Process for preparing carboxylic acids and derivatives thereof

• US 20040210087A1
• Filed: 06/03/2004
• Published: 10/21/2004
• Est. Priority Date: 05/07/2001
• Status: Active Grant

• Current Assignee: Cargill, Inc. (Agricultural Services Division)
• Original Assignee: Cargill, Inc. (Agricultural Services Division)
• Inventors: Abraham, Timothy W, Tsobanakis, Paraskevas, Malsam, Jeffrey, Meng, Xiangsheng
• Granted Patent: US 7,186,856 B2
• Time in Patent Office: Days
• US Class Current: 562/579
• 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 heating an ammonium salt of a carboxylic acid in the presence of an organic amine that is immiscible in water 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 4 wherein said alpha-hydroxy carboxylic acid comprises lactic acid.

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

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

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

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

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

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

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

14. 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.

15. 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.

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

17. A process according to claim 16 wherein said allcyl amine comprises a trialkyl amine.

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

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

20. 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.

21. 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.

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

23. A process according to claim 2 further comprising dehydrating said carboxylic acid to form an unsaturated carboxylic acid.

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

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

26. A process for extracting a carboxylic acid from a fermentation broth comprising:

(a) treating a fermentation broth comprising an ammonium salt of a carboxylic acid with an organic extraction solvent comprising an organic amine that is immiscible in water to form a mixture; and

(b) heating said mixture to split said ammonium salt and form a reaction product comprising said carboxylic acid and said organic amine.

27. A process according to claim 26 wherein said carboxylic acid is a hydroxy-functional carboxylic acid.

28. A process according to claim 26 further comprising separating said carboxylic acid from said organic amine.

29. A process according to claim 26 wherein said ammonium salt is heated in the absence of an acidifying agent to split said salt and form said reaction product.

30. A process according to claim 26 further comprising hydrogenating said carboxylic acid.

31. A process according to claim 27 further comprising dehydrating said carboxylic acid to form an unsaturated carboxylic acid.

32. A process according to claim 31 further comprising esterifying said unsaturated 15 carboxylic acid to form an unsaturated carboxylic acid ester.

33. A process for preparing a carboxylic acid comprising heating an ammonium salt of a carboxylic 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 said salt and form a reaction 20 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, phosphine 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 30 between 8 and 26 carbon atoms, inclusive.

37. A process according to claim 35 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 39 wherein said alpha-hydroxy carboxylic acid comprises lactic acid.

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

43. A process according to claim 42 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxypropionic acid.

44. A process according to claim 42 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxybutyric acid.

45. A process according to claim 42 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxyisobutyric acid.

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

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

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

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

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

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

52. A process according to claim 35 wherein said ammonium salt is heated in the absence of an acidifying agent to split said salt and form said reaction product.

53. A process for extracting a carboxylic acid from a fermentation broth comprising:

(a) treating a fermentation broth comprising an ammonium salt of a carboxylic acid with an organic extraction solvent having a boiling point of at least about 175°

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

(b) heating said mixture to split said ammonium salt and form a reaction product comprising said carboxylic acid and said organic extraction solvent.

54. A process according to claim 53 wherein said carboxylic acid is a hydroxy-functional carboxylic acid.

55. A process according to claim 53 further comprising separating said carboxylic acid from said organic extraction solvent.

56. A process according to claim 53 wherein said ammonium salt is heated in the absence of an acidifying agent to split said salt and form said reaction product.

57. A process according to claim 53 further comprising hydrogenating said carboxylic acid.

58. A process according to claim 54 further comprising dehydrating said carboxylic acid to form an unsaturated carboxylic acid.

59. A process according to claim 58 further comprising esterifying said unsaturated carboxylic acid to form an unsaturated carboxylic acid ester.

60. A process for preparing a carboxylic acid ester comprising heating an ammonium salt of a carboxylic acid and an esterifying agent in the absence of an acidifying agent to split said salt and form an ester comprising the reaction product of said carboxylic acid and said esterifying agent.

61. A process according to claim 60 wherein said carboxylic acid comprises a hydroxy-functional carboxylic acid.

62. A process according to claim 61 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.

63. A process according to claim 61 wherein said hydroxy-functional carboxylic acid comprises an alpha-hydroxy carboxylic acid.

64. A process according to claim 63 wherein said alpha-hydroxy carboxylic acid is selected from the group consisting of lactic acid, malic acid, tartaric acid, glycolic acid, and combinations thereof.

65. A process according to claim 63 wherein said alpha-hydroxy carboxylic acid comprises lactic acid.

66. A process according to claim 60 wherein said hydroxy-functional carboxylic acid comprises a beta-hydroxy carboxylic acid.

67. A process according to claim 66 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxypropionic acid.

68. A process according to claim 66 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxybutyric acid.

69. A process according to claim 66 wherein said beta-hydroxy carboxylic acid comprises 3-hydroxyisobutyric acid.

70. A process according to claim 61 wherein said hydroxy-functional carboxylic acid comprises citric acid.

71. A process according to claim 60 wherein said carboxylic acid comprises a mono-carboxylic acid.

72. A process according to claim 60 wherein said carboxylic acid comprises a poly-carboxylic acid.

73. A process according to claim 60 wherein said esterifying agent has a boiling point greater than 100°

C. when measured at a pressure of 1 atmosphere.

74. A process according to claim 60 wherein said esterifying agent has a boiling point greater than 175°

C. when measured at a pressure of 1 atmosphere.

75. A process according to claim 60 wherein said esterifying agent comprises an alcohol.

76. A process according to claim 75 wherein said alcohol comprises an alkyl alcohol.

77. A process according to claim 76 wherein said alkyl group of said alkyl alcohol is a branched or straight chain allcyl group having between 8 and 26 carbon atoms, inclusive.

78. A process according to claim 75 wherein said alcohol is selected from the group consisting of octanol, decanol, dodecanol, and combinations thereof.

79. A process according to claim 61 further comprising dehydrating said ester to form an unsaturated ester.

80. A process for preparing a carboxylic acid ester from a fermentation broth comprising:

(a) treating a fermentation broth comprising an ammonium salt of a carboxylic acid with an esterifying agent to form a mixture; and

(b) heating said mixture in the absence of an acidifying agent to split said ammonium salt and form an ester comprising the reaction product of said carboxylic acid and said esterifying agent.

81. A process according to claim 80 wherein said carboxylic acid is a hydroxy-functional carboxylic acid.

82. A process ac cording to claim 80 further comprising hydrolyzing said ester to form the corresponding carboxylic acid.

83. A process according to claim 80 wherein said esterifying agent has a boiling point greater than 100°

C. when measured at a pressure of 1 atmosphere.

84. A process according to claim 80 wherein said esterifying agent has a boiling point greater than 175°

C. when measured at a pressure of 1 atmosphere.

85. A process according to claim 80 wherein said esterifying agent comprises an alcohol.

86. A process according to claim 85 wherein said alcohol comprises an alkyl alcohol.

87. A process according to claim 86 wherein said alkyl group of said alkyl alcohol is a branched or straight chain alkyl group having between 8 and 26 carbon atoms, inclusive.

88. A process according to claim 85 wherein said alcohol is selected from the group consisting of octanol, decanol, dodecanol, and combinations thereof.

89. A process according to claim 80 further comprising hydrogenating said ester to produce a hydroxy-functional compound.

90. A process according to claim 81 further comprising dehydrating said ester to form an unsaturated ester.