US4955993A — Semi-permeable hollow fiber gas separation membra…

Claim 1

Independent Claim 79 words

A semi-permeable hollow fiber membrane comprising a hydrophobic polymeric material, which possesses an equilibrium water content at about 25° C. of less than about 1 weight percent, said hollow fiber membrane having a thin non-external discriminating region and at least one generally porous region, wherein the discriminating region functions to selectively separate at least one gaseous component from other gaseous components in a gas mixture, wherein the discriminating region and porous region(s) are comprised of the same polymeric material.

Claim 2

Dependent Claim 79 words

A semi-permeable hollow fiber membrane comprising a hydrophobic polymeric material, which possesses an equilibrium water content at about 25° C. of less than about 1 weight percent, said hollow fiber membrane having a thin non-external discriminating region and at least one generally porous region, wherein the discriminating region functions to selectively separate at least one gaseous component from other gaseous components in a gas mixture, wherein the discriminating region and porous region(s) are comprised of the same polymeric material.

Claim 3

Dependent Claim 42 words

The hollow fiber membrane of claim 1 comprising a thin discriminating region at or near the internal surface of the hollow fiber membrane and a generally porous region extending from the discriminating region to the external surface of the hollow fiber membrane.

Claim 4

Dependent Claim 28 words

The hollow fiber membrane of claim 2 wherein the discriminating region at or near the internal surface of the hollow fiber membrane is formed using a core gas.

Claim 5

Dependent Claim 32 words

The hollow fiber membrane of claim 3 wherein the hydrophobic polymeric material comprises a polycarbonate, polyester, polyestercarbonate, polysulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, polystyrene, polyetheretherketone, polyetherketone, polyetherimide or polyamideimide.

Claim 6

Dependent Claim 19 words

The hollow fiber membrane of claim 4 wherein the hydrophobic polymeric material comprises a polycarbonate, polyphenylene oxide, or polysulfone.

Claim 7

Dependent Claim 15 words

The hollow fiber membrane of claim 5 wherein the hydrophobic polymeric material comprises a polycarbonate.

Claim 8

Dependent Claim 31 words

The hollow fiber membrane of claim 6 wherein the polycarbonate is derived from bisphenols wherein at least about 25 weight percent of the bisphenol moieties in the polycarbonate backbone are tetra-substituted.

Claim 9

Dependent Claim 83 words

The hollow fiber membrane of claim 7 wherein the polycarbonate corresponds to the formula: ##STR6## wherein R is --CO--, --S--, --SO 2 --, --O--, a C 1-6 divalent hydrocarbon radical, a C 1-6 divalent fluorocarbon radical, or an inertly substituted C 1-6 divalent hydrocarbon radical; X at each occurrence is independently hydrogen, chlorine, bromine, fluorine, or C 1-4 alkyl; and n is a positive real number, such that the polycarbonate possesses sufficient molecular weight to prepare a hollow fiber membrane with suitable characteristics.

Claim 10

Dependent Claim 33 words

The hollow fiber membrane of claim 8 wherein the polycarbonate is derived from bisphenols wherein at least about 50 weight percent of the bisphenol moieties in the polycarbonate backbone are bromine or chlorine.

Claim 11

Dependent Claim 28 words

The hollow fiber membrane of claim 9 wherein the oxygen flux through the hollow fiber membrane is at least about 1×10 -6 cm 3 (STP)/(cm 2 s cmHg).

Claim 12

Dependent Claim 23 words

The hollow fiber membrane of claim 10 wherein the gas separation factor for oxygen/nitrogen at about 25° C. is at least about 6.

Claim 13

Dependent Claim 28 words

The hollow fiber membrane of claim 9 wherein the hydrogen flux through the hollow fiber membrane is at least about 1×10 -5 cm 3 (STP)/(cm 2 s cmHg).

Claim 14

Dependent Claim 24 words

The hollow fiber membrane of claim 12 wherein the gas separation factor for hydrogen/light hydrocarbons at about 25° C. is at least about 25.

Claim 15

Dependent Claim 14 words

The hollow fiber membrane of claim 9 wherein the polycarbonate is tetrabromobisphenol A polycarbonate.

Claim 16

Dependent Claim 51 words

The hollow fiber membrane of claim 1 comprising a generally porous region at or near the external surface of the hollow fiber membrane, a generally porous region at or near the internal surface of the hollow fiber membrane, and a thin discriminating region generally situated between the two porous surface regions.

Claim 17

Dependent Claim 32 words

The hollow fiber membrane of claim 15 wherein the hydrophobic polymeric material comprises a polycarbonate, polyester, polyestercarbonate, polysulfone polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, polystyrene, polyetheretherketone, polyetherketone, polyetherimide, or polyamideimide.

Claim 18

Dependent Claim 19 words

The hollow fiber membrane of claim 16 wherein the hydrophobic polymeric material comprises a polycarbonate, polyphenylene oxide, or polysulfone.

Claim 19

Dependent Claim 15 words

The hollow fiber membrane of claim 17 wherein the hydrophobic polymeric material comprises a polycarbonate.

Claim 20

Dependent Claim 31 words

The hollow fiber membrane of claim 18 wherein the polycarbonate is derived from bisphenols wherein at least about 25 weight percent of the bisphenol moieties in the polycarbonate backbone are tetra-substituted.

Claim 21

Dependent Claim 83 words

The hollow fiber membrane of claim 19 wherein the polycarbonate corresponds to the formula: ##STR7## wherein R is --CO--, --S--, --SO 2 --, --O--, a C 1-6 divalent hydrocarbon radical, a C 1-6 divalent fluorocarbon radical, or an inertly substituted C 1-6 divalent hydrocarbon radical; X at each occurrence is independently hydrogen, chlorine, bromine, fluorine, or C 1-4 alkyl; and n is a positive real number, such that the polycarbonate possesses sufficient molecular weight to prepare a hollow fiber membrane with suitable characteristics.

Claim 22

Dependent Claim 33 words

The hollow fiber membrane of claim 20 wherein the polycarbonate is derived from bisphenols wherein at least about 50 weight percent of the bisphenol moieties in the polycarbonate backbone are bromine or chlorine.

Claim 23

Dependent Claim 28 words

The hollow fiber membrane of claim 21 wherein the oxygen flux through the hollow fiber membrane is at least about 1×10 -6 cm 3 (STP)/(cm 2 s cmHg).

Claim 24

Dependent Claim 23 words

The hollow fiber membrane of claim 22 wherein the gas separation factor for oxygen/nitrogen at about 25° C. is at least about 6.

Claim 25

Dependent Claim 28 words

The hollow fiber membrane of claim 21 wherein the hydrogen flux through the hollow fiber membrane is at least about 1×10 -5 cm 3 (STP)/(cm 2 s cmHg).

Claim 26

Dependent Claim 24 words

The hollow fiber membrane of claim 24 wherein the gas separation factor for hydrogen/light hydrocarbons at about 25° C. is at least about 25.

Claim 27

Dependent Claim 14 words

The hollow fiber membrane of claim 21 wherein the polycarbonate is tetrabromobisphenol A polycarbonate.

Claim 28

Dependent Claim 28 words

The hollow fiber membrane of claim 1 wherein within the porous region(s), a substantial majority of the pores are between about 10 to about 10,000 Angstroms in size.

Claim 29

Independent Claim 212 words

A method for separating at least one gaseous component from other gaseous components of a gas mixture comprising: (A) contacting the internal surface of a semi-permeable hollow fiber membrane with a feed gas mixture under pressure, wherein the hollow fiber membrane separates a higher pressure region inside the hollow fiber membrane from a lower pressure region outside of the hollow fiber membrane; (B) maintaining a pressure differential across the hollow fiber membrane under conditions such that at least one gaseous component in the feed gas mixture selectively permeates through the hollow fiber membrane from the inside higher pressure region to the outside lower pressure region; (C) removing from the outside lower pressure region of the hollow fiber membrane permeated gas which is enriched in at least one gaseous component; and (D) removing from the inside higher pressure region of the hollow fiber membrane nonpermeated gas which is depleted in at least one gaseous component; wherein the hollow fiber membrane comprises a hydrophobic polymeric material, which possesses an equilibrium water content at about 25° C. of less than about 1 weight percent, said hollow fiber membrane possessing a thin non-external discriminating region and at least one generally porous region, wherein the discriminating region and porous region(s) are comprised of the same polymeric material.

Claim 30

Independent Claim 212 words

A method for separating at least one gaseous component from other gaseous components of a gas mixture comprising: (A) contacting the internal surface of a semi-permeable hollow fiber membrane with a feed gas mixture under pressure, wherein the hollow fiber membrane separates a higher pressure region inside the hollow fiber membrane from a lower pressure region outside of the hollow fiber membrane; (B) maintaining a pressure differential across the hollow fiber membrane under conditions such that at least one gaseous component in the feed gas mixture selectively permeates through the hollow fiber membrane from the inside higher pressure region to the outside lower pressure region; (C) removing from the outside lower pressure region of the hollow fiber membrane permeated gas which is enriched in at least one gaseous component; and (D) removing from the inside higher pressure region of the hollow fiber membrane nonpermeated gas which is depleted in at least one gaseous component; wherein the hollow fiber membrane comprises a hydrophobic polymeric material, which possesses an equilibrium water content at about 25° C. of less than about 1 weight percent, said hollow fiber membrane possessing a thin non-external discriminating region and at least one generally porous region, wherein the discriminating region and porous region(s) are comprised of the same polymeric material.

Claim 31

Dependent Claim 45 words

The method of claim 28 wherein the hollow fiber membrane comprises a thin discriminating region at or near the internal surface of the hollow fiber membrane and a generally porous region extending from the discriminating region to the external surface of the hollow fiber membrane.

Claim 32

Dependent Claim 27 words

The method of claim 29 wherein the thin discriminating region at or near the internal surface of the hollow fiber membrane is formed using a core gas.

Claim 33

Dependent Claim 30 words

The method of claim 30 wherein the hydrophobic polymeric material comprises a polycarbonate, polyester, polyestercarbonate, polysulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, polyetheretherketone, polyetherketone, polystyrene, polyetherimide, or polyamideimide.

Claim 34

Dependent Claim 17 words

The method of claim 31 wherein the hydrophobic polymeric material comprises a polycarbonate, polypheylene oxide, or polysulfone.

Claim 35

Dependent Claim 13 words

The method of claim 32 wherein the hydrophobic polymeric material comprises a polycarbonate.

Claim 36

Dependent Claim 29 words

The method of claim 33 wherein the polycarbonate is derived from bisphenols wherein at least about 25 weight percent of the bisphenol moieties in the polycarbonate backbone are tetra-substituted.

Claim 37

Dependent Claim 81 words

The method of claim 34 wherein the polycarbonate corresponds to the formula: ##STR8## wherein R is --CO--, --S--, --SO 2 --, --O--, a C 1-6 divalent hydrocarbon radical, a C 1-6 divalent fluorocarbon radical, or an inertly substituted C 1-6 divalent hydrocarbon radical; X at each occurrence is independently hydrogen, chlorine, bromine, fluorine, or C 1-4 alkyl; and n is a positive real number, such that the polycarbonate possesses sufficient molecular weight to prepare a hollow fiber membrane with suitable characteristics.

Claim 38

Dependent Claim 31 words

The method of claim 35 wherein the polycarbonate is derived from bisphenols wherein at least about 50 weight percent of the bisphenol moieties in the polycarbonate backbone are bromine or chlorine.

Claim 39

Dependent Claim 39 words

The method of claim 36 wherein the feed gas mixture contains at least one of the gases selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, water vapor, ammonia, hydrogen sulfide, or light hydrocarbons.

Claim 40

Dependent Claim 26 words

The method of claim 37 wherein the oxygen flux through the hollow fiber membrane is at least about 1×10 -6 cm 3 (STP)/(cm 2 s cmHg).

Claim 41

Dependent Claim 21 words

The method of claim 38 wherein the gas separation factor for oxygen/nitrogen at about 25° C. is at least about 6.

Claim 42

Dependent Claim 26 words

The method of claim 37 wherein the hydrogen flux through the hollow fiber membrane is at least about 1×10 -5 cm 3 (STP)/(cm 2 s cmHg).

Claim 43

Dependent Claim 22 words

The method of claim 40 wherein the gas separation factor for hydrogen/light hydrocarbons at about 25° C. is at least about 25.

Claim 44

Dependent Claim 17 words

The method of claim 37 wherein the feed pressure is between about 35 and about 2000 psig.

Claim 45

Dependent Claim 16 words

The method of claim 42 wherein the temperature is between about 0° and about 150° C.

Claim 46

Dependent Claim 12 words

The method of claim 37 wherein the polycarbonate is tetrabromobisphenol A polycarbonate.

Claim 47

Dependent Claim 54 words

The method of claim 28 wherein the hollow fiber membrane comprises a generally porous region at or near the external surface of the hollow fiber membrane, a generally porous region at or near the internal surface of the hollow fiber membrane, and a thin discriminating region generally situated between the two porous surface regions.

Claim 48

Dependent Claim 31 words

The method of claim 45 wherein the hydrophobic polymeric material comprises a polycarbonate, polyester, polyestercarbonate, polysulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, or polystyrene, polyetheretherketone, polyetherketone, polyetherimide, or polyamideimide.

Claim 49

Dependent Claim 17 words

The method of claim 46 wherein the hydrophobic polymeric material comprises a polycarbonate, polyphenylene oxide, or polysulfone.

Claim 50

Dependent Claim 13 words

The method of claim 47 wherein the hydrophobic polymeric material comprises a polycarbonate.

Claim 51

Dependent Claim 29 words

The method of claim 48 wherein the polycarbonate is derived from bisphenols wherein at least about 25 weight percent of the bisphenol moieties in the polycarbonate backbone are tetra-substituted.

Claim 52

Dependent Claim 81 words

The method of claim 49 wherein the polycarbonate corresponds to the formula: ##STR9## wherein R is --CO--, --S--, --SO 2 --, --O--, a C 1-6 divalent hydrocarbon radical, a C 1-6 divalent fluorocarbon radical, or an inertly substituted C 1-6 divalent hydrocarbon radical; X at each occurrence is independently hydrogen, chlorine, bromine, fluorine, or C 1-4 alkyl; and n is a positive real number, such that the polycarbonate possesses sufficient molecular weight to prepare a hollow fiber membrane with suitable characteristics.

Claim 53

Dependent Claim 31 words

The method of claim 50 wherein the polycarbonate is derived from bisphenols wherein at least about 50 weight percent of the bisphenol moieties in the polycarbonate backbone are bromine or chlorine.

Claim 54

Dependent Claim 39 words

The method of claim 51 wherein the feed gas mixture contains at least one of the gases selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, water vapor, ammonia, hydrogen sulfide, or light hydrocarbons.

Claim 55

Dependent Claim 26 words

The method of claim 52 wherein the oxygen flux through the hollow fiber membrane is at least about 1×10 -6 cm 3 (STP)/(cm 2 s cmHg).

Claim 56

Dependent Claim 21 words

The method of claim 53 wherein the gas separation factor for oxygen/nitrogen at about 25° C. is at least about 6.

Claim 57

Dependent Claim 26 words

The method of claim 52 wherein the hydrogen flux through the hollow fiber membrane is at least about 1×10 -5 cm 3 (STP)/(cm 2 s cmHg).

Claim 58

Dependent Claim 22 words

The method of claim 55 wherein the gas separation factor for hydrogen/light hydrocarbons at about 25° C. is at least about 25.

Claim 59

Dependent Claim 17 words

The method of claim 52 wherein the feed pressure is between about 35 and about 2000 psig.

Claim 60

Dependent Claim 16 words

The method of claim 57 wherein the temperature is between about 0° and about 150° C.

Claim 61

Dependent Claim 12 words

The method of claim 52 wherein the polycarbonate is tetrabromobisphenol A polycarbonate.

Claim 62

Dependent Claim 25 words

The method of claim 29 wherein within the porous region(s), a substantial majority of the pores are about 10 to about 10,000 Angstroms in size.

Claim 63

Dependent Claim 291 words

A process for preparing a semi-permeable hollow fiber membrane comprising: (A) forming a mixture comprising: (i) a hydrophobic polymeric material, other than tetrahalogenated polycarbonate, possessing an equilibrium water content at about 25° C. of less than about 1 weight percent and which is capable of being formed into a membrane, (ii) at least one solvent for the polymeric material, and (iii) at least one non-solvent for the polymeric material; wherein the mixture comprises less than about 1 weight percent water; (B) heating the mixture to a temperature at which the mixture forms a homogeneous fluid and possesses sufficient viscosity at extrusion conditions to permit extrusion of at least one hollow fiber membrane; (C) extruding the mixture into a hollow fiber membrane using a core gas; (D) passing the hollow fiber membrane through at least gaseous quench zone under conditions such that the mixture cools and begins to phase separate while minimizing the loss of solvent(s) and non-solvent(s) from the external surface of the hollow fiber membrane; (E) passing the hollow fiber membrane through at least one liquid quench zone comprising a liquid in which the polymeric material possesses low solubility, wherein a portion of the solvent(s) and non-solvent(s) is removed from the hollow fiber membrane; and (F) simultaneously or consecutively passing the hollow fiber membrane through at least one liquid leach zone comprising a liquid in which the polymeric material possesses low solubility, wherein a significant portion of the remaining solvent(s) and non-solvent(s) are removed from the hollow fiber membrane; wherein the hollow fiber membrane so formed possesses a thin non-external discriminating region and at least one generally porous region, wherein the discriminating layer functions to selectively separate at least one gaseous component from other gaseous components in a gas mixture.

Claim 64

Dependent Claim 291 words

A process for preparing a semi-permeable hollow fiber membrane comprising: (A) forming a mixture comprising: (i) a hydrophobic polymeric material, other than tetrahalogenated polycarbonate, possessing an equilibrium water content at about 25° C. of less than about 1 weight percent and which is capable of being formed into a membrane, (ii) at least one solvent for the polymeric material, and (iii) at least one non-solvent for the polymeric material; wherein the mixture comprises less than about 1 weight percent water; (B) heating the mixture to a temperature at which the mixture forms a homogeneous fluid and possesses sufficient viscosity at extrusion conditions to permit extrusion of at least one hollow fiber membrane; (C) extruding the mixture into a hollow fiber membrane using a core gas; (D) passing the hollow fiber membrane through at least gaseous quench zone under conditions such that the mixture cools and begins to phase separate while minimizing the loss of solvent(s) and non-solvent(s) from the external surface of the hollow fiber membrane; (E) passing the hollow fiber membrane through at least one liquid quench zone comprising a liquid in which the polymeric material possesses low solubility, wherein a portion of the solvent(s) and non-solvent(s) is removed from the hollow fiber membrane; and (F) simultaneously or consecutively passing the hollow fiber membrane through at least one liquid leach zone comprising a liquid in which the polymeric material possesses low solubility, wherein a significant portion of the remaining solvent(s) and non-solvent(s) are removed from the hollow fiber membrane; wherein the hollow fiber membrane so formed possesses a thin non-external discriminating region and at least one generally porous region, wherein the discriminating layer functions to selectively separate at least one gaseous component from other gaseous components in a gas mixture.

Claim 65

Dependent Claim 36 words

The process of claim 61 wherein the temperature, relative humidity, and residence time in the gaseous quench zone are such that water diffuses substantially into the hollow fiber membrane before passing into the liquid quench zone.

Claim 66

Dependent Claim 47 words

The process of claim 62 wherein the hollow fiber membrane so formed possesses a thin discriminating region at or near the internal surface of the hollow fiber membrane and a generally porous region extending from the discriminating region to the external surface of the hollow fiber membrane.

Claim 67

Dependent Claim 17 words

The process of claim 63 wherein the extrusion temperature is between about 50° and about 280° C.

Claim 68

Dependent Claim 12 words

The process of claim 64 wherein the gaseous quench zone comprises air.

Claim 69

Dependent Claim 23 words

The process of claim 65 wherein the gaseous quench zone temperature is in the range of from about 0° to about 120° C.

Claim 70

Dependent Claim 28 words

The process of claim 66 wherein the gaseous quench zone relative humidity at about 24° C. is in the range of from about 20 to about 80 percent.

Claim 71

Dependent Claim 22 words

The process of claim 67 wherein the residence time within the gaseous quench zone is between about 0.05 and about 10 seconds.

Claim 72

Dependent Claim 21 words

The process of claim 68 wherein the liquid quench zone(s) comprise lower alcohols, water, fluorocarbons, lower aliphatic hydrocarbons, or mixtures thereof.

Claim 73

Dependent Claim 89 words

The process of claim 69 wherein the hollow fiber membrane is passed through at least one liquid quench zone and at least one liquid leach zone wherein the hollow fiber membrane is passed through the liquid quench zone(s) under conditions such that the mixture undergoes at least partial phase separation in said quench zone(s), and the hollow fiber membrane is then passed through the liquid leach zone(s) under conditions such that the solvent(s) and non-solvent(s) are substantially removed from the hollow fiber membrane and phase separation is substantially completed.

Claim 74

Dependent Claim 23 words

The process of claim 70 wherein the liquid quench zone(s) temperature is in the range of from about 0° to about 30° C.

Claim 75

Dependent Claim 22 words

The process of claim 71 wherein the residence time within the liquid quench zone(s) is between about 0.05 and about 600 seconds.

Claim 76

Dependent Claim 12 words

The process of claim 72 wherein the liquid quench zone(s) comprise water.

Claim 77

Dependent Claim 21 words

The process of claim 72 wherein the liquid leach zone(s) comprise lower alcohols, water, fluorocarbons, lower aliphatic hydrocarbons, or mixtures thereof.

Claim 78

Dependent Claim 23 words

The process of claim 74 wherein the liquid leach zone(s) temperature is in the range of from about 50° to about 120° C.

Claim 79

Dependent Claim 21 words

The process of claim 75 wherein residence time within the liquid leach zone(s) is between about 0.5 and about 240 minutes.

Claim 80

Dependent Claim 12 words

The process of claim 76 wherein the liquid leach zone(s) comprise water.

Claim 81

Dependent Claim 31 words

The process of claim 76 wherein the hydrophobic polymeric material comprises a non-tetrahalogenated polycarbonate, polyester, polyestercarbonate, polysulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, polystyrene, polyetheretherketone, polyetherketone, polyetherimide, or polyamideimide.

Claim 82

Dependent Claim 18 words

The process of claim 78 wherein the hydrophobic polymeric material comprises a non-tetrahalogenated polycarbonate, polysulfone, or polyphenylene oxide.

Claim 83

Dependent Claim 299 words

The process of claim 78 wherein the solvent comprises a glycol ether corresponding to the formula R 3 O--(CH 2 CH 2 ) r --R 3 wherein R 3 is independently in each occurrence methyl or ethyl, and r is an integer of between about 1 and about 20; a dialkyl ketone wherein the alkyl groups independently are methyl or ethyl; morpholine substituted on the nitrogen atom with an alkyl, formyl, or alkanoyl moiety: pyrrolidinone or N-C 1-4 alkyl, N-C 5-6 cycloalkyl, or N-C 6-10 aryl or alkaryl substituted pyrrolidinone: C 1-4 alkoxycarbonyl, formyl, nitro, or halo substituted benzene: tetrahydrofuran; dimethyl formamide; cyclohexanone; N,N-dimethyl acetamide; acetophenone; methylene chloride; sulfolane; cyclohexyl acetate; 1,1,3,3-tetramethylurea; isophorone; caprolactone; 1-formylpiperidine; methyl salicylate; hexymethylphosphoramide; phenyl ether; or bromoanaphthalene; or mixtures thereof; and wherein the non-solvent comprises a glycol or glycol ether corresponding to the formula R 4 --(CH 2 CH 2 ) q --R 4 wherein R 4 is independently in each occurrence hydrogen or C 1-4 alkyl, and q is an integer of about 1 to about 250; an ester corresponding to the formula R 5 COOR 6 wherein R 5 is hydrogen or C 1-19 alkyl, and R 6 is C 1-10 alkyl; a C 1-10 alkanol; cyclohexane, unsubstituted or substituted with an alkyl, cycloalkyl, or perfluoroalkyl moiety; a C 5-20 alkane; a dialkyl ketone wherein at least one of the alkyl moieties is C 3 or greater; an amide corresponding to the formula R 7 CONHR 8 wherein R 7 is hydrogen or C 1-10 alkyl, and R 8 is C 1-10 alkyl; an acetyl or C 1-10 alkyl nitrile; acetone; a C 1-10 alkyl aldehyde; a trialkyl amine; nitromethane; trialkyl ortho-formate; diacetone alcohol; dimethyl malonate; decahydronaphthalene; tetrahydronaphthalene; malononitrile; dicyclohexyl: ethylene carbonate; sulfolane; alkyl or cycloalkyl substituted benzene; water; or mixtures thereof.

Claim 84

Dependent Claim 64 words

The process of claim 80 wherein the solvent comprises N-methyl-2-pyrrolidinone, ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, acetophenone, methylene chloride, cyclohexanone, or mixtures thereof; and the non-solvent comprises water, diisopropyl ketone, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, hexadecane, diethylene glycol, triethylene glycol, polyethylene glycol with a molecular weight of up to about 1450, 2-ethoxyethanol, carbon tetrachloride, dodecane, or mixtures thereof.

Claim 85

Dependent Claim 77 words

The process of claim 81 wherein the solvent/non-solvent pair is N-methyl-2-pyrrolidinone and triethylene glycol, N-methyl-2-pyrrolidinone and polyethylene glycol with a molecular weight of up to about 1450, ethylene glycol dimethyl ether and water, tetrahydrofuran and water, ethylene glycol dimethyl ether and diisopropyl ketone, tetrahydrofuran and diisopropyl ketone, diethylene glycol dimethyl ether and water, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, acetophenone and diethylene glycol dibutyl ether, methylene chloride and carbon tetrachloride, or acetophenone and hexadecane.

Claim 86

Dependent Claim 28 words

The process of claim 82 wherein the solvent/non-solvent pair is N-methyl-2-pyrrolidinone and triethylene glycol, or N-methyl-2-pyrrolidinone and polyethylene glycol with a molecular weight of up to about 400.

Claim 87

Dependent Claim 55 words

The process of claim 62 wherein the hollow fiber membrane so formed possesses a generally porous region at or near the external surface of the hollow fiber membrane, a generally porous region at or near the internal surface of the hollow fiber membrane, and a discriminating region generally situated between the two porous surface regions.

Claim 88

Dependent Claim 17 words

The process of claim 84 wherein the extrusion temperature is between about 50° and about 280° C.

Claim 89

Dependent Claim 12 words

The process of claim 85 wherein the gaseous quench zone comprises air.

Claim 90

Dependent Claim 23 words

The process of claim 86 wherein the gaseous quench zone temperature is in the range of from about 0° to about 120° C.

Claim 91

Dependent Claim 28 words

The process of claim 87 wherein the gaseous quench zone relative humidity at about 24° C. is in the range of from about 20 to about 80 percent.

Claim 92

Dependent Claim 22 words

The process of claim 88 wherein the residence time within the gaseous quench zone is between about 0.05 and about 10 seconds.

Claim 93

Dependent Claim 21 words

The process of claim 89 wherein the liquid quench zone(s) comprise lower alcohols, water, fluorocarbons, lower aliphatic hydrocarbons, or mixtures thereof.

Claim 94

Dependent Claim 89 words

The process of claim 90 wherein the hollow fiber membrane is passed through at least one liquid quench zone and at least one liquid leach zone wherein the hollow fiber membrane is passed through the liquid quench zone(s) under conditions such that the mixture undergoes at least partial phase separation in said quench zone(s), and the hollow fiber membrane is then passed through the liquid leach zone(s) under conditions such that the solvent(s) and non-solvent(s) are substantially removed from the hollow fiber membrane and phase separation is substantially completed.

Claim 95

Dependent Claim 23 words

The process of claim 91 wherein the liquid quench zone(s) temperature is in the range of from about 0° to about 30° C.

Claim 96

Dependent Claim 22 words

The process of claim 92 wherein the residence time within the liquid quench zone(s) is between about 0.05 and about 600 seconds.

Claim 97

Dependent Claim 12 words

The process of claim 93 wherein the liquid quench zone(s) comprise water.

Claim 98

Dependent Claim 21 words

The process of claim 93 wherein the liquid leach zone(s) comprise lower alcohols, water, fluorocarbons, lower aliphatic hydrocarbons, or mixtures thereof.

Claim 99

Dependent Claim 23 words

The process of claim 95 wherein the liquid leach zone(s) temperature is in the range of from about 50° to about 120° C.

Claim 100

Dependent Claim 21 words

The process of claim 96 wherein residence time within the liquid leach zone(s) is between about 0.5 and about 240 minutes.

Claim 101

Dependent Claim 12 words

The process of claim 96 wherein the liquid leach zone(s) comprise water.

Claim 102

Dependent Claim 31 words

The process of claim 96 wherein the hydrophobic polymeric material comprises a non-tetrahalogenated polycarbonate, polyester, polyestercarbonate, polysulfone, polyolefin, polyphenylene oxide, polyphenylene sulfide, polyether, fluorinated polyimide, polystyrene, polyetherketone, polyetheretherketone, polyetherimide, or polyamideimide.

Claim 103

Dependent Claim 18 words

The process of claim 99 wherein the hydrophobic polymeric material comprises a non-tetrahalogenated polycarbonate, polyphenylene oxide, or polysulfone.

Claim 104

Dependent Claim 299 words

The process of claim 99 wherein the solvent comprises a glycol ether corresponding to the formula R 3 O--(CH 2 CH 2 ) r --R 3 wherein R 3 is independently in each occurrence methyl or ethyl, and r is an integer of between about 1 and about 20; a dialkyl ketone wherein the alkyl groups independently are methyl or ethyl; morpholine substituted on the nitrogen atom with an alkyl, formyl, or alkanoyl moiety; pyrrolidinone or N-C 1-4 alkyl, N-C 5-6 cycloalkyl, or N-C 6-10 aryl or alkaryl substituted pyrrolidinone; C 1-4 alkoxycarbonyl, formyl, nitro, or halo substituted benzene; tetrahydrofuran; dimethyl formamide; cyclohexanone; N,N-dimethyl acetamide; acetophenone; methylene chloride; sulfolane; cyclohexyl acetate; 1,1,3,3-tetramethylurea; isophorone; caprolactone; 1-formylpiperidine; methyl salicylate; hexymethylphosphoramide; phenyl ether; or bromoanaphthalene; or mixtures thereof; and wherein the non-solvent comprises a glycol or glycol ether corresponding to the formula R 4 --(CH 2 CH 2 ) q --R 4 wherein R 4 is independently in each occurrence hydrogen or C 1-4 alkyl, and q is an integer of about 1 to about 250; an ester corresponding to the formula R 5 COOR 6 wherein R 5 is hydrogen or C 1-19 alkyl, and R 6 is C 1-10 alkyl; a C 1-10 alkanol; cyclohexane, unsubstituted or substituted with an alkyl, cycloalkyl, or perfluoroalkyl moiety; a C 5-20 alkane; a dialkyl ketone wherein at least one of the alkyl moieties is C 3 or greater: an amide corresponding to the formula R 7 CONHR 8 wherein R 7 is hydrogen or C 1-10 alkyl, and R 8 is C 1-10 alkyl; an acetyl or C 1-10 alkyl nitrile; acetone: a C 1-10 alkyl aldehyde; a trialkyl amine; nitromethane: trialkyl ortho-formate: diacetone alcohol; dimethyl malonate; decahydronaphthalene; tetrahydronaphthalene; malononitrile; dicyclohexyl; ethylene carbonate; sulfolane; alkyl or cycloalkyl substituted benzene; water; or mixtures thereof.

Claim 105

Dependent Claim 64 words

The process of claim 101 wherein the solvent comprises N-methyl-2-pyrrolidinone, ethylene glycol dimethyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, acetophenone, methylene chloride, cyclohexanone, or mixtures thereof; and the non-solvent comprises water, diisopropyl ketone, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, hexadecane, diethylene glycol, triethylene glycol, polyethylene glycol with a molecular weight of up to about 1450, 2-ethoxyethanol, carbon tetrachloride, dodecane, or mixtures thereof.

Claim 106

Dependent Claim 77 words

The process of claim 102 wherein the solvent/non-solvent pair is N-methyl-2-pyrrolidinone and triethylene glycol, N-methyl-2-pyrrolidinone and polyethylene glycol with a molecular weight of up to about 1450, ethylene glycol dimethyl ether and water, tetrahydrofuran and water, ethylene glycol dimethyl ether and diisopropyl ketone, tetrahydrofuran and diisopropyl ketone, diethylene glycol dimethyl ether and water, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, acetophenone and diethylene glycol dibutyl ether, methylene chloride and carbon tetrachloride, or acetophenone and hexadecane.

Claim 107

Dependent Claim 28 words

The process of claim 103 wherein the solvent/non-solvent pair is N-methyl-2-pyrrolidinone and triethylene glycol, or N-methyl-2-pyrrolidinone and polyethylene glycol with a molecular weight of up to about 400.

Claim 108

Dependent Claim 17 words

The process of claim 63 which comprises the further step of: (G) drying the hollow fiber membrane.

Claim 109

Dependent Claim 25 words

The process of claim 63 wherein within the region(s) a substantial majority of the pores are between about 10 to about 10,000 Angstroms in size.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-09-10	1994-03-12	1994-09-11	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-09-10	1998-03-12	1998-09-11	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-09-10	2002-03-12	2002-09-11	$7700.00	Window Closed / Lapsed

Semi-permeable hollow fiber gas separation membranes possessing a non-external discriminating region

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