Patent DE1035170B successfully refreshed from Google Patents.
US4451270A
Expired / Lapsed
US
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Absorption process for producing oxygen and nitrogen and solution therefor
Assignee: Bend Research Inc
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Filing: 1982-06-30
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Granted: 1984-05-29
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Expires: 2002-06-30
Abstract
Abstract Process for the separation and purification of oxygen and nitrogen is disclosed which utilizes solutions of oxygen carriers to selectively absorb oxygen from a gaseous stream, leaving nitrogen as a byproduct. In the process, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a solvent solution, which absorbs oxygen from an oxygen-containing gaseous feed stream such as atmospheric air and desorbs oxygen to a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form during desorption. In an alternate mode of operation, the carrier solution is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, and at a sufficiently high temperature to keep the carrier in its deoxygenated form during desorption. Under such conditions, exceptionally high oxygen concentrations on the order of 95% to 99% are obtained, as well as a long carrier lifetime in excess of 3 months, making the process commercially feasible.
Inventors
- 👤 Ian C. Roman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 17:10
CPC Classifications
C; C01; C01B; C01B13/00; C01B13/02; C01B13/0229; C01B13/0248; C01B13/0285; B; B01; B01D; B01D53/00; B01D53/14; B01D53/1493; B01D53/34; C01B21/00; C01B21/04; C01B21/0405; C01B21/0411; C01B21/0427; C01B2210/00; C01B2210/0043; C01B2210/0046
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
175 words
A process for the separation and purification of oxygen and nitrogen comprising: (a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having any of the structures ##STR18## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR19## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide; said solution absorbing oxygen from said atmospheric air feed stream; (b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been absorbed; (c) desorbing oxygen from said solution to a gaseous product stream; and (d) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 2
Dependent Claim
175 words
A process for the separation and purification of oxygen and nitrogen comprising: (a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having any of the structures ##STR18## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR19## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide; said solution absorbing oxygen from said atmospheric air feed stream; (b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been absorbed; (c) desorbing oxygen from said solution to a gaseous product stream; and (d) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 3
Dependent Claim
158 words
A process for the separation and purification of oxygen comprising: (a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having any of the structures ##STR20## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR21## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide; said solution absorbing oxygen from said gaseous oxygen-containing feed stream; (b) desorbing oxygen from said solution to a gaseous product stream; and (c) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 4
Dependent Claim
158 words
A process for the separation and purification of oxygen comprising: (a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a metal-containing complex having any of the structures ##STR20## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR21## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide; said solution absorbing oxygen from said gaseous oxygen-containing feed stream; (b) desorbing oxygen from said solution to a gaseous product stream; and (c) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 5
Dependent Claim
38 words
The process of claims 1 or 2 wherein said desorption of oxygen is accomplished by bringing said solution into contact with a gaseous product stream with an oxygen partial pressure substantially less than that of said feed stream.
Claim 6
Dependent Claim
28 words
The process of claims 1 or 2 wherein said desorption of oxygen is accomplished by heating said solution and bringing it into contact with said gaseous product stream.
Claim 7
Dependent Claim
41 words
The process of claims 4 wherein the temperature of the feed stream is between about -50° C. and +95° C. and the temperature of the product stream is at least about 5° C. higher than the temperature of the feed stream.
Claim 8
Dependent Claim
12 words
The process of claim 1 or 2 wherein the metal is cobalt.
Claim 9
Dependent Claim
30 words
The process of claims 3 wherein the oxygen partial pressure of the product stream is at least about 10 mmHg less than the oxygen partial pressure of the feed stream.
Claim 10
Dependent Claim
21 words
The process of claim 7 wherein the oxygen partial pressure of the feed stream is substantially atmospheric or less than atmospheric.
Claim 11
Dependent Claim
35 words
The process of claim 7 wherein the oxygen partial pressure of the feed stream is at least about 10 mmHg higher than atmospheric and the oxygen partial pressure of the product stream is substantially atmospheric.
Claim 12
Dependent Claim
145 words
A process for the separation and purification of oxygen and nitrogen comprising: (a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR22## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR23## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; said solution absorbing oxygen from said atmospheric air feed stream; (b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been absorbed; (c) desorbing oxygen from said solution to a gaseous product stream; and (d) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 13
Dependent Claim
145 words
A process for the separation and purification of oxygen and nitrogen comprising: (a) bringing an atmospheric air feed stream into contact with a solution containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR22## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR23## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; said solution absorbing oxygen from said atmospheric air feed stream; (b) collecting nitrogen from the atmospheric air feed stream after the oxygen has been absorbed; (c) desorbing oxygen from said solution to a gaseous product stream; and (d) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 14
Dependent Claim
107 words
The process of claims 1, 2, or 10 wherein the rates of absorption of oxygen into or desorption of oxygen from said solution are increased either by stirring or otherwise agitating said solution or by increasing the interfacial area between said feed stream and said solution, said interfacial area being increased by any of the following methods: (a) bubbling said feed stream through said solution; (b) spraying said solution through said feed stream; (c) forming a foam of said solution with said feed stream; (d) incorporating said solution into microporous beads; or (e) contacting said solution with said feed stream in a sieve-tray column or packed column.
Claim 15
Dependent Claim
20 words
The process of claims 1, 2 or 10 conducted at a temperature of between about -50° C. and +100° C.
Claim 16
Dependent Claim
63 words
The process of claims 1, 2 or 10 wherein the solvent is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, esters, ethers, other nitrogen-containing liquids, water and mixtures thereof, the axial base is selected from secondary or tertiary nitrogen-atom-containing Lewis bases, imidazoles, ketones, amides, amines, sulfoxides and pyridines, and the oxygen carrier is selected from metal-containing bis(acetylacetone)ethylenediimines, N,N'-bis(salicylidene)ethylenediamines, bis(2-amino-1-benzaldehyde)ethylenediimines, dry-cave compounds, and N,N'-substituted-ethylenediamines.
Claim 17
Dependent Claim
61 words
The process of claim 13 wherein the solvent is selected from at least one of gamma-butyrolactone, dimethylsulfoxide, propylene carbonate, diethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, formamide, gamma-valerolactone, delta-valerolactone, epsilon-caprolactone, tributylphosphate, diglyme and benzonitrile, and the axial base is selected from at least one of 1-methylimidazole, 2-methylimidazole, 1,2,-dimethylimidazole, dimethylsulfoxide, N,N'-diethylethylenediamine, 4-dimethylaminopyridine, 4-aminopyridine, 4,4-bipyridine, 4-methoxypyridine, 4-methylaminopyridine, 3,4-lutidine, 3,5-lutidine, pyridine, 4-methylpyridine, 4-cyanopyridine, pyrazine, 4-pyrrolidinopyridine and piperidine.
Claim 18
Dependent Claim
11 words
The process of claim 14 wherein the oxygen carrier is N,N'-bis(3-methoxysalicylidene)ethylenediaminecobalt(II).
Claim 19
Dependent Claim
11 words
The process of claim 14 wherein the oxygen carrier is N,N'-bis(3-methoxysalicylidene)tetramethylethylenediaminecobalt(II).
Claim 20
Dependent Claim
46 words
The process of claim 14 wherein the oxygen carrier is ##STR24## wherein R 1 is a branched or straight-chain hydrocarbon or hetero-atom-containing bridge; R 2 is hydrogen or methyl; R 3 is methyl or benzyl; and R 4 is alkyl containing 2 to 3 carbon atoms.
Claim 21
Dependent Claim
62 words
The process of claims 1 or 10 wherein desorption is performed in two stages, the first of which results in desorption of a small percentage of the absorbed oxygen and a large percentage of the absorbed nitrogen, and the second stage of which results in desorption of a large percentage of the absorbed oxygen and a small percentage of the absorbed nitrogen.
Claim 22
Dependent Claim
128 words
A process for the separation and purification of oxygen comprising: (a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR25## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR26## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; said solution absorbing oxygen from said atmospheric air feed stream; (b) desorbing oxygen from said solution to a gaseous product stream; and (c) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 23
Dependent Claim
128 words
A process for the separation and purification of oxygen comprising: (a) bringing a gaseous, oxygen-containing feed stream into contact with a solution containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR25## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR26## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; said solution absorbing oxygen from said atmospheric air feed stream; (b) desorbing oxygen from said solution to a gaseous product stream; and (c) collecting oxygen from the product stream after the oxygen has been desorbed.
Claim 24
Dependent Claim
38 words
The process of claims 10 or 19 wherein said desorption of oxygen is accomplished by bringing said solution into contact with a gaseous product stream with an oxygen partial pressure substantially less than that of said feed stream.
Claim 25
Dependent Claim
28 words
The process of claims 10 or 19 wherein said desorption of oxygen is accomplished by heating said solution and bringing it into contact with said gaseous product stream.
Claim 26
Dependent Claim
32 words
The process of claims 10 or 19 wherein the metal is cobalt and the solvent is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, nitrogen-containing liquids, esters, ethers, water and mixtures thereof.
Claim 27
Dependent Claim
11 words
The process of claim 22 wherein the oxygen carrier is N,N'-bis(salicylideneimino)di-n-propylaminecobalt(II).
Claim 28
Dependent Claim
33 words
The process of claims 10 or 19 wherein the oxygen partial pressure of the product stream is at least about 10 mm Hg less than the oxygen partial pressure of the feed stream.
Claim 29
Dependent Claim
23 words
The process of claims 10 or 19 wherein the oxygen partial pressure of the feed stream is substantially atmospheric or less than atmospheric.
Claim 30
Dependent Claim
38 words
The process of claims 10 or 19 wherein the oxygen partial pressure of the feed stream is at least about 10 mm Hg higher than atmospheric and the oxygen partial pressure of the product stream is substantially atmospheric.
Claim 31
Dependent Claim
43 words
The process of claims 10 or 19 wherein the temperature of the feed stream is between about -50° C. and +95° C. and the temperature of the product stream is at least about 5° C. higher than the temperature of the feed stream.
Claim 32
Dependent Claim
114 words
A solution useful for the separation of oxygen and nitrogen from atmospheric air comprising a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a mutual-containing complex having any of the structures ##STR27## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR28## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 33
Dependent Claim
114 words
A solution useful for the separation of oxygen and nitrogen from atmospheric air comprising a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture being capable of dissolving the axial base and the oxygen carrier when they are present together, said axial base being capable of providing a coordinating atom to the oxygen carrier, and said oxygen carrier being a mutual-containing complex having any of the structures ##STR27## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR28## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 34
Dependent Claim
49 words
The solution of claim 28 wherein the solvent is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, ester, ethers, other nitrogen-containing liquids, water and mixtures thereof, and the axial base is selected from Lewis bases containing secondary or tertiary nitrogen atoms, imidazoles, ketones, amides, amines, sulfoxides, pyrazines and pyridines.
Claim 35
Dependent Claim
101 words
The solution of claim 29 wherein the solvent is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, esters, ethers, other nitrogen-containing liquids, water and mixtures thereof, the axial base is selected from at least one of 1-methylimidazole, 2-methylimidazole, 1,2,-dimethylimidazole, dimethylsulfoxide, N,N'-diethylethylenediamine, 4-dimethylaminopyridine, 4-aminopyridine, 4,4-bipyridine, 4-methoxypyridine, 4-methylaminopyridine, 3,4-lutidine, 3,5-lutidine, pyridine, 4-methylpyridine, 4-cyanopyridine, piperidine, 4-pyrrolidinopyridine and pyrazine, and the oxygen carrier is selected from N,N'-bis(3-methoxysalicylidene)ethylenediaminecobalt(II), N,N'-bis(3-methoxysalicylidene)tetramethylethylenediaminecobalt(II), and ##STR29## wherein R 1 is a branched or straight-chain hydrocarbon or hetero-atom-containing bridge; R 2 is hydrogen or methyl; R 3 is methyl or benzyl; and R 4 is alkyl containing 2 to 3 carbon atoms.
Claim 36
Dependent Claim
28 words
The solution of claim 29 wherein the solvent is selected from gamma-butyrolactone and N-methylpyrrolidone or mixtures thereof, the axial base is 4-dimethylaminopyridine and the oxygen carrier is N,N'-bis(3-methoxysalicylidene)tetramethylethylenediaminecobalt(II).
Claim 37
Dependent Claim
32 words
The solution of claim 29 wherein the solvent is selected from gamma-butyrolactone and N-methylpyrrolidone or mixtures thereof, the axial base is selected from 4-aminopyridine and 4-cyanopyridine and the oxygen carrier is N,N'-bis(3-methoxysalicylidene)tetramethylethylenediaminecobalt(II).
Claim 38
Dependent Claim
35 words
The solution of claims 30, 31 or 32 wherein the solvent contains an additive of less than 20 wt%, the additive being selected from the group consisting of water, organic or inorganic acids or bases.
Claim 39
Dependent Claim
84 words
A solution useful for the separation of oxygen and nitrogen from atmospheric air comprising a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR30## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR31## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety.
Claim 40
Dependent Claim
84 words
A solution useful for the separation of oxygen and nitrogen from atmospheric air comprising a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture being capable of dissolving said pentacoordinate oxygen carrier, and said pentacoordinate oxygen carrier being a metal-containing complex having any of the structures ##STR30## wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is --O--, --S--, ##STR31## and R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety.
Claim 41
Dependent Claim
30 words
The solution of claim 34 wherein the metal is cobalt and the solvent is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, nitrogen-containing liquids, esters, ethers, water and mixtures thereof.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-05-29 | 1987-11-28 | 1988-05-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-05-29 | 1991-11-28 | 1992-05-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-05-29 | 1995-11-28 | 1996-05-29 | $7700.00 | Window Closed / Lapsed |