Use of silver-exchanged ionomer membranes for gas separation

• US 5,191,151 A
• Filed: 12/18/1991
• Issued: 03/02/1993
• Est. Priority Date: 12/18/1991
• Status: Expired due to Term

• Current Assignee: Conocophillips Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Lee, Fu-Ming, Eriksen, Odd I., Dahl, Ivar M., Aksnes, Elin
• Primary Examiner(s): McFarlane, Anthony
• Assistant Examiner(s): PHAN, NHAT
• Application Number:
  US07/809,828
• Time in Patent Office: 440 Days
• Field of Search: 585/818, 585/843, 585/844, 55/16
• US Class Current: 95/50
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 69/142 with "carriers"
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: B01D 71/36 Polytetrafluoroethene
• CPC Class Codes: B01D 71/76 Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 rubbers in general B01D71/24
• CPC Class Codes: C07C 7/144 using membranes, e.g. selective permeation

Abstract

A process for separating C₂ -C₄ alkenes from C₁ -C₆ alkanes comprises the presence of water vapor in the alkene/alkane feed and the use of an Ag⁺ -exchanged sulfonated copolymer of tetrafluoroethylene and perfluorovinyl ether having been prepared by one of several specific ion-exchange methods.

Claims

1. In a process for separating at least one alkene containing 2 to 4 carbon atoms per molecule from at least one alkane containing 1 to 6 carbon atoms per molecule contained in a gaseous feed by means of an ionomer membrane, the improvements which comprise:

having water vapor present in said gaseous feed, and

using a silver-exchanged ionomer membrane having been prepared by the preparation method comprising the steps of

(a) contacting (i) an ionomer membrane of a copolymer of tetrafluoroethylene and at least one perfluorovinyl ether containing a terminal sulfonic acid group with (ii) a solution of at least one alkali metal compound, under such conditions as to obtain an alkali-metal-exchanged ionomer membrane;

(b) contacting the thus-obtained alkali-metal-exchanged ionomer membrane with a liquid comprising at least one alcohol containing from 2 to 20 carbon atoms and from 1 to 5 hydroxyl groups per molecule, under such conditions as to obtain a swollen alkali-metal-exchanged ionomer membrane; and

(c) treating the thus-obtained swollen alkali-metal-exchanged ionomer membrane with a solution containing at least one silver compound, under such conditions as to replace alkali metal ions with silver ions in said ionomer membrane.

2. A process in accordance with claim 1, wherein said gaseous feed is substantially saturated with water vapor at the operating conditions of said process.

3. A process in accordance with claim 2, wherein said at least one alkene contained in said gaseous feed is ethylene and said at least one alkane contained in said gaseous feed is ethane.

4. A process in accordance with claim 1, wherein said copolymer of said ionomer membrane used in step (a) has an equivalent weight of about 500-2000.

5. A process in accordance with claim 1, wherein said contacting in step (a) is carried out for about 0.5 to about 50 hours at a temperature of about 30°

-100°

C.

6. A process in accordance with claim 1, wherein said preparation method additionally comprises steps (a1) separating the alkali-metal-exchanged ionomer membrane obtained in step (a) from the solution of at least one alkali metal compound used in step (a), and (a2) heating the separated alkali-metal-exchanged membrane obtained in step (a1) at a temperature in the range of from about 100°

to about 350°

C. for a time period in the range of about 1 minute to about 3 hours and thereafter cooling the thus-heated membrane to a temperature of about 10°

-50°

C. at a rate of about 1°

-5°

C. per second; and

wherein step (b) is carried out with the alkali-metal-exchanged membrane having undergone the treatment of step (a2).

7. A process in accordance with claim 6, wherein said heating in step (a2) is carried out for a time period of about 1-2 hours at a temperature of about 330°

-350°

C.

8. A process in accordance with claim 1, wherein step (b) is carried out for a time period of at least about 0.1 hour at a temperature in the range of about 75°

C. to the normal boiling point of said at least one alcohol.

9. A process in accordance with claim 8, wherein said time period is in the range of about 1 hour to about 50 hours.

10. A process in accordance with claim 8, wherein said at least one alcohol is at least one polyhydric alcohol.

11. A process in accordance with claim 10, wherein said at least one polyhydric alcohol is glycerin.

12. A process in accordance with claim 8, wherein step (b) is carried out with glycerin for a time period of about 1 hour to about 50 hours at a temperature of about 200°

C. to about 290°

C.

13. A process in accordance with claim 1, wherein said at least one silver compound contained in said solution used in step (c) is selected from the group consisting of AgNO₃, AgClO₄ and AgBF₄.

14. A process in accordance with claim 1, wherein the silver concentration in said solution employed in step (c) is in the range of about 0.5 to about 6 gram-equivalents Ag⁺ per liter.

15. A process in accordance with claim 1 comprising the additional step (c1) of separating the silver-exchanged ionomer membrane obtained in step (c) from said solution of at least one silver compound.

16. In a process for separating at least one alkene containing 2 to 4 carbon atoms per molecule from at least one alkane containing 1 to 6 carbon atoms per molecule contained in a gaseous feed by means of an ionomer membrane, the improvements comprise:

having water vapor present in said gaseous feed, and

using a silver-exchanged ionomer membrane having been prepared by the preparation method consisting essentially of the steps of

(A) contacting (i) an ionomer membrane of a copolymer of tetrafluoroethylene and a perfluorovinyl ether containing a terminal sulfonic acid group with (ii) a solution consisting essentially of at least one alkali metal and water, under such conditions as to obtain an alkali-metal-exchanged ionomer membrane, and

(B) treating the alkali-metal exchanged ionomer membrane obtained in step (A) with a solution consisting essentially of at least one silver compound and water, under such conditions as to obtain a substantially silver-exchanged ionomer membrane.

17. A process in accordance with claim 21, wherein said gaseous feed is substantially saturated with water vapor at the operating conditions of said process.

18. A process in accordance with claim 17, wherein said at least one alkene contained in said gaseous feed is ethylene and said at least one alkane contained in said gaseous feed is ethane.

19. A process in accordance with claim 16, wherein said copolymer of said ionomer membrane used in step (A) has an equivalent weight of about 500-2000.

20. A process in accordance with claim 16, wherein said contacting in step (A) is carried out for about 0.5 to about 50 hours at a temperature of about 30°

-100°

C.

21. A process in accordance with claim 16, wherein said at least one alkali metal is sodium.

22. A process in accordance with claim 16, wherein said at least one silver compound contained in said solution used in step (B) is selected from the group consisting of AgNO₃, AgClO₄ and AgBF₄.

23. A process in accordance with claim 16, wherein the silver concentration in said solution employed in step (B) is in the range of about 0.5 to about 6 gram-equivalents Ag⁺ per liter.

24. In a process for separating at least one alkene containing 2 to 4 carbon atoms per molecule from at least one alkane containing 1 to 6 carbon atoms per molecule contained in a gaseous feed by means of an ionomer membrane, the improvements comprise:

having water vapor present in said gaseous feed, and

using a silver-exchanged ionomer membrane having been prepared by the preparation process consisting essentially of the steps of

(1) mixing (α

) a solution of a copolymer of tetrafluoroethylene and a perfluorovinyl ether containing a terminal sulfonic acid group and (β

) at least one silver compound, under such conditions to obtain a solution comprising a silver-exchanged copolymer;

(2) coating a porous support material with the solution obtained in step (1); and

(3) removing solvent contained in the solution used in step (2) from the coated porous support material obtained in step (2).

25. A process in accordance with claim 24, wherein said gaseous feed is substantially saturated with water vapor at the operating conditions of said process.

26. A process in accordance with claim 25, wherein said at least one alkene contained in said gaseous feed is ethylene and said at least one alkane contained in said gaseous feed is ethane.

27. A process in accordance with claim 24, wherein said copolymer used in step (a) has an equivalent weight of about 500-2000.

28. A process in accordance with claim 24, wherein the concentration of said copolymer employed in step (1) is in the range of about 0.1 to about 10 weight percent, and the ratio of gram-equivalents of silver to gram-equivalents of --SO₃ H groups in said copolymer is in the range of about 0.5:

1 to about 50;

1.

29. A process in accordance with claim 28, wherein said ratio is in the range of about 1:

1 to about 40;

1.

30. A process in accordance with claim 24, wherein said porous support material used in step (2) is an inorganic material selected from the group consisting of glass frits, sintered alumina, silica, titania, zirconia, zirconia spinel, mullite, cordierite, magnesium aluminate spinel and aluminosilicates.

31. A process in accordance with claim 30, wherein said support material is a porous alumina tube.

32. A process in accordance with claim 24, wherein the porous support material used in step (2) is made of an organic polymer material.

33. A process in accordance with claim 32, wherein said organic polymer material is polytetrafluoroethylene.

34. In a process for separating at least one alkene containing 2 to about 4 carbon atoms per molecule from at least one alkane containing 1 to 6 carbon atoms per molecule contained in a gaseous feed by means of an ionomer membrane, the improvements which comprise:

having water vapor present in said gaseous feed, and

using a silver-exchanged ionomer membrane having been prepared by the preparation method comprising the steps of

(a) contacting (i) an ionomer membrane of a copolymer of tetrafluoroethylene and at least one perfluorovinyl ether containing a terminal sulfonic acid group with (ii) a solution of at least one alkali metal compound, under such conditions as to obtain an alkali-metal-exchanged ionomer membrane;

(b) contacting the thus-obtained alkali-metal-exchanged ionomer membrane with a liquid comprising at least one alcohol containing from 2 to 20 carbon atoms and from 1 to 5 hydroxyl groups per molecule, under such conditions as to obtain a swollen alkali-metal-exchanged ionomer membrane;

(b1) separating the swollen alkali-metal-exchanged ionomer membrane obtained in step (b) from said at least one alcohol used in step (b);

(b2) immersing the separated swollen alkali-metal-exchanged ionomer membrane obtained in step (b1) in water or, alternatively, in an aqueous solution of an alkali metal compound, for a period of time in the range of about 0.5 day to about 50 days; and

(c) treating the swollen alkali-metal-exchanged ionomer membrane having undergone the treatment of step (b2) with a solution containing at least one silver compound, under such conditions as to replace alkali metal ions with silver ions in said ionomer membrane.

35. A process in accordance with claim 34, wherein said gaseous feed is substantially saturated with water vapor at the operating conditions of said process.

36. A process in accordance with claim 35, wherein said at least one alkene contained in said gaseous feed is ethylene and said at least one alkane contained ins aid gaseous feed is ethane.

37. A process in accordance with claim 34, wherein said copolymer of said ionomer membrane used in step (a) has an equivalent weight of about 500-2000.

38. A process in accordance with claim 34, wherein said contacting in step (a) is carried out for about 0.5 to about 50 hours at a temperature of about 30°

-100°

C.

39. A process in accordance with claim 34, wherein step (b) is carried out for a time period of at least about 0.1 hour at a temperature in the range of about 75°

C. to the normal boiling point of said at least one alcohol.

40. A process in accordance with claim 39, wherein said time period is in the range of about 1 hour to about 50 hours.

41. A process in accordance with claim 39, wherein said at least one alcohol is at least one polyhydric alcohol.

42. A process in accordance with claim 41, wherein said at least one polyhydric alcohol is glycerin.

43. A process in accordance with claim 39, wherein step (b) is carried out with glycerin for a time period of about 1 hour to about 50 hours at a temperature of about 200°

C. to about 290°

C.

44. A process in accordance with claim 34, wherein step (b2) is carried out with water.

45. A process in accordance with claim 34, wherein step (b2) is carried out with an aqueous 0.1-2 molar solution of at least one alkali metal compound.

46. A process in accordance with claim 45, wherein said alkali metal is sodium.

47. A process in accordance with claim 34, wherein said at least one silver compound contained in said solution used in step (c) is selected from the group consisting of AgNO₃, AgClO₄ and AgBF₄.

48. A process in accordance with claim 34, wherein the silver concentration in said solution employed in step (c) is in the range of about 0.5 to about 6 gram-equivalents Ag⁺ per liter.

49. A process in accordance with claim 34, comprising the additional steps of (a1) separating the alkali-metal-exchanged ionomer membrane obtained in step (a) from the solution of at least one alkali metal compound used in step (a), and (a2) heating the separated alkali-metal-exchanged membrane obtained in step (a1) at a temperature in the range of from about 100°

to about 350°

C. for a period fo time in the range of about 1 minute to about 3 hours and thereafter cooling the thus-heated membrane to a temperature of about 10°

-50°

C. at a rate of about 1°

-5°

C. per second; and

wherein step (b) is carried out with the alkali-metal-exchanged ionomer membrane having undergone the treatment of step (a2).

50. A process in accordance with claim 49, wherein said heating in step (a2) is carried out for a time period of about 1-2 hours at a temperature of about 330°

-350°

C.

51. A process in accordance with claim 34, comprising the additional step (c1) of separating the silver-exchanged ionomer membrane obtained in step (c) from said solution of at least one silver compound.