Solvent drying compositions and related methods

文档序号：491539 发布日期：2022-01-04 浏览：43次中文

阅读说明：本技术 溶剂干燥组合物及相关的方法 (Solvent drying compositions and related methods ) 是由柴特拉·普拉卡什唐海明于 2020-04-02 设计创作，主要内容包括：本公开内容涉及溶剂干燥组合物及相关的方法。本公开内容更具体地涉及在使用中从溶剂混合物中释放水的溶剂干燥组合物。本公开内容还涉及用于回收溶剂干燥组合物的方法,更具体地涉及用于回收渗透过程中使用的溶剂干燥组合物的方法。(The present disclosure relates to solvent-dried compositions and related methods. The present disclosure more particularly relates to solvent-dried compositions that release water from a solvent mixture in use. The present disclosure also relates to methods for recovering solvent drying compositions, and more particularly to methods for recovering solvent drying compositions used in osmosis processes.)

1. A solvent-dried composition comprising:

a) complexes of at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound or alkylsulfonic acid or combinations thereof in a solvent comprising

b) At least one amine-containing compound, at least one enolizable carbonyl group, and water,

wherein in use water in the solvent is released to form a water layer which is immiscible with the solvent dry composition.

2. The composition of claim 1, wherein the carboxylic acid-containing compound is selected from one or more of the following:

a) a compound of the formula I,

wherein R is selected from-C₁-C₇alkyl-OH, -C₁-C₇Alkyl, -C₁-C₇alkyl-NH₂、-C₁-C₇alkyl-NHR³and-C₁-C₇Alkyl radical NR³R⁴Wherein each R is³And R⁴Selected from-H, -OH, -halogen, -C₁-C₇Alkyl, -C₁-C₇alkyl-OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups);

b) a polymer containing one or more carboxylic acid groups.

3. The composition of claim 1 or claim 2, wherein the solvent from which the water is recovered comprises at least one amine-containing compound and at least one enolizable carbonyl group.

4. The composition of any one of claims 1 to 3, wherein the solvent comprises at least a secondary or tertiary amine, or a combination thereof.

5. The composition of any one of claims 1 to 4, wherein the solvent comprises at least one enolizable carbonyl group of formula II:

wherein

a)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇Monocyclic or phenyl; or

b)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

c)R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic or 3-15 membered monocyclic heterocyclic ketone or acetophenone.

6. The composition of any one of claims 1 to 5, wherein the carboxylic acid-containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

7. The composition of any one of claims 1 to 5, wherein the alkyl sulfonic acid is isethionic acid.

8. The composition of any one of claims 1 to 7, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:99 or 99: 1.

9. The composition of any one of claims 1 to 8, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:50 or 50: 1.

10. The composition of any one of claims 1 to 9, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:10 or 10: 1.

11. The composition of any one of claims 1 to 10, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:5 or 5: 1.

12. The composition of any one of claims 1 to 11, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:3 or 3: 1.

13. The composition of any one of claims 1 to 12, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:2 or 2: 1.

14. The composition of any one of claims 1 to 12, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1: 1.

15. The composition of any one of claims 1 to 14, wherein the solvent comprises at least one amine-containing compound, wherein the amine can be the same or different from the amine-containing compound in the complex.

16. The composition of any one of claims 1 to 15, wherein at least one amine-containing compound in the complex or solvent is selected from conjugated, aliphatic, unsymmetrical, or cyclic tertiary amines.

17. The composition of claim 16, wherein the tertiary amine-containing compound is selected from the following:

18. the composition of claim 16 or claim 17, wherein the at least one tertiary amine-containing compound is selected from-N (C)₁-C₇Alkyl radical)₃。

19. The composition of any one of claims 16 to 18, wherein the at least one tertiary amine-containing compound is selected from-N (C)₁-C₄Alkyl radical)₃。

20. The composition of any one of claims 16 to 19, wherein the at least one tertiary amine-containing compound is-N (C)₂Alkyl radical)₃(triethylamine).

21. The composition of claim 16 or claim 17, wherein the at least one tertiary amine-containing compound is ethylpiperidine.

22. The composition of any one of claims 5-21, wherein R of formula II₁is-C₁-C₇An alkyl group.

23. The composition of any one of claims 5 to 22, wherein R of formula II₁Further substituted by one or more substituents selected from-OH, -C₁-C₇Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂-C (O) OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

24. The composition of any one of claims 5 to 15, wherein formula II is 2-butanone.

25. The composition of any one of claims 5 to 24, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:99 or 99: 1.

26. The composition of any one of claims 5 to 25, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:50 or 50: 1.

27. The composition of any one of claims 5-26, wherein the molar ratio of the at least one tertiary amine-containing compound to the enolizable carbonyl of formula II is present in a ratio of about 1:10 or 10: 1.

28. The composition of any one of claims 5 to 27, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:5 or 5: 1.

29. The composition of any one of claims 5 to 28, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:3 or 3: 1.

30. The composition of any one of claims 5 to 29, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:2 or 2: 1.

31. The composition of any one of claims 5 to 30, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1: 1.

32. The composition of any one of claims 1 to 31, wherein the at least one amine-or ammonium salt-containing compound and the at least one carboxylic acid-containing compound or alkylsulfonic acid, or a combination thereof, are irreversibly protonated.

33. A complex composition comprising at least one amine or ammonium salt-containing compound and at least an alkyl sulfonic acid or at least one carboxylic acid-containing compound of formula I, or a combination thereof;

the complex is suitable for use in recovering water from a solvent, wherein water is released from the solvent as the composition migrates through the solvent, the released water forming an aqueous layer that is immiscible with the solvent,

and wherein the solvent comprises:

a) at least one amine-containing compound, wherein,

b) at least one enolizable carbonyl group, and

c) and (3) water.

34. The complex of claim 33, wherein said solvent comprises at least a secondary or tertiary amine, or a combination thereof.

35. The complex of claim 33 or claim 34, wherein the solvent comprises at least one enolizable carbonyl of formula II

Wherein

a)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇Monocyclic or phenyl; or

b)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

c)R₁And R₂Together with the carbonyl group of formula I form a 3-15 membered monocyclic or 3-15 membered monocyclic heterocyclic ketone or acetophenone.

36. The complex of any one of claims 33-35, wherein the at least one amine-containing compound of the complex is a secondary or tertiary amine, or a combination thereof.

37. The complex of any one of claims 33 to 36, wherein the carboxylic acid-containing compound of formula I is selected from acetic acid, citric acid, and glycolic acid, or a combination thereof.

38. The complex of any one of claims 33-37, wherein said alkyl sulfonic acid is isethionic acid.

39. The complex of any one of claims 33-38, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:99 or 99: 1.

40. The complex of any one of claims 33-39, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:50 or 50: 1.

41. The complex of any one of claims 33-40, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:10 or 10: 1.

42. The complex of any one of claims 33-41, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:5 or 5: 1.

43. The complex of any one of claims 33-42, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:3 or 3: 1.

44. The complex of any one of claims 33-43, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:2 or 2: 1.

45. The complex of any one of claims 33-44, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1: 1.

46. The complex of any one of claims 33-45, wherein the solvent comprises at least one amine-containing compound, wherein the amine can be the same or different from the amine-containing compound in the complex.

47. The complex of any one of claims 33 to 46, wherein the at least one amine-containing compound of the complex or solvent is selected from conjugated, aliphatic, unsymmetrical, or cyclic tertiary amines.

48. The complex of claim 47, wherein said tertiary amine-containing compound is selected from the group consisting of:

49. the complex of claim 47 or claim 48, wherein said at least one tertiary amine-containing compound is selected from-N (C)₁-C₇Alkyl radical)₃。

50. The complex of any one of claims 47 to 49, wherein said at least one tertiary amine-containing compound is selected from-N (C)₁-C₄Alkyl radical)₃。

51. The complex of any one of claims 47-50, wherein said at least one tertiary amine-containing compoundis-N (C)₂Alkyl radical)₃(triethylamine).

52. The complex of claim 47 or claim 48, wherein said at least one tertiary amine-containing compound is ethylpiperidine.

53. The complex of any one of claims 35-53, wherein R of formula II₁is-C₁-C₇An alkyl group.

54. The complex of any one of claims 35-54, wherein R of formula II₁Further substituted by one or more substituents selected from-OH, -C₁-C₇Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂-C (O) OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

55. The complex of any one of claims 35-55, wherein formula II is 2-butanone.

56. The complex of any one of claims 33-56, wherein the molar ratio of said at least one tertiary amine-containing compound to said one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:99 or 99: 1.

57. The complex of any one of claims 33-57, wherein the molar ratio of said at least one tertiary amine-containing compound to said one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:50 or 50: 1.

58. The complex of any one of claims 33-58, wherein the molar ratio of said at least one tertiary amine-containing compound to said enolizable carbonyl of formula II is present in a ratio of about 1:10 or 10: 1.

59. The complex of any one of claims 33-59, wherein the molar ratio of said at least one tertiary amine-containing compound to said one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:5 or 5: 1.

60. The complex of any one of claims 33-60, wherein the molar ratio of said at least one tertiary amine-containing compound to said one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:3 or 3: 1.

61. The complex of any one of claims 33-61, wherein the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II is present in a ratio of about 1:2 or 2: 1.

62. The complex of any one of claims 33-62, wherein the molar ratio of said at least one tertiary amine-containing compound to said one or more enolizable carbonyl groups of formula II is present in a ratio of about 1: 1.

63. The complex of any one of claims 33 to 63, wherein the at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound or alkylsulfonic acid, or a combination thereof, are irreversibly protonated.

64. A method of recovering water from a solvent, the method comprising the steps of: contacting a solvent drying composition for recovering water from a solvent, said composition comprising the composition of any one of claims 1 to 32, and allowing said complex composition to migrate through said solvent, whereby said water is released from said solvent, forming a water layer that is immiscible with said solvent.

65. A process as claimed in claim 65 wherein said process includes the step of separating said recovered water from said immiscible solvent layer.

66. A method of recovering water from a solvent, the method comprising the steps of: contacting the solvent with the complex composition of any one of claims 33 to 64, and allowing the composition to migrate through the solvent, whereby the water is released from the solvent, forming an aqueous layer that is immiscible with the solvent.

67. A process as claimed in claim 67 wherein said process includes the step of separating said recovered water from said immiscible solvent layer.

68. A process as claimed in claim 65 or claim 66, wherein the process includes the step of contacting the solvent with one or more solvent drying compositions.

69. The method of claim 69, wherein said solvent is repeatedly contacted with one or more solvent dry compositions to repeatedly release water therefrom.

70. The method of claim 70, wherein one or more solvents are repeatedly contacted with one or more solvent drying compositions in a counter current process.

71. A method of recovering water from a solvent, the method comprising the steps of: contacting the solvent with the complex composition of any one of claims 33-64; and allowing the complex to migrate through the solvent whereby the water is released from the solvent to form an aqueous layer that is immiscible with the solvent.

72. A process as claimed in claim 72 wherein said process includes the step of separating said recovered water from said immiscible solvent layer.

73. The method of claim 72 or claim 73, wherein the method comprises the step of contacting the solvent with one or more complex compositions.

74. The method of claim 74, wherein the solvent is repeatedly contacted with one or more complex compositions to repeatedly release water therefrom.

75. The method of claim 75, wherein one or more solvents are repeatedly contacted with one or more complex compositions in a counter current process.

76. A method of recovering water from a solvent using a solvent drying composition comprising a complex of:

a. at least one amine-or ammonium salt-containing compound, and

b. at least one carboxylic acid containing compound or an alkyl sulfonic acid or a combination thereof,

wherein in use, as the composition migrates through the solvent, the water is released from the solvent, the released water forming a water layer that is immiscible with the solvent,

the method comprises the following steps:

1) contacting the solvent-dried composition with the solvent to release the water from the solvent as the composition migrates through the solvent, the released water and solvent-dried composition forming an aqueous layer that is immiscible with the solvent, and

2) recovering the solvent dried composition from the immiscible aqueous layer.

77. The method of claim 77, further comprising the step of recovering the solvent.

78. The method of claim 78, wherein said recovered solvent drying composition is recycled for use in a further solvent drying process.

79. The method of claim 79, wherein the process of recovering the solvent dried composition is a continuous recovery process.

80. The method of any one of claims 77, 79 or claim 80, wherein the step of recovering the solvent dried solution is achieved by one or more of the following techniques: membrane distillation, pervaporation, osmosis, pressure driven membrane processes, osmosis assisted pressure driven membrane processes, pressure assisted osmosis driven membrane processes, filtration, mechanical vapor recompression, evaporation based processes, water specific reactant or crystallization techniques, and the like.

81. The method of claim 81, wherein the step of recovering the solvent dried solution is accomplished by a pressure assisted osmosis technique.

82. A process as claimed in any one of claims 77 to 82, wherein said process includes a coalescing step to recover said solvent dried composition from an aqueous layer immiscible with said solvent.

83. The process of claim 82, wherein an electrostatic coalescer is used in said coalescing step.

84. The method of any one of claims 77-84, wherein the at least one amine-containing compound is a secondary or tertiary amine, or a combination thereof.

85. The method of any one of claims 77-85, wherein the carboxylic acid-containing compound of formula I is selected from acetic acid, citric acid, and glycolic acid, or a combination thereof.

86. The method of any one of claims 77-86, wherein the carboxylic acid-containing compound is a metal salt-carboxylic acid complex.

87. The method of claim 87, wherein the metal salt-carboxylic acid complex is selected from one or more of the following: metal salts having a valence of less than or equal to 6, Na salts, Fe (II) salts, Fe (III) salts, Cu (II) salts, Al (III) salts, Sr (II) salts, Li salts and Ag salts.

88. The method of claim 88, wherein the metal salt is selected from one or more of the following: NaCl, NaCO₃、SrCl₂、AlCl₃、FeCl₃、Fe(NO₃)₃、Fe₂(SO₄)₃、CuCl₂、CuSO₄、Cu(OH)₂AgF, AgCl and AgBr.

89. The process of any one of claims 87 to 89, wherein the carboxylic acid is selected from one or more of: glycolic acid, citric acid, tartaric acid, poly (acrylic acid-co-maleic acid), polyacrylic acid, sarcosine, acetic acid, carbonic acid, and formic acid.

90. The process of any one of claims 77 to 90, said at least one carboxylic acid-containing compound is selected from one or more of:

a) a compound of the formula I,

b) a polymer containing one or more carboxylic acid groups.

91. The method of any one of claims 77-91, wherein the carboxylic acid-containing compound of formula I is selected from acetic acid, citric acid, and glycolic acid, or a combination thereof.

92. The process of any one of claims 77 to 92, wherein said alkyl sulfonic acid is isethionic acid.

93. The method of any one of claims 77-93, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:99 or 99: 1.

94. The method of any one of claims 77-94, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:50 or 50: 1.

95. The method of any one of claims 77-95, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:10 or 10: 1.

96. The method of any one of claims 77-96, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:5 or 5: 1.

97. The method of any one of claims 77-97, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:3 or 3: 1.

98. The method of any one of claims 77-98, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1:2 or 2: 1.

99. The method of any one of claims 77-99, wherein the molar ratio of the at least one amine-or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is about 1: 1.

100. The method of any one of claims 77-100, wherein the complex comprises:

a) at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid containing compound or an alkyl sulfonic acid or a combination thereof,

the complex is irreversibly protonated.

101. The process of any one of claims 77 to 101, wherein said solvent from which said water is recovered comprises at least one amine-containing compound and at least one enolizable carbonyl group.

102. The process of claim 100 wherein said solvent comprises at least one enolizable carbonyl group of formula II:

wherein R is₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇A single ring; or R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic or 3-15 membered monocyclic heterocyclic ketone or acetophenone.

103. The method of any one of claims 77-102, wherein the solvent comprises at least one amine-containing compound, wherein the amine can be the same or different from the amine-containing compound in the complex.

104. The method of any one of claims 77-104, wherein at least one amine-containing compound in the complex or solvent is selected from conjugated, aliphatic, unsymmetrical, or cyclic tertiary amines.

105. The method of claim 105, wherein the tertiary amine-containing compound is selected from the group consisting of:

106. the method of claim 106 wherein the at least one tertiary amine-containing compound is selected from-N (C)₁-C₇Alkyl radical)₃。

107. The method of claim 107, wherein the at least one tertiary amine-containing compound is selected from-N (C)₁-C₄Alkyl radical)₃。

108. The method of claim 108, wherein the at least one tertiary amine-containing compound is-N (C)₂Alkyl radical)₃(triethylamine).

109. The method as recited in claim 109, wherein said at least one tertiary amine-containing compound is ethylpiperidine.

110. The process of claim 110 wherein R of formula II₁is-C₁-C₇An alkyl group.

111. The method of claim 103 or claim 111, wherein R of formula II₁Further substituted by one or more substituents selected from-OH, -C₁-C₇Alkyl, - (C)₁-C₇Alkyl radical)-OH、-NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂-C (O) OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

112. The method of any one of claims 103, 111, or 112, wherein formula II is 2-butanone.

113. The process of any one of claims 102 to 113, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1:99 or 99: 1.

114. The process of any one of claims 102 to 114, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1:50 or 50: 1.

115. The process of any one of claims 102 to 115, wherein said at least one tertiary amine-containing compound is present in a molar ratio to said enolizable carbonyl of formula II of about 1:10 or 10: 1.

116. The process of any one of claims 102 to 116, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1:5 or 5: 1.

117. The process of any one of claims 102 to 117, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1:3 or 3: 1.

118. The process of any one of claims 102 to 118, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1:2 or 2: 1.

119. The process of any one of claims 102 to 119, wherein said at least one tertiary amine-containing compound and said one or more enolizable carbonyl groups of formula II are present in a molar ratio of about 1: 1.

Technical Field

The present disclosure relates to solvent-dried compositions and related methods. The present disclosure more particularly relates to solvent-dried compositions that release water from a solvent mixture in use. The present disclosure also relates to methods for recovering solvent drying compositions, and more particularly to methods for recovering solvent drying compositions used in osmosis processes.

Background

Extracting or drying water from a solvent mixture is often a high energy and time consuming task.

Jessop et al describe in US2014/0076810 reversible water or aqueous solutions and their use. Reversible water or aqueous solutions are formed by adding an ionizable additive comprising an ionizable functional group having at least one nitrogen atom. The additive is further described as a monoamine, diamine, triamine, tetramine, or polyamine, such as a polymer or biopolymer. Reversible water or aqueous solutions can be reversibly switched between an initial ionic strength and an increased ionic strength by using a trigger, e.g. with CO₂、CS₂Or COS bubbled or treated with Bronsted acid (Bronsted acid), such as formic acid, hydrochloric acid, sulfuric acid, or carbonic acid. To achieve this reversibility, the ionic form of the additive should be capable of deprotonation by the action of an ionization trigger. This necessarily requires a reversible interaction between the ionic form of the trigger and the additive, as shown in jessap, figure 1. The reversibility of water or aqueous solutions allows for control of the solubility or insolubility of various hydrophobic liquids or solvents in water or aqueous solutions. This provides for a moderate separation of the hydrophobic solvent from the switchable waterMeans of (4). However, one of the difficulties with jessap work is the difficulty in separating CO2 from the amine to achieve reversible water. Trace amount of CO₂And amines will remain dissolved in the draw solution, with slow heating and stripping (striping) and recovery kinetics, energy intensive, requiring hours to minutes.

It is an object of the present invention to provide a solvent-dried composition that overcomes these difficulties or at least to provide a useful alternative.

Disclosure of Invention

In a first aspect, the present invention provides a solvent drying composition for recovering water from a solvent, the composition comprising a complex of:

a) at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid-containing compound or an alkyl sulfonic acid; or a combination thereof,

wherein in use, as the composition migrates through the solvent, the water is released from the solvent, the released water forming a water layer that is immiscible with the solvent.

In a second aspect, the present invention provides a solvent drying composition comprising:

a) complexes of at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound or alkylsulfonic acid or combinations thereof in a solvent comprising

b) At least one amine-containing compound, at least one enolizable carbonyl group, and water,

wherein in use water in the solvent is released to form an aqueous layer which is immiscible with the solvent dry composition.

In one embodiment, the carboxylic acid-containing compound is selected from one or more of the following:

a) a compound of the formula I,

wherein R is selected from-C₁-C₇alkyl-OH, -C₁-C₇Alkyl, -C₁-C₇alkyl-NH₂、-C₁-C₇alkyl-NHR₃and-C₁-C₇Alkyl radical NR³R⁴Wherein each R is₃And R₄Selected from-H, -OH, -halogen, -C₁-C₇Alkyl, -C₁-C₇alkyl-OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups); and

b) a polymer containing one or more carboxylic acid groups.

In one embodiment, the alkyl sulfonic acid is isethionic acid (isoethionic acid).

In another embodiment, the solvent comprises at least a secondary or tertiary amine or a combination thereof.

In one embodiment, the solvent comprises at least one enolizable carbonyl group of formula II,

wherein

a)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇A single ring; or

b)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

c)R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic ketone or a 3-15 membered monocyclic heterocyclic ketone.

In one embodiment, the carboxylic acid containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

In one embodiment, the molar ratio of the at least one amine or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is selected from about 1:99 or 99: 1; or about 1:50 or 50: 1; or about 1:10 or 10: 1; or about 1:5 or 5: 1; or about 1:3 or 3: 1; or about 1:2 or 2: 1; or about 1: 1.

In a third aspect, the present invention provides a solvent drying composition comprising:

a) the following complex, at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid-containing compound of formula I in a solvent,

wherein R is selected from-C₁-C₇alkyl-OH, -C₁-C₇Alkyl, -C₁-C₇alkyl-NH₂、-C₁-C₇alkyl-NHR₃and-C₁-C₇Alkyl radical NR₃R₄Wherein each R is₃And R₄Selected from-H, -OH, -halogen, -C₁-C₇Alkyl, -C₁-C₇alkyl-OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups); or an alkyl sulfonic acid; or a combination thereof; the solvent comprises:

c) at least one amine-containing compound, at least one enolizable carbonyl group, and water,

wherein in use water in the solvent is released to form a water layer which is immiscible with the solvent dry composition.

In one embodiment, the complex of at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound of formula 1 is irreversibly protonated.

In another embodiment, the solvent comprises at least a secondary or tertiary amine or a combination thereof.

In one embodiment, the solvent comprises at least one enolizable carbonyl group of formula II,

wherein

d)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇A single ring; or

e)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

f)R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic ketone or a 3-15 membered monocyclic heterocyclic ketone.

In one embodiment, the carboxylic acid containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

In one embodiment, the alkyl sulfonic acid is isethionic acid.

In one embodiment, the complex of at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound of formula I is irreversibly protonated.

In a fourth aspect, the present invention provides a complex composition, wherein the complex comprises at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound selected from one or more of the following:

a) a compound of the formula I,

b) a polymer containing one or more carboxylic acid groups; or an alkyl sulfonic acid; or combinations thereof

The complexes are suitable for recovering water from a solvent, wherein upon migration of the composition through the solvent, water is released from the solvent, the released water forming an aqueous layer immiscible with the solvent

And wherein the solvent comprises:

a) at least one amine-containing compound, wherein,

b) at least one enolizable carbonyl group, and

c) and (3) water.

In another embodiment, the solvent comprises at least a secondary or tertiary amine or a combination thereof.

In one embodiment, the solvent comprises at least one enolizable carbonyl group of formula II,

wherein

a)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇A single ring; or

b)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

c)R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic ketone or a 3-15 membered monocyclic heterocyclic ketone.

In one embodiment, the at least one amine-containing compound of the complex is a secondary or tertiary amine or a combination thereof.

In one embodiment, the carboxylic acid containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

In one embodiment, the alkyl sulfonic acid is isethionic acid.

In one embodiment, the molar ratio of at least the amine or ammonium salt containing compound to the at least one carboxylic acid containing compound or alkyl sulfonic acid or combination thereof is selected from about 1:99 or 99: 1; or about 1:50 or 50: 1; or about 1:10 or 10: 1; or about 1:5 or 5: 1; or about 1:3 or 3: 1; or about 1:2 or 2: 1; or about 1: 1.

In one embodiment, the complex of at least one amine-or ammonium salt-containing compound and at least one carboxylic acid-containing compound of formula I is irreversibly protonated.

In a fifth aspect, the present invention provides a method of recovering water from a solvent, the method comprising the steps of: contacting a solvent drying composition for recovering water from a solvent, said composition comprising a complex of:

a) at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid-containing compound, or an alkyl sulfonic acid; or a combination thereof;

and allowing the complex composition to migrate through the solvent, whereby the water is released from the solvent, forming an aqueous layer that is immiscible with the solvent.

In one embodiment, the method comprises the step of separating the recovered water from the immiscible solvent layer.

In one embodiment, the solvent comprises:

a) at least one amine-containing compound, wherein,

b) at least one enolizable carbonyl group.

In a sixth aspect, the present invention provides a method of recovering water from a solvent, the method comprising the steps of: contacting a solvent drying composition for recovering water from a solvent, said composition comprising

a) At least one amine-containing compound, wherein,

b) at least one enolizable carbonyl group,

contacting the solvent with a complex composition, wherein the complex comprises at least one amine-or ammonium salt-containing compound and at least:

(a) an alkyl sulfonic acid; or

(b) At least one carboxylic acid-containing compound of formula I,

allowing the complex composition to migrate through the solvent whereby the water is released from the solvent forming a water layer that is immiscible with the solvent.

In one embodiment, the method comprises the step of separating the recovered water from the immiscible solvent layer.

In one embodiment, the solvent comprises:

a) at least one amine-containing compound, wherein,

b) at least one enolizable carbonyl group.

In another aspect, the present invention provides a method of recovering water from a solvent using a solvent drying composition as defined above, the composition comprising a complex of:

a) at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid-containing compound or an alkyl sulfonic acid; or a combination thereof,

wherein in use, as the composition migrates through the solvent, the water is released from the solvent, the released water forming a water layer that is immiscible with the solvent;

the method comprises the following steps:

2) recovering the solvent dried composition from the immiscible aqueous layer.

In one embodiment, the method comprises the step of recovering the solvent.

In one embodiment, the recovered solvent drying composition is recycled for use in a further solvent drying process. In a preferred embodiment, the process of recovering the solvent dried composition is a continuous recovery process.

In one embodiment, the step of recovering the solvent dried solution is accomplished by one or more of the following techniques: membrane distillation, pervaporation, osmosis, pressure driven membrane processes, osmosis assisted pressure driven membrane processes, pressure assisted osmosis driven membrane processes, filtration, mechanical vapor recompression, evaporation based processes, water specific reactant or crystallization techniques, and the like.

In one embodiment, the step of recovering the solvent dry solution is accomplished by a pressure assisted osmosis technique.

In one embodiment, the at least one carboxylic acid-containing compound is selected from one or more of the following:

a) a compound of the formula I,

b) a polymer containing one or more carboxylic acid groups.

In one embodiment, the alkyl sulfonic acid is isethionic acid.

In one embodiment, the carboxylic acid containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

In another embodiment, the at least one amine-containing compound is a secondary or tertiary amine or a combination thereof.

In one embodiment, the carboxylic acid-containing compound is a metal salt-carboxylic acid complex.

In one embodiment, the metal salt-carboxylic acid complex is selected from one or more of the following: metal salts having a valence of less than 6,4, such as Na salts, fe (ii) salts, fe (iii) salts, cu (ii) salts, al (iii) salts, sr (ii) salts, Li salts and Ag salts. In one embodiment, the metal salt has a valence of less than 4.

In one embodiment, the carboxylic acid containing compound of formula I is selected from acetic acid, citric acid and glycolic acid or a combination thereof.

In one embodiment, the complex comprises:

a) at least one amine-or ammonium salt-containing compound, and

b) at least one carboxylic acid-containing compound or an alkyl sulfonic acid; or a combination thereof,

the complex is irreversibly protonated.

In one embodiment, the solvent from which the water is recovered comprises at least one amine-containing compound and at least one enolizable carbonyl group.

In another embodiment, the solvent comprises at least a secondary or tertiary amine or a combination thereof.

In one embodiment, the solvent comprises at least one enolizable carbonyl group of formula II,

wherein

a)R₁And R₂Is independently selected from-C₁-C₇Alkyl or-C₃-C₇A single ring; or

b)R₁Or R₂One of them is selected from-O- (C)₁-C₇Alkyl) and the other is selected from-C₁-C₇Alkyl, or

c)R₁And R₂Together with the carbonyl group of formula II form a 3-15 membered monocyclic ketone or a 3-15 membered monocyclic heterocyclic ketone or acetophenone.

The foregoing brief summary broadly describes the features and technical advantages of certain embodiments of the present invention. Other technical advantages will be described in the following detailed description and examples of the present invention.

The novel features which are believed to be characteristic of the invention will be better understood from the detailed description of the invention when considered in connection with any accompanying figures and examples. However, the drawings and examples provided herein are intended to help illustrate the invention or to help understand the invention, and are not intended to limit the scope of the invention.

Brief Description of Drawings

Figure 1 shows a calibration curve of ethylpiperidine concentration at lower concentrations.

Figure 2 shows the drying capacity of various amine/acid complexes compared to the prior art.

FIG. 3 shows the drying capacity of various amine/amino acid complexes.

Figure 4 schematically shows five countercurrent regeneration processes using commercial brine.

Fig. 5 shows a graph of various water contents in each stage of the countercurrent regeneration process outlined in fig. 4.

Fig. 6 schematically shows a process diagram of a pressure-assisted osmosis process for recovering a solvent dried composition.

Figure 7 shows a process diagram of a continuous process system for recovering a solvent drying composition.

Figure 8 shows a graph of reverse osmosis flux (LMH) data and% rejection data for a 20% (by volume) diluted dry solvent solution at 60 bar.

Figure 9 shows the flux data results obtained from 5 different membranes at different pressures.

Figure 10 shows the% rejection results obtained from 5 different membranes at different pressures.

FIG. 11 shows a process diagram for recovering a solvent dried composition using an electrostatic coalescer.

Detailed Description

The following description sets forth a number of exemplary configurations, parameters, and the like. It should be recognized, however, that such description is not intended as a limitation on the scope of the present invention, but is provided as a description of exemplary embodiments.

Definition of

In each case herein, the terms "comprising", "including" and the like are to be interpreted broadly, without limitation, in the description, embodiments and examples of the invention. Thus, unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive sense, i.e., in a sense that "includes but is not limited to".

The term "about" or "approximately" generally means within 20%, more preferably within 10% and most preferably within 5% of a given value or range. Alternatively, the term "about" means within a logarithm (i.e., an order of magnitude) of a given value, preferably within 2 times the given value.

As used herein, the term "at least one amine-or ammonium salt-containing compound" is meant to include-NH₃、-NHR³or-NR³R⁴A radical or-NH₄ ⁺With the proviso that ammonium bicarbonate is excluded, wherein each R is³And R⁴Selected from-H, -OH, -halogen, -C₁-C₇Alkyl, -C₁-C₇alkyl-OH, -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups);

as used herein, the term "carboxylic acid-containing compound" is any compound having-COOH groups or salts thereof, including polymeric compounds, such as polyacrylic acid, copolymers, such as poly (acrylic acid-co-maleic acid) solutions, and the like.

As used herein, the term "alkylsulfonic acid" includes those having the formula R-S (O)₂Any compound of OH function or salt thereof, wherein R is C₁-C₇Alkyl radical, wherein C₁-C₇Alkyl is as defined below.

As used herein, the term "C₁-C₇Alkyl "refers to a fully saturated branched or unbranched hydrocarbon moiety, which may be straight or branched with a specific range of 1 to 7 carbons. Preferably, the alkyl group contains 1 to 7 carbon atoms, or 1 to 4 carbon atoms. C₁-C₇Representative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2-dimethylpentyl, 2, 3-dimethylpentyl, n-heptyl, and the like. For example, expression C₁-C₄Alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl and isobutyl. In one embodiment, C₁-C₇The alkyl group may be substituted with one or more of the following groups: -halogen, -OH, -CN, -NO₂、-CΞCH、-SH、-C₁-C₇Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂、-O(C₁-C₇Alkyl), -C (O) -O (-C)₁-C₇Alkyl), -C (O) OH; -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

As used herein, the term "C₃-C₇Monocyclic "is a 3-, 4-, 5-, 6-or 7-membered saturated or unsaturated monocyclic ring. Representative of C₃-C₇Monocyclic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and cycloheptyl. In one embodiment, C₃-C₇Monocyclic cycloalkyl groups may be substituted with one or more of the following groups: -halogen, -OH, -CN, -NO₂、-CΞCH、-SH、-C₁-C₇Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂、-O(C₁-C₇Alkyl), -C (O) -O (-C)₁-C₇Alkyl), -C (O) OH; -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

The term "3-to 15-membered monocyclic ketone" refers to a 3-to 15-membered non-aromatic monocyclic ring system containing a ketone functionality. Representative examples of 3-to 15-membered monocyclic ketones include, but are not limited to, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, cyclotridecanone; cyclotetradecone and cyclopentadecanone.

In one embodiment, the 3-to 15-membered monocyclic ketone can be substituted with one or more of the following groups: -halogen, -OH, -CN, -NO₂、-CΞCH、-SH、-C₁-C₇Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂、-O(C₁-C₇Alkyl), -C (O) -O (-C)₁-C₇Alkyl), -C (O) OH; -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups).

The term "3-to 15-membered monocyclic heterocyclic ketone" means: (i) a 3-or 4-membered non-aromatic monocyclic cycloalkyl group in which 1 of the ring carbon atoms is replaced by N, O or S atom; or (ii) a 5-to 15-membered non-aromatic monocyclic cycloalkyl group in which 1 to 4 of the ring carbon atoms are independently replaced by N, O or an S atom. Representative examples of 3-to 15-membered monocyclic heterocyclic ketones having one N, O or S atom include, but are not limited to, oxirane-2-one, thiopyran-2-one, oxetan-3-one, azetidin-3-one, thien-2-one, thien-3-one, dihydrofuran-2 (3H) -one, dihydrofuran-3 (2H) -one, pyrrolidin-3-one, dihydrothiophene-3 (2H) -one, dihydrothiophene-2 (3H) -one, tetrahydro-2H-pyran-2-one, dihydro-2H-pyran-3 (4H) -one, dihydro-2H-pyran-4 (3H) -one, dihydropyran-2H-4 (3H) -one, and the like, Piperidin-3-one, piperidin-4-one, tetrahydro-2H-thiopyran-2-one, dihydro-2H-thiopyran-3 (4H) -one, and,dihydro-2H-thiopyran-4 (3H) -one, oxepan-2-one, oxepan-3-one, oxepan-4-one, thieepan-2-one, thieepan-3-one, thieepan-4-one, azepan-3-one, azepan-4-one, oxepin-2-one, sheepsyclooctane-3-one, oxepin-4-one, oxepin-5-one, thiepin-2-one, thiepin-3-one, thiepin-4-one, thiepin-5-one, azacyclooctan-3-one, oxepin-2-one, oxepin-3-one, oxepin-4-one, oxepin-5-one, oxepin-3-one, oxepin-one, and their pharmaceutically acceptable salts, Azacyclooctan-3-one, azocane-4-one, azocane-5-one, azenan-3-one, azenan-4-one, azenan-5-one, oxacyclononan-2-one, oxacyclononan-3-one, oxacyclononan-4-one, oxacyclononan-5-one, thiacyclononan-2-one, thiacyclononan-3-one, thiacyclononan-4-one, thiacyclononan-5-one, oxacycloundecan-2-one, oxacycloundecan-3-one, oxacycloundecan-4-one, oxacycloundecan-5-one, oxacycloundecan-6-one, Azacycloundecan-3-one, azacycloundecan-4-one, azacycloundecan-5-one, azacycloundecan-6-one, thiacycloundecan-2-one, thiacycloundecan-3-one, thiacycloundecan-4-one, thiacycloundecan-5-one, thiacycloundecan-6-one, oxacyclododecan-2-one, oxacyclododecan-3-one, oxacyclododecan-4-one, oxacyclododecan-5-one, oxacyclododecan-6-one, oxacyclododecan-7-one, azacyclododecan-3-one, azacyclododecan-4-one, azacyclododecan-5-one, Azacyclododecan-6-one, azacyclododecan-7-one, thiacyclododecan-2-one, thiacyclododecan-3-one, thiacyclododecan-4-one, thiacyclododecan-5-one, thiacyclododecan-6-one, thiacyclododecan-7-one, oxatridecan-2-one, oxatridecan-3-one, oxatridecan-4-one, oxatridecan-5-one, oxatridecan-6-one, oxatridecan-7-one, azacyclotridecan-3-one, azacyclotridecan-4-one, azacyclotridecan-5-one, azacyclotridecan-6-one, Azacyclotridecan-7-one, thietane-2-one, thietane-3-one, thietane-4-one, thietane-5-one, thietane-6-one, thietaneCyclotridecan-7-one, oxetanetradecan-2-one, oxetanetradecan-3-one, oxetanetradecan-4-one, oxetanetradecan-5-one, oxetanetradecan-6-one, oxetanetradecan-7-one, oxetanetradecan-8-one, azetidin-3-one, azetidin-4-one, azetidin-5-one, azetidin-6-one, azetidin-7-one, azetidin-8-one, thietane-2-one, thietane-3-one, thietane-4-one, thietane-5-one, Thiocyclotetradecan-6-one, thietanetetradecan-7-one, thietanetetradecan-8-one, oxacyclopentadecan-2-one, oxacyclopentadecan-3-one, oxacyclopentadecan-4-one, oxacyclopentadecan-5-one, oxacyclopentadecan-6-one, oxacyclopentadecan-7-one, oxacyclopentadecan-8-one, azacyclopentadecan-3-one, azacyclopentadecan-4-one, azacyclopentadecan-5-one, azacyclopentadecan-6-one, azacyclopentadecan-7-one, azacyclopentadecan-8-one, thiacyclopentadecan-2-one, thiacyclopentadecan-3-one, Thiapentadecan-4-one, thiapentadecan-5-one, thiapentadecan-6-one, thiapentadecan-7-one, thiapentadecan-8-one. In one embodiment, a 3-to 15-membered monocyclic heterocyclic ketone group may be substituted with one or more of the following groups: -halogen, -OH, -CN, -NO₂、-CΞCH、-SH、-C₁-C₆Alkyl, - (C)₁-C₇Alkyl) -OH, -NH₂、-NH(C₁-C₇Alkyl), -N (C)₁-C₇Alkyl radical)₂、-O(C₁-C₇Alkyl), -C (O) -O (-C)₁-C₇Alkyl), -C (O) OH; -C (O) -H or-C (O) - (C)₁-C₇Alkyl groups). For the avoidance of doubt, a 3-to 5-membered monocyclic heterocyclic ketone does not include any amide groups in which the enolizable carbonyl group of the ketone is adjacent to the N atom in the ring structure.

As used herein, the term "halogen" refers to-F, -Cl, -Br, or-I.

The term "enolizable carbonyl" means a compound having one or more carbonyl functional groups, and wherein at least one of the carbonyl functional groups has an alpha hydrogen (H α) that can be removed by a base to form an enolate and then an enol, as shown in the reaction scheme below.

It is to be understood that the term enolizable carbonyl as used in this specification does not include compounds having only aldehyde functional groups, compounds having only carboxylic acid functional groups, compounds having only amide functional groups, compounds having only acyl halide functional groups, or acetylacetone. Enolizable carbonyl groups of the present invention include those exemplified in the specification, and also include, but are not limited to, the following enolizable carbonyl groups: 1-acetonaphthone, 2-acetonaphthone, 4-methyl-1-acetonaphthone, 1 '-hydroxy-2' -acetonaphthone, 2 '-hydroxy-1' -acetonaphthone, 2-methoxy-1-acetonaphthone, 4-fluoro-1-acetonaphthone; 2-acetylphenanthrene, 3-acetylphenanthrene, 4-acetylphenanthrene, 9-acetylphenanthrene, 6-bromo-9-acetylphenanthrene, 9-fluoro-10-acetylphenanthrene, 9-fluorenone oxime, 2-nitro-9-fluorenone, 3-nitro-9-fluorenone, 4-nitro-9-fluorenone, 2, 6-dinitro-9-fluorenone, 2, 7-dinitro-9-fluorenone, 2,3, 7-trinitro-9-fluorenone, 2-fluoro-9-fluorenone, 1-bromo-9-fluorenone, 2, 7-dichloro-9-fluorenone, 2, 7-dibromo-9-fluorenone, 2-hydroxy-9-fluorenone, 4-hydroxy-9-fluorenone; 1-methylfluoren-9-one; 4-methylfluoren-9-one; 3, 4-dihydro-2 (1H) -quinolinone, 7-hydroxy-3, 4-dihydro-2 (1H) -quinolinone, 6-hydroxy-3, 4-dihydro-2 (1H) -quinolinone, 8-bromo-2, 3-dihydro-4 (1H) -quinolinone, 3-butyl-4-hydroxy-1-methyl-2 (1H) -quinolinone, 6-fluoro-4, 4-dimethyl-3, 4-dihydro-2 (1H) -quinolinone, 8-fluoro-4, 4-dimethyl-3, 4-dihydro-2 (1H) -quinolinone, 2, 6-dimethyl-4 (1H) -quinolinone, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof, 3-butyl-4-hydroxy-1-methyl-2 (1H) -quinolinone, 1-indanone, 5, 6-dimethoxy-1-indanone, 6-bromo-1-indanone, 6-methoxy-1-indanone, 2-bromo-1-indanone, 4-bromo-1-indanone, 5-chloro-1-indanone, 6-chloro-1-indanone, 4, 7-dimethyl-1-indanone, 2-methyl-1-indanone, 4-methyl-1-indanone, 5-fluoro-1-indanone, 6- (trifluoromethyl) -1-indanone, 4-methoxy-1-indanone, 3, 5-dimethoxy-1-indanone, 4, 7-dimethoxy-1-indanone, 5-hydroxy-1-indanone, 4-hydroxy-1-indanone, 7-hydroxy-1-indanone, 2-indanone oxime, 2, 2-bis (methylthio) -1-indanone, (2, 4-dimethoxyphenyl) acetone, 3, 5-dimethoxyacetophenone, 4- (4-methoxyphenyl) -2-butanone, 3-methoxyphenylacetone, 4-methoxyacetophenone, 4-methoxy-2-phenylacetophenone, 2, 5-dimethylphenylacetone, 3,4, 5-trimethoxyphenylacetone, 3, 5-trimethoxyphenylacetone, 2-methylketobutyric acid, 2-dimethylphenylacetone, 3,4, 5-dimethylphenylacetone, 4-hydroxy-3-phenylbutan-2-one, 3-hydroxy-4-phenylbutan-2-one, 3-hydroxy-3-phenylbutan-2-one, 4-hydroxy-4-phenylbutan-2-one, 1-hydroxy-3-phenylbutan-2-one, 3-hydroxy-1, 3-diphenylbutan-2-one, 4-hydroxyphenylacetone, 3, 4-dihydroxyphenylacetone, 4-nitrophenylacetone, acetophenone, 4-methylacetophenone, benzylacetone, 3-methylphenylacetone, 4-methylphenylacetone, 4-ethylphenylacetone, 1-phenylbutan-2-one, 3-phenylbutan-2-one, 4-phenylbutan-2-one, 1-bromo-4-phenylbutan-2-one, 3-methyl-1-phenylbutan-2-one, 3-methyl-4-phenylbutan-2-one, ethylphenylketone, butylphenyl ketone, cyclopropylphenyl ketone, cyclopentylphenyl ketone, cyclobutylphenyl ketone, cyclohexylphenyl ketone, 2-phenylcyclopentanone, 3-phenylcyclopentanone, 2-phenylcyclohexanone, 3-phenylcyclohexanone, 2-phenylcycloheptanone, 3-phenylcycloheptanone, 4-chlorophenylacetone, 4-chloro-2-phenylacetophenone, 3-phenylbutan-2-one, and mixtures thereof, 2, 6-dichlorophenylacetone, 3-chlorophenylacetone, 2, 6-difluorophenylacetone, 1-bromo-1-phenylbutan-2-one, 3-bromo-4-phenylbutan-2-one, 1-bromo-4-phenylbutan-2-one, 3-chloro-4-phenylbutan-2-one, 2-acetylthiophene, cyclopropyl-2-thiophenone, 2-acetylfuran, 2-furylmethyl ketone, 1-acetylpyrrole, 2-acetylpyrrole, 4-methyl-2-phenylacetophenone, 1, 3-diphenylpropanone, 4-diphenylbutan-2-one, benzophenone, 2-bromopropylketone, 2-acetylketone, 2-benzoylketone, 4-methyl-2-phenylacetophenone, 1, 3-diphenylpropan-2-one, 4-diphenylbutan-2-one, benzophenone, 2-fluoropropanone, and mixtures thereof, 4-naphthyl phenone, 2-benzoylpyridine, 3-benzoylpyridine, 4-benzoylpyridine, 2- (4-chlorobenzoyl) pyridine, 2-benzoylthiophene, 2-benzoylpyrrole, bis (3-thienyl) methanone, 3-phenyl-1- (2-thienyl) -2-propen-1-one and piperonyl acetone.

The term "amine-containing compound" includes any compound comprising one or more amine functional groups, but excludes heterocyclic amines in which the heterocycle includes an oxygen or sulfur atom and at least one amine group; such as 4-ethylmorpholine.

The term "tertiary amine-containing compound" preferably means a compound having at least one tertiary amine group, but it is understood that the compound may have more than one tertiary amine group, or further may be a mixture of tertiary amine-containing compounds. Preferably, the tertiary amine-containing compound is a base, such as a lewis base. If the base is a Lewis base, it is envisaged that a Lewis adduct may be formed with the enolizable carbonyl group. In one embodiment, preferably, the tertiary amine-containing compound is immiscible with water at 20 degrees Celsius or above 20 degrees Celsius at one standard atmosphere of pressure. The solution may include a combination of more than one tertiary amine-containing compound. The tertiary amine-containing compound can be aliphatic, conjugated, asymmetric, or cyclic, or a combination thereof.

Examples of suitable tertiary amine-containing compounds include the following:

in one embodiment, the tertiary amine-containing compound is selected from the group consisting of 1-ethylpyrrolidine, ethylpiperidine, 2-methylpyridine, and N-methylpiperidine.

In one embodiment, the tertiary amine-containing compound is selected from-N (C)₁-C₇Alkyl radical)₃. In another embodiment, the tertiary amine-containing compound is selected from the group consisting of-N (C)₁-C₄Alkyl radical)₃. In another embodiment, the tertiary amine-containing compound is-N (C)₂Alkyl radical)₃(triethylamine).

It will be appreciated that the tertiary amine-containing compounds listed above are sufficiently simple to produce on an industrial scale.

It is to be understood that the molar ratio of the at least one tertiary amine-containing compound to the one or more enolizable carbonyl groups of formula II can be in a range including about 1:99 or 99: 1; about 1:50 or 50: 1; about 1:10 or 10: 1; about 1:5 or 5: 1; about 1:3 or 3: 1; a number of molar ratios of about 1:2 or 2:1 or about 1:1 are present.

It is understood that the molar ratio of the at least one amine or ammonium salt-containing compound to the at least one carboxylic acid-containing compound or alkylsulfonic acid, or combination thereof, is selected from about 1:99 or 99: 1; or about 1:50 or 50: 1; or about 1:10 or 10: 1; or about 1:5 or 5: 1; or about 1:3 or 3: 1; or about 1:2 or 2: 1; or about 1: 1.

Examples

The examples described herein are provided to illustrate specific embodiments of the invention and are not intended to limit the invention in any way. Those of ordinary skill in the art, with the benefit of the disclosure and teachings herein, may generate additional embodiments and variations without undue experimentation. All such embodiments and variations are considered a part of the present invention.

Preparation example

Preparation example 1 Water-absorbent solvent mixture solution

Preparation of water-absorbing solvent mixtures for testing purposes. The following procedure was used to produce a standard aqueous solvent mixture solution.

1. Commercially available analytical grade 2-butanone (also known as methyl ethyl ketone MEK) and Triethylamine (TEA) were mixed at a molar ratio of 2:1 in table 1 below to produce a water absorbing solvent mixture (anhydrous) in its "dry" state:

table 1:

total amount of the solvent mixture (L) obtained	2-butanone (L)	Triethylamine (L)
			1	0.563	0.437
2	1.125	0.875
			5	2.813	2.187
10	5.626	4.374
			20	11.253	8.747

2. 10% deionized water was added to the solvent mixture in the amount shown in table 2 below and shaken thoroughly. The addition of water to the solvent mixture produces a "wet solvent mixture".

Table 2:

3. once the wet solvent mixture is prepared, various complexes of [ amine + carboxylic acid containing compound ] can be studied as drying agents, i.e. agents for removing water from the solvent mixture. This would involve adding the selected desiccant to the wet solvent mixture under vigorous shaking. The desiccant was added in a 2:1 ratio of water to desiccant as shown in table 3.

Table 3:

4. the two liquids were completely separated.

5. The desiccant (bottom layer) was decanted and disposed of.

6. Standard addition tests (in triplicate) were performed to calculate the concentration of water in the sample using gas chromatography.

All GC data were collected on a SHIMADZU Nexis2030 gas chromatograph equipped with a SUPELCO WATERCOL 1910 column. The GC parameters were set as follows:

the column method comprises the following steps:

rate (. degree.C./min)	Temperature (. degree.C.)	Retention time (min)
			100.00	2.55
25.0	168.0	5.0

The total program time is 10:27min

PREPARATION EXAMPLE 2 desiccant Complex

The desiccant complex was formulated as citric acid to ethylpiperidine in a 1:1 molar ratio, followed by the addition of a 10% excess of citric acid to ensure that all ethylpiperidines have complexed to form a complex [ amine + carboxylic acid containing compound ] to remove any possibility of "free" ethylpiperidines.

Example 1 Water absorption of various complexes [ Ammonian + Carboxylic acid-containing Compounds ]

Some complexes of amine with citric acid or amine with glycolic acid were evaluated for regenerant capability. A complex of citric acid and glycolic acid was prepared at the same molar concentration of 6.9 mol/kg. Various combinations of solvent mixtures were prepared as outlined in table 4 below for reaction with 6.9mol/kg citric acid or glycolic acid to form various complexes [ amine + carboxylic acid containing compounds ], and then tested for their water absorbing capacity:

table 4: composition of various solvent mixtures

Mixtures of solvents	Molar ratio of
		Triethylamine MEK	0.5:1
Ethyl piperidine MEK	0.5:1
		(Triethylamine: ethylpiperidine): MEK	(0.3:0.2):1

The complexes [ amine + carboxylic acid containing compounds ] obtained were tested for water recovery capacity by the following procedure:

0.2ml of each complex was added to 20ml of the wet solvent mixture (prepared according to preparation example 1 above).

The resulting mixture was mixed by a vortex mixer for 30 seconds and then separated by a centrifuge equipped with a 4-arm horizontal rotor with a diameter of 130mm at 4000rpm for 60 seconds.

Residual water in the solvent mixture was measured by standard addition methods using gas chromatography.

The results obtained are listed in table 5.

Table 5: the composition of the novel amine/acid complex combinations (by contacting the acid + amine complex with a wet solvent mixture) and their water absorption capacity.

TEA ═ triethylamine; EP ═ ethylpiperidine; IBA ═ isobutylamine; PYR ═ pyrrolidine

The results shown in table 5 show that the amine/acid salt also exhibits a regenerating water absorbing capacity and therefore may also function as a regenerant. At the same concentration, citrate has better water absorption than glycolate.

Example 1 (continuous) -Water-absorption of various composites [ ammonium salt + carboxylic acid-containing Compound ]

The water recovery capacity of the ammonium salt and citric acid complex was evaluated. A mixture of dry and wet solvents was prepared as in preparation 1 above.

Ammonium citrate was prepared as follows:

citric acid (13.96g,0.073mol) was added to 10ml of 28 wt% aqueous ammonia (NH4OH:2.55g, 0.073 mol).

The mixture was stirred at room temperature for 30 minutes.

A saturated solution was prepared as follows:

an amount of acid was added to 10mL of distilled water.

The solution was stirred at room temperature.

Once no more acid is dissolved, the stirring is stopped and a saturated solution is used.

In table 6, some potential ammonium salt regenerants were made into saturated solutions. The regenerant compositions and sources are listed in the table. The procedure for measuring water absorption capacity was as follows:

0.2ml of each rejuvenating agent was added to 20ml of the wet solvent mixture.

It was mixed by a vortex mixer for 30 seconds and then separated by a centrifuge equipped with a 4-arm horizontal rotor with a diameter of 130mm at 4000rpm for 60 seconds.

The remaining water in the solvent mixture was checked by GC by standard addition methods.

Table 6: potential ammonium salt regenerant

Ammonium citrate was prepared as described above.

A series of carboxyl-containing compounds were tested to determine their water absorption capacity. As described above, a wet solvent mixture sample was prepared according to the above preparation example 1. Various carboxylic acid-containing compounds were purchased from Sigma-Aldrich, such as poly (acrylic acid-co-maleic acid) solution, poly (acrylic acid), glycolic acid, and tartaric acid. Carboxylic acid-containing compounds were prepared as shown in table 6 and table 7. The samples in table 6 were diluted to half concentration and used for testing, which was evaluated in table 7.

Table 7: the table shows the potential acids at a molar concentration of-COOH of 9.80mol/kg

The molar concentration of-COOH (mol/kg) was calculated using the following formula:

table 8: the table shows the potential carboxylic acids at a molar concentration of 0.200mol/kg

Molar concentration (mol/kg) was calculated using the following formula:

the following steps were taken to measure the water release capacity of these carboxylic acid group containing candidates:

0.2ml of each carboxylic acid-containing compound are added to 20ml of the wet solvent mixture.

The resulting combination was mixed by the apparatus of the mixer for 30 seconds and then separated by a centrifuge equipped with a 4-arm horizontal rotor with a diameter of 130mm at 4000rpm for 60 seconds.

The remaining water in the solvent mixture was checked by GC by standard addition methods.

Observation and analysis:

table 9: water absorption Capacity of half the concentrations of the various acids in Table 7

Table 10: water absorption Capacity of the various acids in Table 7

Table 11: water absorption Capacity of the various acids in Table 8

The results show that increasing the-COOH concentration also increases the water-absorbing capacity. Poly (acrylic acid-co-maleic acid) shows the best potential as a regenerant at low concentrations.

EXAMPLE 2 amine Complex exchange experiment

This experiment was performed to determine how much amine exchange (cross-over) could be detected between the amine and the solvent mixture in the desiccant composite. The desiccant composite was tested against the solvent mixture at 7.1% humidity. The solvent mixture contained TEA to MEK prepared according to preparation example 1 in a molar ratio of 1: 2. Equal volumes of the wet solvent mixture and desiccant were mixed and the resulting combination was vortexed for 30 seconds and then separated by a centrifuge equipped with a 4-armed horizontal rotor 130mm in diameter at 4000rpm for 60 seconds. The samples were allowed to equilibrate overnight before testing. The results are shown in table 12, and the gas chromatography calibration curve for ethylpiperidine is shown in fig. 1.

Table 12:

samples of wet solvent mixture (MEK: TEA)	Ethylpiperidine (ppm) measured in a solvent mixture
		7.1％	2289

It can be seen that very little ethylpiperidine (in ppm) is exchanged into the solvent mixture, meaning that the [ ethylpiperidine + citric acid ] complex largely maintains its integrity as a complex throughout the passage of the complex through the (MEK: TEA) solvent mixture. Very little ethylpiperidine was measured in the solvent mixture. The ethylpiperidine is expected to exchange and equilibrate with triethylamine measuring up to about 168,000 ppm.

Example 3

Various complexes [ amine + carboxylic acid containing compounds ] were tested for drying ability and compared to water recovery agents disclosed in Jessop et al, US 2014/0076810.

The wet solvent (TEA: MEK 1:2) prepared according to preparation example 1 was used and its water content was measured using gas chromatography. To 20ml of the wet solvent mixture, 0.2ml of the following drying agent was prepared and added to the solvent mixture, and then the water content of the wet solvent mixture was re-measured using gas chromatography. Will be prepared by adding tea₂CO₃(0.0098mol,1.60g) preparation of TEA: CO₂Was added to distilled water (0.0556,1 g). 9.8mol/kg TEA: CO were formed and used₂A mixture of (a). TEA: formic acid, TEA: citric acid and TEA: glycolic acid was at the same molar concentration of 9.8mol/kg and was used to generate the results shown in table 13 and figure 2.

Table 13:

the results in table 13 and figure 2 show that when compared to the system described in jessap et al, US2014/0076810, triethylamine: citric acid complex and triethylamine: glycolic acid complex provides greater or comparable water removal.

Example 4: measurement of carboxylic acid: the pH of the triethylamine complex to demonstrate the irreversibility of protonation of the carboxylic acid/triethylamine complex.

The irreversibility of the protonation of carboxylic acid in the complex can be shown by comparing the change in pH showing that substantially all free protons have been removed when triethylamine was added-see table 14. The pH data also supports the fact that the amines are predominantly in salt form.

Table 14:

example 5: amino acid + amine combination

A series of amino acids were tested as carboxyl-containing compounds to determine their water absorption capacity. As above, a wet solvent mixture sample was prepared according to the above preparation example 1. Amino acids were purchased from Sigma-Aldrich. Amines + various amino acid combinations were tested for drying ability.

The wet solvent (TEA: MEK 1:2) prepared according to preparation example 1 was used and its water content was measured using gas chromatography. To 20ml of the wet solvent mixture, 0.2ml of the following drying agent was prepared and added to the solvent mixture, and then the water content of the wet solvent mixture was re-measured using gas chromatography. The saturated amino acid solution was mixed with TEA to form TEA: lysine, TEA: glycine, TEA: sarcosine and TEA N, N-dimethylglycine complex and was used to generate the results shown in table 15 and figure 3.

Table 15:

the results in table 15 and figure 3 show triethylamine: the amino acid complex can be used as a drying agent. The composite is capable of drying a wet solvent by efficiently removing water.

Example 6: combinations of different desiccants

A water-absorbing solvent mixture was prepared according to example 1 above. Synthetic brine was added to the water absorbing solvent mixture at a ratio of 20: 1. (20 parts of a water-absorbent solvent mixture: 1 part of brine). The synthetic brine had a composition detailed in table 16.

Table 16: synthetic brine composition

Salt (salt)	g/l
		NaCl	22.8
MgCl₂	0.2348
		KCl	0.1206
CaCl₂	2.4459
		SrCl₂	0.289
BaCl₂	0.3044

After the brine was added to the water-absorbing solvent mixture, the humidity of the solvent mixture was determined to be 8.136% by gas chromatography. A series of desiccants were prepared according to table 17.

Table 17: composition of drying agent

0.2ml of the drying agent prepared according to compositions 1 to 7 was added to 20ml of the wet solvent mixture prepared above. The combination of desiccant and wet solvent mixture was mixed by vortexing, and then the layers were centrifuged. The humidity of the solvent mixture was then measured again by gas chromatography to determine how much water had been removed from the wet solvent mixture by the desiccant. The results are shown in Table 18.

Table 18: viscosity, pH and conductivity of the desiccant

MA ═ methoxyacetic acid

The results from table 18 show that the combination of methoxyacetic acid with tartaric and glycolic acid provides higher osmotic pressure. In contrast, when the desiccant combination comprises lysine, the osmotic pressure of the desiccant is lower. It can also be seen that the viscosity of the desiccant combination is also different. The combination of tartaric acid and citric acid had the highest viscosity.

Example 7: combinations of different desiccants with different solvent drying mixtures

A series of solvent drying mixtures were prepared as shown in table 19. The molar ratio of amine to ketone was 1: 2.

Watch 19

Gas chromatography calibration for the preparation of solvent mixtures. These were prepared using 0.5, 0.49, 0.48, 0.47, 0.46 and 0.45ml of absorbent with 0, 0.01, 0.02, 0.03, 0.04 and 0.05ml of water, respectively. Desiccants were prepared according to table 20.

Table 20: drying agent

The ability of the ketone/amine solvent mixture to absorb water was tested according to the following procedure:

10ml of distilled water are added to 10ml of the ketone/amine mixture in a volume ratio of 1: 1.

1 the resulting mixture was vortexed for 30 seconds and then heated to 50 ℃.

After 21-2 hours, the top layer of the vortexed mixture was analyzed by gas chromatography.

3 the humidity of the mixture of methyl ethyl ketone and ethyl piperidine was measured to be 12.6%.

The moisture content of the 4-cyclohexanone and ethylpiperidine mixture was measured to be 8.3%.

The moisture content of the mixture of 5-methyl ethyl ketone and 4-ethyl morpholine was not measurable, since the mixture did not separate into two phases even when heated to 70 ℃.

The moisture content of the mixture of 6-cyclohexanone and 4-ethylmorpholine was not measurable, since the mixture did not separate into two phases even when heated to 70 ℃.

The ability of the desiccant to release water in the ketone/amine solvent mixture was also tested. The following desiccants were prepared by adding an excess of amine, triethylamine (10 ml for citric acid, glycolic acid, tartaric acid, 5ml for lysine) to the desiccants detailed in table 20. The resulting desiccant, amine combination was then analyzed for pH, viscosity and conductivity at about 19.3 ℃. The results obtained are shown in Table 21.

TABLE 21

It can be observed that viscosity and conductivity are obtained from various combinations. For example, the combination of lysine and TEA produced the highest viscosity, while the combination of glycolic acid and TEA produced the lowest viscosity. The humidity of various solvent mixtures (ketone plus amine) with different desiccant combinations (acid plus amine) was analyzed by GC and the results are shown in table 22 below.

Table 22:

EP ═ ethylpiperidine; CH ═ cyclohexanone; 4-EM is 4-ethyl morpholine NN-DMA-N, N-diethyl methylamine

As can be seen from the results in table 22, the desiccant did not dry each amine: the ketone solution, and notably the solution containing 4-Ethylmorpholine (EM), became more wet after mixing with the desiccant.

Example 8-use of counter-current regeneration to optimize recovery and reduce reverse osmosis requirements using commercial brine samples

A series of mixtures of methyl ethyl ketone and triethylamine (absorbent) was prepared by adding 1mL of commercially available brine to 20mL of methyl ethyl ketone and triethylamine (2% wet MEK to TEA ratio 1: 2). The resulting sample was vortexed for 30 seconds and centrifuged for 1 minute (4000 RPM). The commercially available brine samples had the following compositions summarized in table 23.

Table 23: brine sample 1 composition

Analyte	Concentration (mg/L)
		Alkalinity, bicarbonate as CaCO₃	293.000
Chloride compound	1950.000
		Sulfates of sulfuric acid	5950.000
Barium salt	0.012
		Calcium carbonate	501.000
Magnesium alloy	359.000
		Manganese oxide	0.011
Potassium salt	3.620
		Sodium salt	3100.000
Strontium salt	6.930
		Boron	30.700
Iron	ND
		Total dissolved solids	12300.000

For initial experiment a (standard regeneration) -see fig. 4, the absorbent was regenerated 5 times with pure regenerant (1 mL). Pure regenerant was prepared in a stepwise manner using 1 liter of water, 1322 g of citric acid, 112 g of CuCl2 (dihydrate), 2.22 liters of triethylamine and 0.25 liters of methyl ethyl ketone (2-butanone).

Figure 4 shows the steps in this experiment:

-the diluted regenerant from the 2 nd regeneration is reused for the 1 st regeneration of the next stage.

-the diluted regenerant from the 3 rd regeneration is reused for the 2 nd regeneration of the next stage.

-the diluted regenerant from the 4 th regeneration is reused for the 3 rd regeneration of the subsequent stage.

The 5 th regeneration always used pure regenerant (1mL) -indicated as PP regenerant in figure 4.

-the diluted regenerant from the 5 th regeneration is reused for the 4 th regeneration of the next stage.

The gas chromatographic analysis used in each step of the countercurrent regeneration process was performed using the parameters described below: all GC data were collected on a SHIMADZU Nexis2030 gas chromatograph equipped with an SH-Rxi-624Sil MS column. The GC parameters were set as follows:

GC column method:

rate (. degree.C./min)	Temperature (. degree.C.)	Retention time (min)
				100.0	2.00
10.00	125.0	0.00
			50.00	200.0	3.00

Total program time 9.00 minutes

GC analysis was performed to determine the presence of water in the absorbent and to track the reduction in water content in the absorbent during each stage of absorbent regeneration or drying. The GC results are shown in table 24 below and plotted in fig. 5.

Table 24:

from the above results it can be seen that after the 5 th regeneration, even after re-use of the regenerant in all other stages, the results are quite stable and finally yield a very low water percentage (1.3%).

The inventors of the present application have determined that the water recovery performance of the complex [ amine + carboxylic acid containing compound ] is superior to the water recovery agent described in Jessop et al US2014/0076810 (as shown in example 3). Without wishing to be bound by any theory of mechanism, it is noteworthy that the [ amine + carboxylic acid containing compound ] of the present invention is irreversibly protonated, however jespo et al, US2014/0076810 clearly teach that amines should not be irreversibly protonated. Unlike that described in jessap, which requires the convertibility function of the desiccant, this example shows that convertibility is not a necessary function of the desiccant/regenerant. The inventors of the present application were also able to determine that when the complex [ amine + carboxylic acid containing compound ] is mixed with the solvent mixture [ amine + enolizable carbonyl + water ], the amine of the complex may be the same or different from the amine in the solvent mixture. This is because the complex substantially maintains the integrity of the complex as it passes through the solvent mixture, unlike that described in Jessop. This also means that the complex or salt form of the amine is irreversible by temperature or air stripping.

Example 9

The diluted solvent dried solution is treated with a reverse osmosis membrane. The diluted solvent dried solution (20 liters) contained 20 vol% of the solvent dried composition and 80 vol% of distilled water. By mixing (FeCl)₃) And citric acid in a molar ratio of 1:10, and then diluting the dissolved composition with 80% distilled water to prepare a diluted solvent-dried composition. The 20% (by volume) of the solvent dried composition had a Total Dissolved Solids (TDS) of about 287 grams. Referring to fig. 6, a reverse osmosis system is illustrated comprising the following components:

1 feed tank consisting of a dilute dry solution of solvent

2 flow meter at feed outlet

3 film alignment by manipulation of Pump speed (Dow FILTEC)^TMSeawater reverse osmosis element SW30-2540, effective area 2.8m2) pressure front high pressure pump for closed loop control

4 film Container

5 concentrate stream with restriction valve

6 permeate effluent

7 permeate collection tank

8 control valve

Before using the permeation system shown in fig. 6, the membrane in membrane vessel 4 was conditioned by flowing deionized water through the membrane for 2 hours, then metered in with a dilute solvent dry solution. The diluted solvent dry solution from feed tank 1 is pushed to a high pressure level using high pressure pump 3. The semi-permeable membrane within each membrane container 4 confines a substantial portion of the solvent drying composition. Only the permeate, consisting of low dissolved salts and water, passes through the membrane, while the concentrate stream 5 is fed back to the feed tank 1. The permeate effluent 6 is sent to a permeate collection tank 7. The conductivity of the permeate was measured as an indicator of permeate mass and% rejection.

Measurement conditions were as follows:

maximum operating temperature: 40 deg.C

Maximum membrane operating temperature: 45 deg.C

Pressure (bar): 60

Permeate flow rate and conductivity measurements of the concentrate and permeate were collected at the time intervals mentioned below.

Table 25: feeding: 20% (by volume) diluted solvent dry solution

Time	Flux (LMH)	Retention%
			60 bar	2	3.51	97.33
4	3.58	98.22
				6	3.74	98.32
8	3.56	98.25
				10	3.45	98.13
12	3.25	97.93
				14	2.98	97.71
16	2.88	97.38
				18	2.74	97.04
20	2.68	97.01
				30	1.80	94.30
40	1.75	93.77
				50	1.63	93.68
60	0.65	93.00
				70	0.09	93.03

The results shown in table 25 are also plotted in fig. 8.

Osmolality and concentration measurements: samples of 100. mu.l were taken from the feed and permeate and run through a permeameter. The units were converted from mOsmol/kg to atm, and the salt concentrations in the two streams were calculated and tabulated.

Flux, salt rejection and water recovery were calculated using the following formulas.

Flux measurement:

% salt rejection by conductivity method:

% salt rejection as determined by osmotic pressure:

water recovery% -method 1:

water recovery% -method 2:

a second embodiment of the process of the present invention is shown in figure 7. This embodiment illustrates a process wherein more than one solvent drying composition regeneration step may be used to recover the solvent drying composition complex. As shown in fig. 7, after the industrial process involving the removal of water from the brine feed, the diluted regenerant (dilute solvent dry composition) is recovered from coalescer column COL-102. The diluted solvent dried composition is then subjected to a multi-stage reverse osmosis recovery stage to concentrate (i.e., remove water) the solvent dried composition (regenerant) in a continuous loop operation, thereby recovering the regenerant, which is then sent back to an early stage of the industrial process to facilitate the removal of water from the brine solution. It is to be understood that the coalescer column may be an electrostatic coalescer column, as the solvent drying composition is a good insulator, and electrostatic coalescence may improve the overall performance of the process. FIG. 11 shows a process diagram including an electrostatic coalescer (COL-202).

Example 10 other membranes

Various other membranes were also tested and compared to the membranes used above under the following conditions:

solvent dry composition-diluted solvent dry composition was prepared by dissolving (FeCl3) and citric acid together in a molar ratio of 1:10, and then diluting the dissolved composition with 80% distilled water. The 20% (by volume) of the solvent dried composition had a Total Dissolved Solids (TDS) of about 287 grams.

Example 10.1 Membrane 1 TriSep^TM TS-80

Film specification:

flux (GFD/psi): 220/110

Maximum operating pressure (bar): 41

Maximum operating temperature (. degree. C.): 45

Chlorine resistance: 0.1ppm of

Effective area of the membrane: 0.0142m²

Feed solution: 5% solvent dry solution (by volume).

Film 1 results:

the results of the flux and salt rejection data at various pressures and times are shown in tables 26-28 below.

Table 26: TriSep^TMFlux (LMH) and% salt rejection data for TS-80

Pressure (Bar)	Permeate flux (LMH)	Retention%
			20	11.15	59.09
25	11.59	59.97
			30	14.46	60.47
35	17.71	60.31

Table 27: TriSep^TMTS-80 flux (LMH) at regular intervals at different pressures

Pressure (Bar)	20	25	30	35
					Time (min)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)
5	10.72	11.04	15.41	18.10
					10	11.74	12.51	13.53	16.56
15	10.50	11.55	14.82	18.02
					20	11.38	11.74	14.44	18.54
25	11.10	11.18	14.59	17.32
					30	11.48	11.55	13.96	17.74

Osmolarity data

Table 28: calculated% rejection using osmolarity measurements of the feed and permeate streams

Pressure (Bar)	Osmotic pressure of feed (bar)	Osmotic pressure of permeate (bar)	Reduction of%
				20.00	2.71	1.22	54.79
25.00	2.68	1.16	56.80
				30.00	2.74	1.20	56.21
35.00	2.67	1.24	53.64

Example 10.2 Membrane 2 Dow filmtec Flat Membrane, SW30XLE, PA-TFC, RO

Film specification:

flux (GFD/psi): 23-29/880

Maximum operating pressure (bar): 68.9

Maximum operating temperature (. degree. C.): 45

Chlorine resistance: 0.1ppm of

Effective area of the membrane: 0.0142m²

Feed solution: 5% solvent dry solution (by volume)

Film 2 results:

the results of the flux and salt rejection data at different pressures and times are shown in tables 28-30 below.

Table 29: flux (LMH) and% salt rejection data

Pressure (Bar)	Permeate flux (LMH)	Retention%
			20	7.08	62.48
25	8.82	69.39
			30	11.09	80.25
35	14.98	86.79
			40	18.49	88.57

Table 30: flux (LMH) at regular time intervals at different pressures

Pressure (Bar)	20	25	30	35	40
						Time (min)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)
5	7.10	9.30	11.26	13.98	17.59
						10	7.18	8.45	11.21	16.74	18.34
15	6.87	8.41	11.26	14.90	18.11
						20	7.24	8.54	11.04	14.56	18.97
25	6.84	9.35	11.21	14.73	18.68
						30	7.28	8.86	10.59	14.97	19.27

Osmolarity data

Table 31: the% cut off was calculated using osmotic pressure measurements of the feed and permeate streams

Example 10.3 membrane 3Toray flat sheet membrane-UTC-82V, PA, RO membrane specification:

flux (GFD/psi): 27/798

Maximum operating pressure (bar): 55

Maximum operating temperature (. degree. C.): 25

Effective area of the membrane: 0.0142m²

Feed solution: 5% solvent dry solution (by volume).

Film 3 results:

the results of the flux and salt rejection data at different pressures and times are shown in tables 32-34 below.

Table 32: flux (LMH) and% salt rejection data

Pressure (Bar)	Permeate flux (LMH)	Retention%
			20	23.84	67.11
25	27.73	76.30
			30	29.67	75.17
35	34.30	78.22
			40	38.96	81.86
45	48.59	85.65

Table 33: flux (LMH) at regular time intervals at different pressures

Pressure (Bar)	20	25	30	35	40
						Time (min)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)
5	25.18	27.65	30.36	35.88	38.70
						10	23.41	28.21	29.80	35.95	38.28
15	23.88	27.34	29.87	33.18	38.79
						20	23.73	27.37	30.22	33.33	38.45
25	23.49	27.30	29.54	34.90	38.70
						30	23.32	28.53	28.25	32.54	40.82

Calculating the osmotic pressure:

table 34: the% cut off was calculated using osmotic pressure measurements of the feed and permeate streams

Example 10.4: membrane 4Synder Flat Membrane, NFX, PA-TFC, NF

Film specification:

flux (GFD/psi): 20-25/110

Maximum operating pressure (bar): 30

Maximum operating temperature (. degree. C.): 35

Chlorine resistance (ppm hours): 500

Effective area of the membrane: 0.0142m²

Feeding solution: 5% solvent dry solution (by volume).

Film 4 results:

the results of the flux and salt rejection data at different pressures and times are shown in tables 35-37 below.

Table 35: flux (LMH) and% salt rejection data

Pressure (Bar)	Permeate flux (LMH)	Retention%
			20	40.49	56.55
25	47.45	54.67
			30	59.05	52.42
35	65.62	53.39

Table 36: flux (LMH) at regular time intervals at different pressures

Pressure (Bar)	20	25	30	35
					Time (min)	Flux (LMH)	Flux (LMH)	Flux (LMH)	Flux (LMH)
5	42.81	44.20	55.79	63.78
					10	45.63	45.21	54.29	67.38
15	42.69	49.94	59.36	67.25
					20	35.56	49.94	63.56	60.23
25	38.45	48.21	60.41	68.34
					30	37.77	47.17	60.87	66.76

Calculating the osmotic pressure:

table 37: the% cut off was calculated using osmotic pressure measurements of the feed and permeate streams

Example 10.5Dow filmtec Flat Membrane, SW30HR, PA-TFC, RO Membrane

Film specification:

flux (GFD/psi): 18-24/800

Maximum operating pressure (bar): 68.9

Maximum operating temperature (. degree. C.): 45

Chlorine resistance (ppm hours): 0.1

Effective area of the membrane: 0.0142m²

Feed solution: 5% solvent dry solution (by volume).

As a result:

the results of the flux and salt rejection data at different pressures and times are shown in tables 38-40 below.

Table 38: flux (LMH) and% salt rejection data

Pressure (Bar)	Permeate flux (LMH)	Retention%
			35	7.74	84.78
40	13.18	93.32

Table 39: flux (LMH) at regular time intervals at different pressures

Pressure (Bar)	35	40
			Time (min)	Flux (LMH)	Flux (LMH)
5	7.43	12.08
			10	7.65	20.79
15	7.75	11.58
			20	7.47	11.47
25	7.93	11.65
			30	8.23	11.51

Calculating the osmotic pressure:

table 40: the% cut off was calculated using osmotic pressure measurements of the feed and permeate streams

The results for the various films are shown in figures 9 and 10. As can be seen from fig. 9 and 10, the results of the membranes enable recovery of water from dilute solvent drying solutions using a range of commercially available membranes.

Example 11: it was determined whether different metal salts affected the water capacity of the solvent drying composition.

A series of solvent-dried compositions were prepared with different metal salts and their respective water capacities were determined by gas chromatography. A solvent dried composition was prepared as follows:

1. an amount of the specific metal salt (detailed in table 41 below) was added to a solution of citric acid (6.6gm or 0.340mol) in distilled water (5 ml).

2. The resulting mixture was stirred at 80 ℃ for 20 minutes.

3. An excess of triethylamine was added to the stirred mixture from step 2 to produce a solvent dried composition.

Table 41:

the properties of the solvent dried compositions prepared are detailed in table 42 below:

watch 42

It can be seen that the viscosity of each solvent dried composition varies with the metal salt. The solvent dried composition described above is then reacted with a moisture absorbent as follows:

1. 0.2ml of each of the solvent dry compositions listed in table X was added to 20ml of the moisture absorbent.

2. The resulting mixture was mixed by a vortex mixer for 30 seconds and then separated by a centrifuge.

3. GC analysis of the water remaining in the absorbent after mixing with the solvent dried composition was analyzed and the results are shown in table 43 below.

TABLE 43 Water absorption Capacity of regenerants

As can be seen from the results shown in Table 43, the water-absorbing capacity of each solvent-dried composition does not substantially change depending on the metal salt.

The invention and its embodiments have been described in detail. However, the scope of the present invention is not intended to be limited to the particular embodiments of any process, manufacture, composition of matter, compounds, means, methods, and/or steps described in the specification. Various modifications, substitutions, and variations can be made to the disclosed materials without departing from the spirit and/or essential characteristics of the present invention. Accordingly, one of ordinary skill in the art will readily appreciate from the disclosure that subsequent modifications, substitutions, and/or variations performing substantially the same function or achieving substantially the same result as the embodiments described herein may be utilized according to the related embodiments of the present invention. Thus, the following claims are intended to encompass within their scope modifications, substitutions, and variations to the combinations, kits, compounds, means, methods, and/or steps disclosed herein.

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