Asymmetric gas separation membranes

• US 4,472,175 A
• Filed: 06/30/1983
• Issued: 09/18/1984
• Est. Priority Date: 06/30/1983
• Status: Expired due to Term

• Current Assignee: Permea Incorporated (Linde Plc)
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Zampini, Anthony, Malon, Raymond F.
• Primary Examiner(s): Spitzer, Robert H.
• Application Number:
  US06/509,626
• Time in Patent Office: 446 Days
• Field of Search: 55/16, 55/158, 210/500.2
• US Class Current: 95/51
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation

Abstract

Asymmetric gas separation membranes of materials having selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture, exhibit significantly improved permeation selectivities for the at least one gas when the asymmetric membrane is contacted on one or both surfaces with an effective amount of a Br nsted-Lowry acid. The improved asymmetric gas separation membranes, process for producing the improved membrane, and processes utilizing such membranes for selectively separating at least one gas from a gaseous mixture by permeation are disclosed.

Claims

1. An asymmetric gas separation membrane exhibiting substantially improved gas separation selectivity comprising, a preformed asymmetric separation membrane of material having selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture which has been contacted on one or both surfaces with an effective amount of a Br nsted-Lowry acid, wherein with respect to the at least one gas, the acid contacted membrane exhibits a separation factor significantly greater than the separation factor exhibited by the membrane before acid contact.

2. The improved asymmetric gas separation membrane of claim 1 wherein the Br nsted-Lowry acid is a hydrohaloacid.

3. The improved asymmetric gas separation membrane of claim 1 wherein the separation factor for the one gas of the gas mixture is increased by at least 100%.

4. The improved asymmetric gas separation membrane of claim 2 wherein the improvement in separation factor for the one gas of the gas mixture is accomplished with a reduction in permeability of not more than about 50%.

5. The improved asymmetric gas separation membrane of claim 1 wherein the material of the asymmetric membrane is comprised of a material selected from the group consisting of polymers and copolymers and substituted polymers of polyethers, polysulfones, polyaryleneoxides, polyethersulfones, cellulose esters, and copolymers of styrene and acrylonitrile.

6. The improved asymmetric gas separation membrane of claim 1 wherein the at least one gas is selected from the group consisting of carbon monoxide, nitrogen, oxygen, helium, methane, ethane, hydrogen, and carbon dioxide.

7. The improved asymmetric gas separation membrane according to claim 1 wherein the separation factor for the separation of hydrogen from a gaseous mixture comprised of hydrocarbons of 1 to about 5 carbon atoms is improved by at least about 200%.

8. The improved asymmetric gas separation membrane according to claim 7 wherein the separation factor for the separation of hydrogen from a gaseous mixture comprised of hydrocarbons of 1 to about 5 carbon atoms is greater than the intrinsic separation factor of the membrane material in dense film form.

9. The improved asymmetric gas separation membrane according to claim 1 wherein the improved acid contacted asymmetric membrane exhibits a separation factor for the separation of CO₂ from methane of at least about 200% over the non-acid treated asymmetric membrane.

10. The improved asymmetric gas separation membrane according to claim 1 wherein the Br nsted-Lowry acid is mixed with a Lewis acid.

11. A process for improving the selectivity of an asymmetric gas separation membrane of material exhibiting selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture comprising:

contacting the preformed asymmetric gas separation membrane with an effective amount of a Br nsted-Lowry acid which is volatile at ambient conditions, the acid being contacted with one or both surfaces of the membrane for a period sufficient with respect to the at least one gas to improve the separation factor significantly greater than the separation factor exhibited by the membrane before acid treatment; and

removing the residual acid through vaporization.

12. The process according to claim 11 wherein the Br nsted-Lowry acid is a hydrohaloacid and the contact time for the acid with the preformed asymmetric gas separation membrane varies from about 15 seconds to about 30 minutes.

13. The process according to claim 11 wherein the Br nsted-Lowry acid is in a vapor state when contacted with the preformed asymmetric gas separation membrane.

14. The process according to claim 11 wherein the Br nsted-Lowry acid is in a liquid state when contacted with the preformed asymmetric gas separation membrane.

15. The process according to claim 11 wherein the improved asymmetric gas separation membrane is washed after acid removal and aged in a nitrogen environment from about 2 hours to about 24 hours.

16. The process according to claim 11 wherein the material of the preformed asymmetric gas separation membrane is comprised of a material selected from the group consisting of polymers and copolymers and substituted polymers of polyethers, polysulfone, polyethersulfone, polyphenylene oxide, styrene acrylonitrile copolymers, and cellulose acetate.

17. The process according to claim 11 wherein the acid is a mixture of Br nsted-Lowry and Lewis acids.

18. A process for improving the selectivity of a multicomponent membrane for gas separations wherein an asymmetric membrane is coated with one or more materials, said multicomponent membrane exhibiting selectivity permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of the gaseous mixture comprising, contacting the preformed multicomponent gas separation membrane with an effective amount of a Br nsted-Lowry acid which is volatile at ambient conditions, the acid being contacted with one or both surfaces of the multicomponent membrane for a period sufficient with respect to the at least one pair of gases to improve the separation factor.

19. The process according to claim 18 wherein the improved multicomponent gas separation membrane is contacted with a hydrohaloacid for a period varying from about 15 seconds to about 30 minutes.

20. The process according to claim 18 wherein the acid is in a vapor state when contacted with the preformed multicomponent gas separation membrane.

21. The process according to claim 18 wherein the acid is in a liquid state when contacted with the multicomponent gas separation membrane, the acid being volatile at ambient conditions.

22. The process according to claim 18 wherein the acid is a mixture of Br nsted-Lowry and Lewis acids.

23. The process according to claim 18 wherein the improved multicomponent gas separation membrane is washed after acid removal and aged in a nitrogen environment from about 2 hours to about 24 hours.

24. A multicomponent gas separation membrane exhibiting improved gas separation selectivity and resistance to hydrocarbons degradation, comprising, an asymmetric membrane coated with one or more materials, said membrane having selective permeation of at least one of a gaseous mixture over that of one or more remaining gases of the gaseous mixture which has been contacted on one or both surfaces with an effective amount of a Br nsted-Lowry acid, wherein with respect to the at least one gas, the acid contacted multicomponent gas separation membrane exhibits an improved separation factor greater than the separation factor exhibited by the multicomponent gas separation membrane before acid treatment.

25. The improved membrane of claim 24 wherein the Br nsted-Lowry acid is a hydrohaloacid.

26. The improved membrane of claim 24 wherein the improvement in separation factor for the one gas of the gas mixture is accomplished without reduction in permeability.

27. A process for separating at least one gas of a gaseous mixture from at least one other gas and said gaseous mixture by selective permeation and providing a permeated product containing at least one permeating gas comprising:

contacting the gaseous mixture with one surface of an asymmetric gas separation membrane exhibiting substantially improved gas separation selectivity, the asymmetric gas separation membrane having been contacted on one or both surfaces with an effective amount of a Br nsted-Lowry acid, wherein with respect to the at least one gas, the acid contacted asymmetric separation membrane exhibits an improved separation factor significantly greater than the separation factor exhibited by the asymmetric membrane before acid treatment; and

removing from the vicinity of an opposite surface from the contact surface, a permeated product having a different proportion of said at least one gas of said gaseous mixture to said at least one other gas of said gaseous mixture than the proportion of the gaseous mixture of said at least one gas to said at least one other gas.

28. A process for separating at least one gas in a gaseous mixture from at least one other gas in said gaseous mixture by selective permeation and providing a permeated product containing at least one permeating gas by contacting the gaseous mixture with one surface of a multicomponent gas separation membrane exhibiting improved gas separation selectivity and resistance to hydrocarbons which is comprised of an asymmetric membrane coated with one or more materials, said membrane having selective permeation of at least one of a gaseous mixture over that of one or more remaining gases of the gaseous mixture which has been contacted on one or both surfaces with a Br nsted-Lowry acid, wherein with respect to the at least one gas, the acid contacted multicomponent gas separation membrane exhibits an improved separation factor greater than the separation factor exhibited by the multicomponent gas separation before acid treatment;

and removing from the vicinity of an opposite, noncontacted membrane surface a permeated product having a different proportion of said at least one gas of said gaseous mixture to said at least one other gas of said gaseous mixture than the proportion in the gaseous mixture of said at least one gas to said at least one other gas.