Polynorbornene pervaporation membrane films, preparation and use thereof
View Patent ↗Embodiments in accordance with the present invention provide forming polynorbornenes useful for forming pervaporation membranes, the membranes themselves and methods of making such membranes.
1. A pervaporation membrane, comprising:
a vinyl addition polynorbornene polymer having a Mw of at least about 5,000, the vinyl addition polynorbornene polymer comprising at least two different repeat units, wherein one of the repeat units, has a fluorinated carbinol moiety pendant group, the pervaporation membrane comprising a preferential permeability to a volatile organic over water, such permeability increasing with increasing organic concentration of a feed stream.
2. The pervaporation membrane according to claim 1 in a form of a tubular hollow fiber, a dense film flat sheet, or a thin film composite.
3. The pervaporation membrane according to claim 1 , wherein the vinyl addition polynorbornene polymer comprises at least three different repeat units.
4. A pervaporation membrane, comprising:
a polynorbornene polymer having a Mw of at least about 5,000, the vinyl addition polynorbornene polymer comprising at least two different repeat units, wherein one of the repeat units has a fluorinated carbinol moiety pendant group.
5. The pervaporation membrane according to claim 4 in a form of a tubular hollow fiber, a dense film flat sheet, or a thin film composite.
6. The pervaporation membrane according to claim 4 the pervaporation membrane comprising a preferential permeability to a volatile organic over water, such permeability increasing with increasing organic concentration of a feed stream.
7. The pervaporation membrane according to claim 4 , wherein the polynorbornene polymer comprises at least three different repeat units.
8. The pervaporation membrane according to claim 6 , wherein the volatile organic comprises butanol.
9. The pervaporation membrane according to claim 6 having a flux for butanol of at least about 100g/(m 2 ·h) from a fermentation broth comprising at least 1% by weight butanol, wherein the flux for butanol is an amount of butanol (q) that flows through a unit area (m 2 ) of the pervaporation membrane per unit of time (h).
10. The pervaporation membrane according to claim 4 , comprising a co-polymer of HFANB and C 1 -C 10 alkylNB.
11. A method of separating an organic product from a fermentation broth comprising the organic product, comprising:
charging the fermentation broth to a pervaporation module comprising a vinyl addition polynorbornene pervaporation membrane, the vinyl addition polynorbornene pervaporation membrane comprising a polynorbornene polymer having a Mw of at least about 5,000, the vinyl addition polynorbornene polymer comprising at least two different repeat units, wherein one of the repeat units has a fluorinated carbinol moiety pendant group; and
collecting a permeate vapor comprising the organic product from the pervaporation module.
12. The method according to claim 11 , wherein the fermentation broth charged to the pervaporation module has a temperature from about 30° C. to about 90° C.
13. The method according to claim 11 , wherein a vacuum from about 1 inHg to about 25 inHg is applied to the pervaporation module.
14. The method according to claim 11 , wherein the vinyl addition polynorbornene pervaporation membrane comprises at least three different repeat units.
15. A method of separating butanol from a fermentation broth comprising butanol, comprising:
charging the fermentation broth to a pervaporation module comprising a polynorbornene pervaporation membrane, the vinyl addition polynorbornene pervaporation membrane comprising a polynorbornene polymer having a Mw of at least about 5,000, the vinyl addition polynorbornene polymer comprising at least two different repeat units, wherein one of the repeat units has a fluorinated carbinol moiety pendant group; and
collecting a permeate vapor comprising butanol from the pervaporation module.
16. The method according to claim 15 , wherein the fermentation broth charged to the pervaporation module has a temperature from about 30° C. to about 90° C.
17. The method according to claim 15 , wherein a vacuum from about 1 inHg to about 25 inHg is applied to the pervaporation module.
18. The method according to claim 15 , wherein the polynorbornene pervaporation membrane comprises at least four different repeat units.
19. The method according to claim 15 , wherein the polynorbornene pervaporation membrane comprises at least three different repeat units.
20. The method according to claim 15 , wherein the polynorbornene pervaporation membrane comprises hydroxyhexafluoroisopropyl norbornene repeat units.
21. The method according to claim 15 , wherein the polynorbornene pervaporation membrane has a separation factor of at least about 15 for butanol from a fermentation broth comprising at least 1% by weight butanol.
22. The method according to claim 15 , wherein the polynorbornene pervaporation membrane has a flux of at least about 100 g/(m 2 ·h) for butanol from a fermentation broth comprising at least 1% by weight butanol.
23. The method according to claim 15 , wherein the polynorbornene pervaporation membrane comprises a polynorbornene polymer over a non-polynorbornene filtering component.
24. The method according to claim 15 , wherein the polynorbornene pervaporation membrane comprises hydroxyhexafluoroisopropyl norbornene repeat units and C 1 -C 10 alkyl norbornene repeat units.
25. The method according to claim 15 , wherein the polynorbornene pervaporation membrane has a thickness from about 0.1 micron to about 500 microns.
26. The method according to claim 15 , wherein the pervaporation feed stream comprise a biobutanol fermentation broth.