Claims
- 1. A process for the preparation of a carboxylic acid salt by dehydrogenation of a primary alcohol, the process comprising:
contacting an alkaline mixture comprising said primary alcohol with a dehydrogenation catalyst, said catalyst comprising a copper-containing active phase at the surface thereof and a supporting structure that is resistant to deformation under the conditions of the dehydrogenation reaction.
- 2. A process as set forth in claim 1 wherein said supporting structure comprises a non-brittle material that has a yield strength of at least about 100 MPa.
- 3. A process as set forth in claim 2 wherein said supporting structure comprises a metal sponge containing at least about 15% by weight non-copper metal and at least about 10% by weight copper.
- 4. A process as set forth in claim 2 wherein the active phase at the surface of said catalyst comprises at least about 50% by weight copper.
- 5. A process as set forth in claim 4 wherein said active phase contains less than about 1% by weight of a metal oxide other than cuprous oxide.
- 6. A process as set forth in claim 4 wherein said active phase contains less than about 1% by weight of cuprous oxide.
- 7. A process as set forth in claim 4 wherein said active phase contains at least about 1% by weight of a supplemental metal selected from the group consisting of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel, bismuth, tin, antimony, lead, and germanium, and mixtures thereof.
- 8. A process as set forth in claim 2 wherein said supporting structure comprises a metal containing at least about 10% by weight non-copper metal.
- 9. A process as set forth in claim 8 wherein said catalyst comprises a metal sponge.
- 10. A process according to claim 8, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 11. A process according to claim 8, wherein said metal support comprises at least about 10% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 12. A process as set forth in claim 8 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 13. A process as set forth in claim 8 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 14. A process as set forth in claim 8 wherein said catalyst comprises a particulate catalyst, the particles of which have the structure of claim 2.
- 15. A process according to claim 8, wherein said primary alcohol comprises a compound corresponding to the formula:
- 16. A process according to claim 8, wherein said carboxylic acid salt comprises an alkali metal salt of (a) iminodiacetic acid, (b) glycine, or (c) an N-alkyl-glycine.
- 17. A process according to claim 8, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 18. A process according to claim 17, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 19. A process as set forth in claim 2 wherein the catalyst comprises a metal sponge and said supporting structure comprises at least about 10% by weight non-copper metal and from about 2% to about 30% by weight copper.
- 20. A process as set forth in claim 19 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 21. A process as set forth in claim 19 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 22. A process as set forth in claim 19 wherein said catalyst comprises a particulate catalyst, the particles of which have the structure of claim 2.
- 23. A process according to claim 19, wherein said primary alcohol comprises a compound corresponding to the formula:
- 24. A process according to claim 23, wherein R1 and R2 are independently hydrogen; —(CH2)x—(CH3)m, x being an integer ranging from 0 to about 19, m being either 1 or 2;—(CH2)y—OH, y being an integer ranging from 1 to about 20; (CH2)z—COOH, z being an integer ranging from 1 to about 19; or phosphonomethyl.
- 25. A process according to claim 24, wherein n is 2; R1 is hydrogen; and R2 is hydrogen, hydrocarbyl, or substituted hydrocarbyl.
- 26. A process according to claim 25, wherein R2 is hydrocarbyl.
- 27. A process according to claim 26, wherein R2 is —(CH2)x—(CH3)m.
- 28. A process according to claim 27, wherein R2 is —CH3.
- 29. A process according to claim 23, wherein said primary alcohol is selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
- 30. A process according to claim 23, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 31. A process according to claim 30, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 32. A process as set forth in claim 19, wherein the supporting structure of said metal sponge comprises at least about 50% by weight non-copper metal.
- 33. A process according to claim 32, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 34. A process according to claim 33, wherein said supporting structure comprises at least about 50% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 35. A process according to claim 34, wherein said supporting structure comprises at least about 50% nickel.
- 36. A process according to claim 34, wherein said supporting structure comprises at least about 50% cobalt.
- 37. A process as set forth in claim 2 wherein said catalyst has a substantially homogeneous structure containing at least about 15% by weight non-copper metal and at least about 10% by weight copper.
- 38. A process as set forth in claim 2 wherein said catalyst comprises a monophasic alloy containing at least about 15% by weight non-copper metal and at least about 10% by weight copper.
- 39. A process as set forth in claim 2 wherein said catalyst has a heterogeneous structure comprising a support comprising a metal containing at least about 10% by weight non-copper metal and a surface active phase containing at least about 50% by weight copper.
- 40. A process as set forth in claim 2 wherein said supporting structure comprises a metal sponge containing at least about 15% by weight non-copper metal and at least about 10% by weight copper.
- 41. A process as set forth in claim 2 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 42. A process as set forth in claim 2 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 43. A process as set forth in claim 42 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
- 44. A process as set forth in claim 42 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge support.
- 45. A process as set forth in claim 2 wherein said catalyst comprises a particulate catalyst.
- 46. A process according to claim 2, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 47. A process according to claim 46, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 48. A process according to claim 2, wherein said process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
- 49. A process for the preparation of a carboxylic acid salt by dehydrogenation of a primary alcohol, the process comprising:
contacting an alkaline mixture comprising said primary alcohol with a dehydrogenation catalyst, said catalyst comprising a metal sponge comprising a copper-containing active phase at the surface thereof and a supporting structure that contains at least about 10% by weight non-copper metal.
- 50. A process as set forth in claim 49 wherein the copper content of said surface active phase exceeds the copper content of said supporting structure.
- 51. A process as set forth in claim 50 wherein said surface active phase contains at least about 50% by weight copper and said supporting structure contains at least about 15% by weight non-copper metal.
- 52. A process as set forth in claim 50 wherein said supporting structure contains between about 2% and about 30% by weight copper.
- 53. A process according to claim 52, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 54. A process according to claim 52, wherein said metal support comprises at least about 10% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 55. A process as set forth in claim 52 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 56. A process as set forth in claim 52 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 57. A process as set forth in claim 56 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
- 58. A process as set forth in claim 56 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge support.
- 59. A process as set forth in claim 52 wherein said catalyst comprises a particulate catalyst.
- 60. A process according to claim 52, wherein said primary alcohol comprises a compound corresponding to the formula:
- 61. A process according to claim 60, wherein R1 and R2 are independently hydrogen; —(CH2)x—(CH3)m, x being an integer ranging from 0 to about 19, m being either 1 or 2;—(CH2)y—OH, y being an integer ranging from 1 to about 20; (CH2)z—COOH, z being an integer ranging from 1 to about 19; or phosphonomethyl.
- 62. A process according to claim 61, wherein n is 2; R1 is hydrogen; and R2 is hydrogen, hydrocarbyl, or substituted hydrocarbyl.
- 63. A process according to claim 62, wherein R2 is hydrocarbyl.
- 64. A process according to claim 63, wherein R2 is —(CH2)x—(CH3)m.
- 65. A process according to claim 64, wherein R2 is —CH3.
- 66. A process according to claim 65, wherein said primary alcohol is selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
- 67. A process as set forth in claim 50 wherein said catalyst has a substantially homogeneous structure containing at least about 10% by weight non-copper metal and at least about 15% by weight copper.
- 68. A process as set forth in claim 50 wherein said catalyst comprises a monophasic alloy containing at least about 10% by weight non-copper metal and at least about 15% by weight copper.
- 69. A process as set forth in claim 50 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 70. A process as set forth in claim 50 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 71. A process as set forth in claim 70 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
- 72. A process as set forth in claim 70 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge support.
- 73. A process as set forth in claim 50 wherein said catalyst comprises a particulate catalyst.
- 74. A process according to claim 50, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 75. A process according to claim 74, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 76. A process according to claim 50, wherein said process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
- 77. A process for making a salt of disodium iminodiacetic acid, the process comprising contacting a dehydrogenation catalyst with an aqueous mixture comprising an alkali metal hydroxide and diethanolamine, wherein:
said catalyst comprises a copper-containing active phase at the surface of a metal support, said metal support comprising at least about 50% by weight of a non-copper metal selected from the group consisting of nickel, cobalt, iron and tin, or a combination thereof.
- 78. A process as set forth in claim 77 wherein said metal support is a metal sponge support.
- 79. A process as set forth in claim 77, wherein said active phase at the surface of said metal support comprises at least about 50% by weight copper.
- 80. A process according to claim 77, wherein said metal support comprises at least about 50% by weight nickel.
- 81. A process according to claim 77, wherein said metal support comprises at least about 50% by weight cobalt.
- 82. A process according to claim 77, wherein said primary alcohol comprises a compound corresponding to the formula:
- 83. A process according to claim 77, wherein said carboxylic acid salt comprises an alkali metal salt of (a) iminodiacetic acid, (b) glycine, or (c) an N-alkyl-glycine.
- 84. A process according to claim 77, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 85. A process according to claim 84, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 86. A process according to claim 77, wherein said process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
- 87. A process according to claim 77, wherein said metal sponge support further comprises about 2% to about 30% by weight copper metal.
- 88. A process according to claim 87, wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 to about 0.5 grams of copper per gram of said metal sponge support.
- 89. A process according to claim 87, wherein said metal sponge support has deposited thereon a copper-containing outer stratum.
- 90. A process according to claim 87, wherein said process further comprises phosphonomethylating said disodium iminodiacetic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 91. A process according to claim 90, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 92. A process according to claim 87, wherein said process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
- 93. A process for making a salt of a carboxylic acid, the process comprising contacting a catalyst with an alkaline mixture comprising a primary alcohol, wherein:
said catalyst is characterized as being formed by a process comprising depositing a copper-containing active phase on the surface of a metal sponge support, said metal sponge support comprising at least about 60% by weight of a non-copper metal and about 2% to about 30% by weight copper.
- 94. A process according to claim 93, wherein said catalyst comprises a surface stratum comprising said copper-containing active phase, said surface stratum containing between about 0.005 to about 0.5 grams of copper per gram of said metal sponge support.
- 95. A process as set forth in claim 93 wherein said catalyst has a copper-containing outer stratum deposited thereon.
- 96. A process according to claim 95, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 97. A process according to claim 95, wherein said copper-containing outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
- 98. A process according to claim 93, wherein said primary alcohol comprises a compound corresponding to the formula:
- 99. A process according to claim 93, wherein said carboxylic acid salt comprises an alkali metal salt of (a) iminodiacetic acid, (b) glycine, or (c) an N-alkyl-glycine.
- 100. A process according to claim 93, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
- 101. A process according to claim 100, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
- 102. A catalyst composition comprising a metal sponge comprising a copper-containing active phase at the surface thereof and a supporting structure that contains at least about 10% by weight non-copper metal.
- 103. A catalyst as set forth in claim 102 wherein said supporting structure comprises a non-brittle material that has a yield strength of at least about 100 MPa.
- 104. A catalyst as set forth in claim 103 wherein the active phase at the surface of said catalyst comprises at least about 50% by weight copper.
- 105. A catalyst according to claim 103, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 106. A catalyst according to claim 103, wherein said metal support comprises at least about 10% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 107. A catalyst as set forth in claim 103 wherein said supporting structure comprises at least about 10% by weight non-copper metal and from about 2% to about 30% by weight copper.
- 108. A catalyst as set forth in claim 107, wherein the supporting structure of said metal sponge comprises at least about 50% by weight non-copper metal.
- 109. A catalyst according to claim 108, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 110. A catalyst according to claim 108, wherein said supporting structure comprises at least about 50% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 111. A catalyst according to claim 110, wherein said supporting structure comprises at least about 50% nickel.
- 112. A catalyst according to claim 110, wherein said supporting structure comprises at least about 50% cobalt.
- 113. A catalyst as set forth in claim 103 wherein said catalyst has a substantially homogeneous structure containing at least about 10% by weight non-copper metal and at least about 15% by weight copper.
- 114. A catalyst as set forth in claim 103 wherein said catalyst comprises a monophasic alloy containing at least about 10% by weight non-copper metal and at least about 8% by weight copper.
- 115. A catalyst as set forth in claim 103 wherein said catalyst has a heterogeneous structure comprising a support comprising a metal containing at least about 10% by weight non-copper metal and a surface active phase containing at least about 50% by weight copper.
- 116. A catalyst as set forth in claim 103 wherein said supporting structure comprises a metal sponge containing at least about 15% by weight non-copper metal and at least about 10% by weight copper.
- 117. A catalyst as set forth in claim 103 wherein said catalyst comprises a surface stratum comprising said active phase, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
- 118. A catalyst as set forth in claim 103 wherein said catalyst comprises a metal sponge support having deposited thereon a copper-containing outer stratum.
- 119. A catalyst as set forth in claim 118 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
- 120. A catalyst as set forth in claim 118 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge support.
- 121. A catalyst as set forth in claim 103 wherein said catalyst comprises a particulate catalyst.
- 122. A catalyst composition comprising a metal sponge support, wherein said catalyst is characterized as being produced by a process comprising depositing a copper-containing active phase on the surface of a metal sponge support containing at least about 60% by weight non-copper metal and from about 2% to about 30% by weight copper metal.
- 123. A catalyst according to claim 122, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 124. A catalyst according to claim 123, wherein said copper-containing active phase is deposited onto the surface of said metal sponge support by a method comprising an electrochemical displacement reaction of the metal of the support with copper ions.
- 125. A catalyst according to claim 122, wherein said metal sponge support contains at least about 60% by weight of a non-copper metal selected from the group consisting of nickel, zinc, tin, cobalt and iron, or a combination thereof.
- 126. A catalyst according to claim 122, wherein said metal sponge support contains at least about 60% by weight nickel.
- 127. A process for making an oxidation catalyst, the process comprising depositing a copper-containing active phase onto the surface of a metal support comprising at least about 10% of a non-copper metal and from about 2% to about 30% copper.
- 128. A process according to claim 127, wherein said process further comprises contacting said metal support with a reducing agent before depositing said copper-containing active phase.
- 129. A process according to claim 127, wherein said non-copper metal comprises metal having a reduction potential which is less than about +343 mVolts vs. NHE.
- 130. A process according to claim 127, wherein said copper-containing active phase is deposited onto the surface of said metal support by a method comprising an electrochemical displacement reaction of the metal of the support with copper ions.
- 131. A process according to claim 130, wherein said process comprises conducting said electrochemical displacement reaction under basic conditions.
- 132. A process according to claim 131, wherein said process further comprises conducting said electrochemical displacement reaction under acidic conditions.
- 133. A process according to claim 127, wherein said copper-containing active phase is deposited onto the surface of said metal support by a method comprising electroless plating.
- 134. A process according to claim 133, wherein said copper-containing active phase is deposited onto said surface of said metal support in the presence of a chelating agent.
- 135. A process according to claim 134, wherein said chelating agent is an amine.
- 136. A process according to claim 134, wherein said chelating agent is nitrilotriacetic acid or a salt thereof.
- 137. A process according to claim 134, wherein said chelating agent is ethylenediaminetetraacetic acid or a salt thereof.
- 138. A process according to claim 133 wherein said copper-containing active phase is deposited onto said surface of said metal support in the presence of a non-aqueous solvent.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of pending U.S. patent application Ser. No. 09/547,373 (filed Apr. 11, 2000). The entire text of U.S. patent application Ser. No. 09/547,373 is hereby incorporated herein by reference.
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
09547373 |
Apr 2000 |
US |
Child |
09832541 |
Apr 2001 |
US |