EP0098731A1
Expired / Lapsed
EP
⏱️ 0.0 years remaining
Method for producing oxygen and nitrogen and membrane therefor
Assignee: Bend Research Inc
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Filing: 1983-06-29
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Granted: —
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Expires: 2003-06-29
Abstract
Abstract In a process for the separation and purification of oxygen and nitrogen a membrane containing in solution a metallo--organic oxygen carrier capable of reversibly binding molecular oxygen is utilised to selectively transport oxygen from one gaseous stream (feed stream) to another, leaving nitrogen as a byproduct when the feed stream is atmospheric air. The membrane separates the gaseous feed stream such as atmospheric air and the gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane, while the product stream is maintained at sufficiently low oxygen pressure to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane and/or the feed stream is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane and the product stream is maintained at a sufficiently high temperature to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. Under such conditions, the carrier acts as a shuttle, picking up oxygen atthe feed side of the membrane, diffusing across the membrane as the oxygenated complex, releasing oxygen to the product stream and then diffusing back to the feed side to repeat the process. Exceptionally and unexpectedly high O z /Nz selectivity, of the order 10 to 30, is obtained, as well as exceptionally high oxygen permeability, of the order of 6 to 15 x 10 -8 cm 3 -cm/cm 2 -sec-cmHg, as well as a long membrane life of in excess of 3 months, making the process commercially feasible.
Inventors
- 👤 Ian C. Palmer Products Department Roman
- 👤 Richard W. Baker
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-31 16:45
CPC Classifications
C; C01; C01B; C01B13/00; C01B13/02; C01B21/00; C01B21/04; C01B21/0405; C01B21/0411; C01B21/0427; B; B01; B01D; B01D53/00; B01D53/14; B01D53/1493; B01D53/22; B01D53/228; B01D53/229; B01D61/00; B01D61/38; C01B13/0229; C01B13/0248; C01B13/0251; C01B13/0255; C01B21/0433; C01B21/0438; C01B21/0444; C01B2210/00; C01B2210/0043; C01B2210/0046; Y; Y10; Y10T; Y10T436/00; Y10T436/25; Y10T436/25375; Y10T436/255
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
179 words
A process for the production of oxygen comprising contacting an oxygen-containing gas with a membrane containing a metallo-organic compound having oxygen-complexing capability so as to cause absorption of oxygen from said oxygen-containing gas, said membrane separating said oxygen-containing gas into a feed stream on one side of said membrane and.a product stream on the other side of said membrane, and desorbing and collecting oxygen from said product stream side of said membrane characterized in that said metallo-organic compound is present in a membrane support in a solution containing a solvent or solvent mixture and an axial base, said solvent or solvent mixture being capable of dissolving the axial base and the metallo-organic compound when they are present together, said axial base being capable of providing a coordinating atom to the metallo-organic compound, and said metallo-organic compound having any of the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -0-, -S-, R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 2
Dependent Claim
179 words
A process for the production of oxygen comprising contacting an oxygen-containing gas with a membrane containing a metallo-organic compound having oxygen-complexing capability so as to cause absorption of oxygen from said oxygen-containing gas, said membrane separating said oxygen-containing gas into a feed stream on one side of said membrane and.a product stream on the other side of said membrane, and desorbing and collecting oxygen from said product stream side of said membrane characterized in that said metallo-organic compound is present in a membrane support in a solution containing a solvent or solvent mixture and an axial base, said solvent or solvent mixture being capable of dissolving the axial base and the metallo-organic compound when they are present together, said axial base being capable of providing a coordinating atom to the metallo-organic compound, and said metallo-organic compound having any of the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -0-, -S-, R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 3
Dependent Claim
33 words
The process of claim 1 wherein said desorbing is accomplished by maintaining the temperature on the product-stream side of said membrane substantially higher than the temperature on the feed-stream side of said membrane.
Claim 4
Dependent Claim
37 words
The process of claim 1 wherein said desorbing is accomplished by maintaining the oxygen partial pressure on the product-stream side of said membrane substantially lower than the oxygen partial pressure on the feed-stream side of said membrane.
Claim 5
Dependent Claim
12 words
The process of claim 1 wherein said oxygen-containing gas is atmospheric air.
Claim 6
Dependent Claim
17 words
The process of claim 4 further including collecting nitrogen from the feed stream side of said membrane.
Claim 7
Dependent Claim
19 words
The process of claims 1, 2, 3, 4 or 5 wherein said membrane support is a microporous polymeric film.
Claim 8
Dependent Claim
47 words
The process of claim 6 wherein the microporous polymeric film membrane support is selected from polysulfones, polyamides, cellulose esters and other cellulose derivatives, polyhalogenated hydrocarbons such as polytetrafluoroethylenes, polyvinylhalides, polyvinyli- denehalides, polyesters, nylons, polyurethanes, polyolefins: such as polypropylene, polycarbonates, polysaccharides, polyorganosilanes, and polyorganosiloxanes such as silicone rubber.
Claim 9
Dependent Claim
19 words
The process of claims 1, 2, 3, 4 or 5 wherein said membrane support is a nonporous polymeric film.
Claim 10
Dependent Claim
33 words
The process of claim 3 wherein the oxygen partial pressure on the product-stream side of said membrane is at least about 10 mmHg less than the oxygen partial pressure on the feed-stream side.
Claim 11
Dependent Claim
52 words
The process of claim 3 wherein the oxygen partial pressure on the feed-stream side of said membrane is substantially atmospheric or less than atmospheric and the oxygen partial pressure on the product-stream side of said membrane is at least about 10 mmHg less than the oxygen partial pressure on the feed-stream side.
Claim 12
Dependent Claim
39 words
.11. The process of claim 3 wherein the oxygen partial pressure on the feed-stream side of said membrane is at least about 10 mmHg higher than atmospheric and the oxygen partial pressure on the product-stream side is substantially atmospheric.
Claim 13
Dependent Claim
15 words
The process of claim 1 conducted at a temperature of between about -50°C and +100°C.
Claim 14
Dependent Claim
46 words
The process of claim 2 wherein the temperature on the feed-stream side of said membrane is between -50°C and +95°C and the temperature on the product-stream side of the membrane is. at least about 5°C higher than the temperature on the feed-stream side of the membrane.
Claim 15
Dependent Claim
10 words
The process of claim 1 wherein the metal is cobalt.
Claim 16
Dependent Claim
65 words
The process of claims 1, 2, 3, 4 or 5 wherein the solvent or solvent mixture is selected from lactones, sulfoxides, nitriles, amines, amides, esters, ethers, and other nitrogen-containing liquids, the axial base is selected from secondary or tertiary nitrogen-atom-containing Lewis bases, imidazoles, ketones, amides, amines, sulfoxides, pyridines and pyrazines, and the oxygen carrier is selected from metal-containing bis(acetylacetone)ethylenediimines, N,N'-bis (salicyclidene)ethylenediimines, dry-cave compounds, and N,N'-substituted-ethylenediamines.
Claim 17
Dependent Claim
66 words
The process of claim 14 wherein the solvent or solvent mixture is selected from at least one of gamma-butyrolactone, dimethylsulfoxide, propylene carbonate, diethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, gamma-valerolactone, delta-valerolactone, e p silon-caprolactone, tributylphosphate, dimethylformamide, 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 N-methylpyrazinimum halides.
Claim 18
Dependent Claim
13 words
The process of claim 16 wherein the metallo-organic compound is N,N'-bis(salicyli- deneimino)di-n-propylamine cobalt(II).
Claim 19
Dependent Claim
13 words
The process of claim 16 wherein the metallo-organic compound is N,N'-bis(3-methoxy- salicylidene) ethylenediaminecobalt(II).
Claim 20
Dependent Claim
12 words
The process of claim 16 wherein the metallo-organic compound is N,N'-bis(3-methoxysalicylidene)tetra- methylethylenediaminecobalt(II).
Claim 21
Dependent Claim
45 words
The process of claim 16 wherein the metallo-organic compound is 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 22
Dependent Claim
169 words
A process for the production of oxygen comprising contacting an oxygen-containing gas with a membrane containing a metallo-organic compound having oxygen-complexing capability so as to cause absorption of the oxygen from said oxygen containing gas, said membrane separating said oxygen-containing gas into a feed stream on one side of said membrane and a product stream on the other side of said membrane, and desorbing and collecting oxygen from said product stream side of said membrane characterized in that said metallo-organic compound is present in a membrane support in a solution containing a solvent or solvent mixture selected from at least one of gamma-butyrolactone, dimethylsulfoxide, propylene carbonate, diethylsulfoxide, N-methypyrrolidone, dimethylacetamide, dimethylformamide, formamide, gamma- caprolactone, tributylphosphate, diglyme and benzonitrile, and said metallo-organic compound is a pentacoordinate metal-containing complex having any of the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -O-, -S-, R is hydrogen, alkyL, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 23
Dependent Claim
169 words
A process for the production of oxygen comprising contacting an oxygen-containing gas with a membrane containing a metallo-organic compound having oxygen-complexing capability so as to cause absorption of the oxygen from said oxygen containing gas, said membrane separating said oxygen-containing gas into a feed stream on one side of said membrane and a product stream on the other side of said membrane, and desorbing and collecting oxygen from said product stream side of said membrane characterized in that said metallo-organic compound is present in a membrane support in a solution containing a solvent or solvent mixture selected from at least one of gamma-butyrolactone, dimethylsulfoxide, propylene carbonate, diethylsulfoxide, N-methypyrrolidone, dimethylacetamide, dimethylformamide, formamide, gamma- caprolactone, tributylphosphate, diglyme and benzonitrile, and said metallo-organic compound is a pentacoordinate metal-containing complex having any of the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -O-, -S-, R is hydrogen, alkyL, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 24
Dependent Claim
164 words
A. membrane useful for the production of oxygen comprising a membrane support, a solvent or solvent mixture, an axial base and a metallo-organic compound having oxygen-complexing ability characterized in that the membrane support is a microporous poly- meric film selected from polysulfones, polyamides, cellulose esters and other cellulose derivatives, polyhalogenated hydrocarbons such as polytetrafluoroethylenes, polyvinyl halides, polyvinylidene halides, polyesters, nylons, polyurethanes, polyolefins such as polypropylene, polycarbonate, polysaccharides, polyorganasilanes, and polyorganosiloxanes such as silicone rubber; the solvent or solvent mixture is selected from lactones, lactams, sulfoxides, nitriles, amines, amides, esters, ethers and other nitrogen-containing liquids; the axial base is selected from Lewis base; containing secondary or tertiary nitrogen atoms, imidazoles, ketones, amides, amines, sulfoxides, pyrazines and pyridines, and the metallo-organ.ic compound is a metal-containing complex having the structure wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -0-, -S-, R is hydrogen, alkyl, aryl,halagen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 25
Dependent Claim
164 words
A. membrane useful for the production of oxygen comprising a membrane support, a solvent or solvent mixture, an axial base and a metallo-organic compound having oxygen-complexing ability characterized in that the membrane support is a microporous poly- meric film selected from polysulfones, polyamides, cellulose esters and other cellulose derivatives, polyhalogenated hydrocarbons such as polytetrafluoroethylenes, polyvinyl halides, polyvinylidene halides, polyesters, nylons, polyurethanes, polyolefins such as polypropylene, polycarbonate, polysaccharides, polyorganasilanes, and polyorganosiloxanes such as silicone rubber; the solvent or solvent mixture is selected from lactones, lactams, sulfoxides, nitriles, amines, amides, esters, ethers and other nitrogen-containing liquids; the axial base is selected from Lewis base; containing secondary or tertiary nitrogen atoms, imidazoles, ketones, amides, amines, sulfoxides, pyrazines and pyridines, and the metallo-organ.ic compound is a metal-containing complex having the structure wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -0-, -S-, R is hydrogen, alkyl, aryl,halagen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 26
Dependent Claim
110 words
The membrane of claim 22 wherein the solvent is selected from at least one of gamma-butyrolactone, dimethylsulfoxide, propylene carbonate, diethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, gamma-valerolactone, delta-valerolactone, dimethylformamide, formamide, epsilon-caprolactone, tributylphosphate, diglyme and benzonitrile, 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 N-methylpyrazinimum halides, and the metallo-organic compound is selected from N,N'-bis(salicylideneimino)di-n-propylamine cobalt(II), N,N'-bis(3-methoxysalicylidene) ethylene- diaminecobalt(II),N,N'-bis(3-methoxysalicylidene)tetra- methylethylenediaminecobalt(II) and wherein R l 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 27
Dependent Claim
29 words
The membrane of claim 22 wherein the solvent is selected from qamma-butyrolactone and N-methylpyrrolidone and mixtures thereof, the axial basee is 4-dimethylaminopyridine and the metallo-organic compound is N,N'-bis(3-methoxysalicylidene)tetramethylethyl- enediaminecobalt(II).
Claim 28
Dependent Claim
12 words
The membrane of claim 22 wherein the metallo-organic compound is N,N'-bis(3-methoxysalicylidene) tetramethylethylenediaminecobalt(II).
Claim 29
Dependent Claim
33 words
The membrane of claim 22 wherein the solvent is selected from gamma-butyrolactone and N-methylpyrrolidone and mixtures thereof, the axial base is 4 - aminopyridine and 4-cyanopyridine and the metallo-organic compound is N,N'-bis(3-methoxysalicylidene) tetramethylethylenediaminecobalt(II).
Claim 30
Dependent Claim
37 words
The membrane of claim 22 wherein the solvent or solvent mixture contains an additive selected from the group consisting of less than or equal to 20% by weight water and an organic or inorganic acid or base.
Claim 31
Dependent Claim
105 words
A membrane useful for the.production of oxygen comprising a membrane support, a solvent or solvent mixture, and a metallo-organic compound having oxygen-complexing capability characterized in that said solvent or solvent mixture is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, nitrogen-containing liquids, esters, ethers, water and mixtures thereof, and said metallo-organic compound is a pentacoordinate metal-containing complex having the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -O-, -S-, -P- or -N-; R R R R R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
Claim 32
Dependent Claim
105 words
A membrane useful for the.production of oxygen comprising a membrane support, a solvent or solvent mixture, and a metallo-organic compound having oxygen-complexing capability characterized in that said solvent or solvent mixture is selected from lactones, lactams, sulfoxides, nitriles, amides, amines, nitrogen-containing liquids, esters, ethers, water and mixtures thereof, and said metallo-organic compound is a pentacoordinate metal-containing complex having the structures wherein M is a metal selected from cobalt, iron, copper, nickel, manganese, ruthenium or rhodium; X is -O-, -S-, -P- or -N-; R R R R R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety; and Y is halide, nitrate, thiocyanate or cyanide.
References Cited (Backward Citations)
US4032617A
Cited
US4011306A
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