Process for recovery of ammonia from an ammonia-containing gas mixture

• US 5,009,678 A
• Filed: 10/31/1989
• Issued: 04/23/1991
• Est. Priority Date: 10/31/1989
• Status: Expired due to Fees

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Union Carbide Industrial Gases Technology Corporation
• Inventors: Perrin, Jerry E., Bikson, Benjamin, Nelson, Joyce K.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/429,817
• Time in Patent Office: 539 Days
• Field of Search: 55/16, 55/70, 55/158
• US Class Current: 95/47
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: C01C 1/12 Separation of ammonia from gases and vapours as part of the ammonia synthesis process C01C1/04
• CPC Class Codes: C08G 65/48 Polymers modified by chemical after-treatment
• CPC Class Codes: C08J 2371/12 Polyphenylene oxides
• CPC Class Codes: C08J 5/2256 based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation

Abstract

Composite semi-permeable membranes comprised of an extremely thin layer of a sulfonated polysulfone polymer coated on a porous support are useful in processes for the selective permeation of ammonia from a mixture of gases containing the ammonia component in admixture with other gaseous components.

Claims

1. A process for separating ammonia from a gaseous mixture thereof with other gaseous components which comprises contacting said gaseous mixture with one side of a gas separation composite membrane comprising a porous support coated with a thin layer of a cation exchange type polymer containing the sulfonic acid ion exchange group in the polymer molecule represented by the general formula:

##STR9## wherein A, B, D and E are unsubstituted or substituted arylene groups with at least one A, B, D, E groups in the polymer chain repeat unit substituted by a free sulfonic acid group or its salified form;

R and R'"'"' can be the same or different and represent an alkyl group or a halogenated alkyl group having from 1 to 4 carbon atoms;

b represents the polymer average molecular weight, generally above about 10,000;

c, d and e are integers having a value of from zero to about 6; and

the degree of sulfonation --S_n is from about 0.2 to about 2; and

recovering the permeate and retentate components, said polymer providing enhanced selectivity and permeability characteristics for the selective permeation and separation of ammonia as the permeate component from the other components of the gaseous mixture comprising retentate components.

2. A process as claimed in claim 1 wherein said polymer average molecular weight is from about 25,000 to about 80,000.

3. A process as claimed in claim 2 wherein the degree of sulfonation is from about 0.4 to about 1.5.

4. A process as claimed in claim 1 wherein R'"'"' is methyl.

5. A process as claimed in claim 1 wherein R'"'"' is trifluoromethyl.

6. A process as claimed in claim 1 wherein A, B, D, E are p-phenylene groups.

7. A process as claimed in claim 1 wherein the degree of sulfonation is from about 0.4 to about 1.5.

8. A process as claimed in claim 1 wherein said cation exchange polymer is a sulfonated polyether sulfone in which the repeating unit in the chain has the general formula:

##STR10## wherein b and S_n are as defined in claim 1.

9. A process as claimed in claim 1 wherein said cation exchange polymer is a sulfonated polyether ether sulfone in which the repeating unit in the chain has the general formula:

##STR11## wherein b and S_n are as defined in claim 1.

10. A process as claimed in claim 1 wherein said cation exchange polymer is a sulfonated polysulfone in which the repeating unit in the chain has the general formula:

##STR12## wherein b, R, R'"'"' and S_n are as defined in claim 1.

11. A process as claimed in claim 10 wherein R'"'"' is trifluoromethyl.

12. A process as claimed in claim 10 wherein and R'"'"' is methyl.

13. A process as claimed in claim 10 wherein the sulfonic acid group is in the salified form wherein the cation is NH₄, Cu or Co.

14. A process as claimed in claim 10 wherein R'"'"' is trifluoromethyl.

15. A process as claimed in claim 10 wherein said thin layer is from about 200 to about 7,000 Angstroms thick.

16. A process as claimed in claim 10 wherein said thin layer comprises a thin coating layer less than about 10,000 Angstroms thick, the material of said thin layer comprising at least 50 percent by weight of said sulfonated polysulfone.

17. A process as claimed in claim 1 wherein said thin layer comprises a thin coating less than about 10,000 Angstroms thick.

18. A process as claimed in claim 17 wherein the material of said thin layer comprises at least 50 percent by weight of sulfonated polysulfone of the general formula:

##STR13## wherein b, R, R'"'"' and S_n are as defined in claim 1.

19. A process as claimed in claim 18 wherein said sulfonated polysulfone is in the salified form wherein the cation is the ammonium group, an alkali metal atom, an alkaline earth metal atom, a transition metal atom, or an organic salt-forming group.

20. A process as claimed in claim 18 wherein the degree of sulfonation of the polysulfone polymer comprising said thin layer is such that the number of sulfonic groups is from about 0.5 to about 2 milliequivalents per gram of dry polymer in acid form.

21. A process as claimed in claim 17 wherein said sulfonated polysulfone is sulfonated bisphenol-A polysulfone.

22. A process as claimed in claim 17 wherein said sulfonated polysulfone is poly[oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4-phenylene[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]1,4-phenylene].

23. A process as claimed in claim 1 wherein said thin layer is from about 500 to about 3,000 Angstroms thick.

24. The process of claim 1 in which said gaseous mixture comprises ammonia and hydrogen, said ammonia as the permeate component being separated from a retentate component comprising hydrogen.