueous mixture including an ammonium salt of a carboxylic acid;

adding an organic solvent to the aqueous mixture, wherein the organic solvent is an amine that is immiscible in water or an organic solvent having a boiling point of at least 175°

C. when measured at a pressure of 1 atmosphere;

heating the ammonium salt and form a reaction mixture comprising the carboxylic acid and the organic solvent; and

adding an esterifying agent to the reaction mixture to form an ester comprising the reaction product of the carboxylic acid and the esterifying agent.

76. A process according to claim 75, wherein said carboxylic acid comprises a hydroxy-functional carboxylic acid.

77. A process according to claim 76, wherein the hydroxy-functional carboxylic acid is selected from the group consisting of alpha hydroxy-functional carboxylic acids, beta hydroxy-functional carboxylic acids, gamma hydroxy-functional carboxylic acids, epsilon hydroxy-functional carboxylic acids, and combinations thereof.

78. A process according to claim 76, wherein the hydroxy-functional carboxylic acid is selected from the group consisting of lactic acid, malic acid, tartaric acid, glycolic acid, and combinations thereof.

79. A process according to claim 76, wherein the hydroxy-functional carboxylic acid comprises a beta-hydroxy carboxylic acid.

80. A process according to claim 75, wherein the esterifying agent has a boiling point greater than 100°

C. when measured at a pressure of 1 atmosphere.

81. A process according to claim 75, wherein the esterifying agent has a boiling point greater than 175°

C. when measured at a pressure of 1 atmosphere.

82. A process according to claim 75, wherein the esterifying agent comprises an alkyl alcohol.

83. A process according to claim 82, wherein an alkyl group of said alkyl alcohol is a branched or straight chain alkyl group having between 8 and 26 carbon atoms, inclusive.

84. A process according to claim 75, further comprising dehydrating the ester to form an unsaturated ester.

85. A process according to claim 75, further comprising hydrogenating the ester group to produce a hydroxy-functional compound.

86. A process according to claim 75, wherein the aqueous mixture including an ammonium salt of a carboxylic acid is produced by adding a neutralizing component to a fermentation broth.

87. A process according to claim 86, wherein the neutralizing component comprises ammonia or an amine having a boiling point no greater than 175°

C.

88. A process according to claim 75, wherein the process is conducted in the absence of an acidifying agent other than the carboxylic acid of the ammonium salt.

89. A process for preparing 3-hydroxypropionic acid, comprising heating an ammonium salt of a 3-hydroxypropionic acid in the presence of an organic amine that is immiscible in water to split the salt and form a reaction product comprising 3-hydroxypropionic acid and the organic amine.

90. A process for preparing 3-hydroxypropionic acid, comprising heating an ammonium salt of a 3-hydroxypropionic acid in the presence of an organic solvent having a boiling point of at least 175°

C. when measured at a pressure of 1 atmosphere to split the salt and from a reaction product comprising 3-hydroxypropionic acid and the organic solvent.