US 4,542,010 A · Method and apparatus for producing oxygen and nitrogen and membrane therefor

Abstract

Process and apparatus for the separation and purification of oxygen and nitrogen as well as a novel membrane useful therein are disclosed. The process utilizes novel facilitated transport membranes to selectively transport oxygen from one gaseous stream to another, leaving nitrogen as a byproduct. In the method, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a polar organic membrane which separates a gaseous feed stream such as atmospheric air and a 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 a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. In an alternate mode of operation, 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 at the 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.sub.2 /N.sub.2 selectivity, on the order of 10 to 30, is obtained, as well as exceptionally high oxygen permeability, on the order of 6 to 15.times.10.sup.-8 cm.sup.3 -cm/cm.sup.2 -sec-cmHg, as well as a long membrane life of in excess of 3 months, making the process commercially feasible.

Claims36

Dependent claims

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane and nitrogen from the feed-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base, and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 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.

4 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 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.

4 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane at least approximately 5.degree. C. higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane and nitrogen from the feed-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR22## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR23## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

4 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the temperature on the product-stream side of said membrane at least approximately 5.degree. C. higher than the temperature on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR24## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR25## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

4 more elements

A process for the separation and purification of oxygen and nitrogen comprising:

(a) bringing atmospheric air into contact with a membrane, said membrane separating said atmospheric air into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane and nitrogen from the feed-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture and pentacoordinate oxygen carrier being in the liquid phase when present together, 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 ##STR26## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR27## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety.

2 more elements

A process for the separation and purification of oxygen comprising:

(a) bringing a gaseous oxygen-containing stream into contact with a membrane, said membrane separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane and a product stream on the other side of said membrane,
(b) maintaining the oxygen partial pressure on the product-stream side of said membrane at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane,
(c) collecting oxygen from the product-stream side of said membrane,
(d) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture and a pentacoordinate oxygen carrier, said solvent or solvent mixture and pentacoordinate oxygen carrier being in the liquid phase when present together, 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 ##STR28## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR29## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety.

2 more elements

A membrane useful for the separation of oxygen and nitrogen from atmospheric air comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support, a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR35## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;

X is --O--, --S--, ##STR36## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means and nitrogen from the feed-stream side of said membrane means;
(e) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR40## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR41## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

5 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) means for maintaining the oxygen partial pressure on the product-stream side of said membrane means at least approximately 10 mmHg lower than the oxygen partial pressure on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent, an axial base, an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR42## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR43## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

5 more elements

Apparatus for the separation and purification of oxygen and nitrogen comprising:

(a) membrane means,
(b) means for bringing atmospheric air into contact with said membrane means, said membrane means separating said atmospheric air into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means at least approximately 5.degree. C. higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means and nitrogen from the feed-stream side of said membrane means,
(e) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR44## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR45## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

5 more elements

Apparatus for the separation and purification of oxygen comprising:

(a) membrane means,
(b) means for bringing a gaseous oxygen-containing stream into contact with said membrane means, said membrane means separating said gaseous oxygen-containing stream into a feed stream on one side of said membrane means and a product stream on the other side of said membrane means,
(c) temperature maintenance means for maintaining the temperature on the product-stream side of said membrane means at least approximately 5.degree. C. higher than the temperature on the feed-stream side of said membrane means,
(d) means for collecting oxygen from the product-stream side of said membrane means,
(e) said membrane comprising a membrane support which is a nonporous polymeric film or a microporous polymeric film selected from polysulfones, polyamides, regenerated cellulose, polyhalogenated hydrocarbons, polyesters, polyurethanes, polyolefins, polycarbonates, polysachharides, polyorganosilanes, and polyorganosiloxanes, said membrane support containing a solvent or solvent mixture, an axial base and an oxygen carrier, said solvent or solvent mixture, axial base and oxygen carrier being in the liquid phase when present together, 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 ##STR46## wherein M is cobalt, iron, copper, nickel, manganese, ruthenium or rhodium;
X is --O--, --S--, ##STR47## R is hydrogen, alkyl, aryl, halogen, alkoxy or a nitrogen-containing moiety;
and
Y is halide, nitrate, thiocyanate or cyanide.

5 more elements

Dependencies are inferred from the claim text.

Method and apparatus for producing oxygen and nitrogen and membrane therefor

Life of this patent

Method and apparatus for producing oxygen and nitrogen and membrane therefor

Life of this patent

Abstract

Claims36