Durable asymmetric composite membrane
Durable asymmetric composite membranes consisting of a film of cross-linked sulfonated poly(ether ether ketone) adhered to a sheet of sulfonated microporous poly(ethylene) are disclosed. The membranes have application in the recovery of water from feed streams were the ability to clean in situ is desirable, for example in dairy processing. Methods of preparing cross-linked sulfonated poly(ether ether ketone) suitable for use as a rejection layer in such membranes are also disclosed.
1. A method of removing water from a feed stream that is a dairy product comprising the step of exposing the first layer of an asymmetric composite membrane to the feed stream at a pressure and temperature sufficient to produce a permeate, where the asymmetric composite membrane comprising a first layer of cross-linked sulfonated poly(ether ether ketone) adhered to a second layer of sulfonated microporous poly(ethylene).
2. The method of claim 1 where the feed stream is milk.
3. The method of claim 2 where the pressure is in the range 20 to 40 Bar.
4. The method of claim 3 where the temperature is in the range 4 to 20° C.
5. A method of preparing a cross-linked sulfonated poly(ether ether ketone) comprising the step of incubating in the presence of a Friedel-Crafts type catalyst a mixture of a chlorosulfonated poly(ether ether ketone) and a C 2-9 -dioyl halide cross-linking agent solvated in a non-aqueous reactive solvent at a temperature substantially below 180° C. for a period of time sufficient to provide the cross-linked sulfonated poly(ether ether ketone).
6. The method of claim 5 where the Friedel-Crafts type catalyst is ferric chloride (FeCl 3 ).
7. The method of claim 6 where the C 2-9 -dioyl halide is an acyclic, aliphatic C 2-6 -dioyl chloride.
8. The method of claim 7 where the C 2-9 -dioyl halide is butanedioyl dichloride.
9. The method of claim 8 where the non-aqueous reactive solvent is a cycloalkanone.
10. The method of claim 9 where the non-aqueous reactive solvent is cyclopentanone.
11. The method of claim 5 where the temperature is in the range 120° C. to 170° C.
12. The method of claim 5 where the period of time is 15 to 105 minutes.
13. An asymmetric composite membrane comprising a first layer of cross-linked sulfonated poly(ether ether ketone) adhered to a second layer of sulfonated microporous poly(ethylene).
14. The membrane of claim 13 where the thickness of the first layer is in the range 0.1 to 50 μM and the thickness of the second layer is in the range 5 to 200 μM.
15. The membrane of claim 14 where the thickness of the first layer is in the range 1 to 5 μM and the thickness of the second layer is in the range 5 to 20 μM.
16. The membrane of claim 13 where the first layer of cross-linked sulfonated poly(ether ether ketone) is prepared according to a method comprising the step of incubating in the presence of a Friedel-Crafts type catalyst a mixture of a chlorosulfonated poly(ether ether ketone) and a C 2-9 -dioyl halide cross-linking agent solvated in a non-aqueous reactive solvent at a temperature substantially below 180° C. for a period of time sufficient to provide the cross-linked sulfonated poly(ether ether ketone).