Organic fluid permeation through fluoropolymer membranes
Separation of the components of liquid mixtures is achieved by contacting a liquid mixture with a nonporous membrane having a fluoropolymer selectively permeable layer and imposing a pressure gradient across the membrane from feed side to permeate side. Unusually high transmembrane flux is obtained when the membrane is subjected to one or more process conditions prior to separation. These include (a) leaving some residual amount of membrane casting solvent in the membrane, and (b) contacting the membrane with a component of the mixture to be separated for a duration effective to saturate the membrane with the component.
1. A selectively permeable membrane formed by the process comprising the steps of:
(A) providing a polymeric composition comprising repeating units of a polymerized perfluorinated monomer,
(B) dissolving the polymeric composition in a liquid medium, thereby forming a membrane casting solution,
(C) depositing the casting solution onto a support structure to form thereon a membrane precursor that comprises a residual amount of the liquid medium within the membrane precursor,
(D) optionally draining free-flowing membrane casting solution from the membrane precursor, and
(E) removing from the membrane precursor a fraction of the residual amount of the liquid medium effective to produce a nonporous selectively permeable membrane which has a pressure normalized solvent flux (PNSF) for N-hexane of at least 23 Lm 2 -hr-MPa.
2. The selectively permeable membrane of claim 1 in which the nonporous selectively permeable membrane is structurally modified relative to a basic state attained by a conventional nonporous selectively permeable membrane, the conventional nonporous selectively permeable membrane being formed by (i) depositing the casting solution onto the support structure to form thereon a membrane precursor that comprises a residual amount of the liquid medium within the membrane precursor and (ii) rapidly and substantially completely removing from the membrane precursor the residual amount of the liquid medium effective to produce the conventional nonporous selectively permeable membrane.
3. The selectively permeable membrane of claim 1 in which the liquid medium consists essentially of fluorinated solvent for the polymeric composition.
4. The selectively permeable membrane of claim 1 in which the liquid medium present in the nonporous selectively permeable membrane after step (E) is between 0.1% and about 15%.
5. The selectively permeable membrane of claim 1 in which the liquid medium consists essentially of at least one fluorinated chemical compound.
6. The selectively permeable membrane of claim 1 in which the liquid medium comprises about 1-99 wt. % of at least one fluorinated chemical compound and a complementary amount of at least one non-fluorinated chemical compound.
7. The selectively permeable membrane of claim 1 in which the process further includes the step of removing the selectively permeable membrane from the support structure to provide a monolithic membrane.
8. The selectively permeable membrane of claim 1 in which the membrane has an active layer that is selectively permeable to a component of a liquid mixture and in which the process further comprises the step (F) of contacting the active layer with at least one component of the liquid mixture for a duration effective for the component to saturate the selectively permeable membrane.
9. The selectively permeable membrane of claim 8 in which the duration is at least about 1 hour.
10. The selectively permeable membrane of claim 9 in which the contacting step is at about atmospheric pressure.
11. The selectively permeable membrane of claim 1 in which the polymeric composition has oxygen permeability of at least about 500 barrers.
12. The selectively permeable membrane of claim 1 in which liquid medium is contained in the selectively permeable membrane after removing a fraction of the residual amount of the liquid medium.