ISOMER SEPARATION WITH HIGHLY FLUORINATED POLYMER MEMBRANES

Abstract

Separation of linear and branched alkane isomers via selective permeation through a composite membrane is disclosed. The separation layer in the composite membrane is fabricated from a blend of at least two different fluoropolymer compositions, A and B, in which composition A has a normal-alkane isomer permeability that is greater than composition B. Composition B has a normal alkane to branched-alkane isomer selectivity that is equal or greater than composition A. The separation layer in the composite membrane has a normal-alkane permeability that is greater than composition B and a normal-alkane to branched alkane isomer selectivity that is greater than composition A.

Claims

1. A composite membrane comprising a non-porous separation layer comprising a blend of fluoropolymers comprising: a) fluoropolymer composition A; and b) fluoropolymer composition B; wherein fluoropolymer composition A has a normal-alkane isomer permeability that is greater than fluoropolymer composition B; and wherein fluoropolymer composition B has a normal alkane to branched-alkane isomer selectivity that is equal or greater than fluoropolymer composition A; and wherein the composite membrane has a normal-alkane permeability that is greater than fluoropolymer composition B and a normal-alkane to branched-alkane isomer selectivity that is greater than fluoropolymer composition A.

2. The composite membrane of claim 1, in which at least one of the fluoropolymer compositions is a copolymer comprising a perfluorinated and cyclic repeat-unit.

3. The composite membrane of claim 1, in which at least one of the fluoropolymer compositions is a copolymer comprising repeat units derived from perfluoro(2,2-dimethyl-1,3-dioxole).

4. The composite membrane of claim 1, in which at least one of the fluoropolymer compositions is a copolymer of perfluoro(2,2-dimethyl-1,3-dioxole) and tetrafluoroethylene.

5. The composite membrane of claim 1, in which at least one of the fluoropolymer compositions is perfluorinated.

6. The composite membrane of claim 1, wherein the blend of fluoropolymer contains no more than 90% of fluoropolymer composition A or 90% of fluoropolymer composition B.

7. A process for the pervaporation separation of organic-compound mixtures using a composite membrane having a feed side and a permeate side, wherein the process comprises: a) providing said composite membrane comprising a non-porous separation layer comprising a blend of fluoropolymer comprising: i) fluoropolymer composition A; and ii) fluoropolymer composition B; wherein fluoropolymer composition A has a normal-alkane isomer permeability that is greater than fluoropolymer composition B; and wherein fluoropolymer composition B has a normal-alkane to branched-alkane isomer selectivity that is equal or greater than fluoropolymer composition A; and b) exposing the feed-side of the composite membrane to a flowing first organic-compound mixture; and c) providing a driving force and producing a second organic-compound mixture at the permeate-side of the composite membrane that is enriched in at least one of the components of the first organic-compound mixture; and wherein the composite membrane has a normal-alkane permeability that is greater than fluoropolymer composition B and a normal-alkane to branched-alkane isomer selectivity that is greater than fluoropolymer composition A.

8. The process of claim 7, in which at least one of the fluoropolymer compositions is a copolymer comprising a perfluorinated and cyclic repeat-unit.

9. The process of claim 7, in which at least one of the fluoropolymer compositions is a copolymer comprising repeat units derived from perfluoro(2,2-dimethyl-1,3-dioxole).

10. The process of claim 7, in which at least one of the fluoropolymer compositions is a copolymer of perfluoro(2,2-dimethyl-1,3-dioxole) and tetrafluoroethylene.

11. The process of claim 7, in which at least one of the fluoropolymer compositions is perfluorinated.

12. The process of claim 7, in which at least one of the components of the first organic-compound mixture is selected from a group consisting of C4 to C12 linear alkanes, C4 to C12 branched alkanes, and C4 to C12 cyclic alkanes.

13. The process of claim 7, wherein the blend of fluoropolymer contains no more than 90% of fluoropolymer composition A or 90% of fluoropolymer composition B.

14. The process of claim 7, wherein the driving force is provided by a pressure differential across the feed-side and the permeate-side or providing a flow of sweep gas across the permeate side.

15. The process of claim 7, wherein the composite membrane further comprises a porous support having a porosity of 40% or greater and an average pore size between 0.1 m and 0.1 m.

16. A method of a making a composite membrane comprising: a) providing a porous-layer support; b) providing a blend of fluoropolymers comprising: i) fluoropolymer composition A; and ii) fluoropolymer composition B; c) coating the blend of fluoropolymers on the porous support layer to produce a non-porous separation layer on the porous-layer support; wherein fluoropolymer composition A has a normal-alkane isomer permeability that is greater than fluoropolymer composition B; and wherein fluoropolymer composition B has a normal-alkane to branched-alkane isomer selectivity that is equal or greater than fluoropolymer composition A; and wherein the composite membrane has a normal-alkane permeability that is greater than fluoropolymer composition B and a normal-alkane to branched-alkane isomer selectivity that is greater than fluoropolymer composition A.

17. The method of claim 16, wherein the blend of fluoropolymers is a solvent mixture further comprising a solvent, and wherein the blend of fluoropolymer concentration in the solution mixture is no more than 1%.

18. The method of claim 17, wherein coating the blend of fluoropolymers on the porous support layer comprises solution casting.

19. The method of claim 17, wherein the non-porous separation layer has a thickness of no more than 2 m.

20. The method of claim 19, further comprising annealing the non-porous separation layer on the porous support at a temperature between 50 C. and 250 C. for a time of between 1 and 60 minutes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0018] As used herein, the terms comprises, comprising, includes, including, has, having or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. In addition, use of a or an are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0019] Certain exemplary embodiments of the present invention are described herein. The described embodiments are only for purposes of illustrating the present invention and should not be interpreted as limiting the scope of the invention. Other embodiments of the invention, and certain modifications, combinations and improvements of the described embodiments, will occur to those skilled in the art and all such alternate embodiments, combinations, modifications, improvements are within the scope of the present invention. Certain additional terms are also used and some of them are further defined within the following detailed description of the invention.

[0020] Fluorinated polymers or fluoropolymers are useful materials for fabrication of the membrane separation layer of the invention. A fluoropolymer is a material containing carbon-fluorine groups. By a carbon-fluorine group is meant a group wherein a fluorine atom is directly bonded to carbon while a carbon-hydrogen group is a group wherein a hydrogen atom is bound directly to a carbon atom. Thus CF2-groups contains two carbon fluorine groups, while a CH.sub.3 group contains three carbon-hydrogen groups. Thus in a homopolymer of, for example, vinylidene fluoride, in which the repeat groups are CH.sub.2CF.sub.2, the carbon-hydrogen groups and the carbon-fluorine groups are each 50% of the total of carbon-hydrogen plus carbon-fluorine groups present. The relative amount of carbon-fluorine and carbon-hydrogen groups present can be determined by for example NMR spectroscopy, using .sup.13C NMR, or a combination of .sup.19F and .sup.1H NMR spectroscopy. In the fluoropolymers of invention herein, of the total of the carbon-hydrogen groups and the carbon fluorine groups preferably at least 10% are carbon-fluorine groups, preferably 50% or more, and very preferably 75% or more. Especially preferred are perfluoropolymers or fluoropolymers in which there are no carbon-hydrogen groups in the polymer-backbone repeating units. Such fluoropolymers may have very small amounts of adventitious carbon-hydrogen groups in the backbone from impure monomers, or groups such as initiator fragments bonded to chains.

[0021] As previously noted, fluoropolymers that are copolymer compositions comprising cyclic repeat-units from perfluoro(2,2-dimethyl-1,3-dioxole) (PDD) are amorphous, glassy, soluble, and preferred for use as either the high permeability or high-selectivity component in the blend for the separation layer, depending on the PDD mole fraction in the copolymer. Certain compositions that comprise PDD with tetrafluoroethylene are commercially available as Teflon AF (The Chemours Co., Wilmington, Del.). For further information about Teflon AF, see P.R. Resnick et al. in Teflon AF Amorphous Fluoropolymers, J. Schiers, Ed., Modern Fluoropolymers, John Wiley & Sons, New York 1997 397-420, which is hereby incorporated by reference. In general, a copolymer composition having a PDD mole fraction greater than 0.8 is preferred for the high permeability component, component A, of the separation layer whereas a PDD mole fraction less than 0.7 is preferred for the high selectivity component, component B. For either component, the copolymer may also comprise other repeat units containing functional groups such as perfluoroether, ester, alcohol, carboxylate, or other heteroatoms such as chlorine. Alternatively, other fluoropolymer compositions comprising cyclic repeat-units that are different from PDD may also be used, primarily for the high selectivity component of the separation layer. Some of these other fluoropolymers are also commercially available and include Hyflon (Solvay, Houston Tex.) and Cytop (AGC Inc, Chemicals Company, Tokyo Japan).

[0022] Dilute fluoropolymer solutions for each of the high permeability component, component A, and high-selectivity component, component B, for the separation layer are prepared in solvents suitable for casting and at concentrations that are preferably less than 1%, and more preferably between 0.05% and 0.5%. Suitable solvents or solvent mixtures are those that are miscible, dissolve the fluoropolymers, and evaporate at an appropriate rate to form the blended separation layer in a timely manner. For example, suitable solvents include, but are not limited to, fluorinated solvents such as Novec FC770, Novec HFE7200, Novec HFE7300, and Opteon SF10. The solutions are subsequently blended to a desired component ratio by quantitative mixing of appropriate quantities of each solution.

[0023] Solution casting is a preferred film forming technique to fabricate the separation layer of the composite membrane. Preferred casting techniques include but are not limited to ring casting, dip-coating, spin-coating, slot-die coating, and Mayer rod coating. The blended fluoropolymer solution is cast onto a suitable substrate such as a porous-layer support and the solvent(s) are evaporated to form the blended separation layer. Residual or trace solvent(s) remaining in the layer should not interfere with subsequent processing steps. The separation layer is thin and preferably about 0.01-m to about 2-m, and more preferably 0.1-m to 0.5-m. The separation layer preferably has a permeance at least 5 times greater than the porous-layer support, more preferably at least 10 times. Permeance, or pressure normalized flux, is usually reported in gas permeance units or GPU and has units of 10.sup.6cm.sup.3(STP)/cm.sup.2/sec/cmHg. Permeability is further normalized for thickness with units of 10.sup.10cm.sup.3(STP)cm/cm.sup.2/sec/cmHg and reported in Barrer.

[0024] The porous-layer support reinforces the separation layer and helps to strengthen the composite membrane as a whole such that the membrane may be fabricated into more complex geometries such as spiral-wound or hollow-fiber membrane modules. The porous-layer support may be in the form of a flat sheet, hollow fiber, or tube. Suitable materials for a porous-layer support include but are not limited to polyvinylidine fluoride, expanded polytetrafluoroethylene, polyacrylonitrile, polysulfone, and polyethersulfone. The porous-layer support may also comprise an even stronger backing material such as porous non-woven polyester or polypropylene. Porous inorganic substrates such as silica or alumina are also suitable materials for the porous-layer support. Permeate should flow relatively unobstructed through the usually much thicker porous-layer support having a preferred open porosity that is 40% or greater. The average pore size is preferably less 0.1-m and more preferably between 0.01 and 0.03-m.

[0025] The composite membrane may be subjected to a thermal treatment step annealed to remove residual or trace solvents, and to further improve mechanical durability and long-term permeance and selectivity performance. The separation layer is annealed by heating the composite membrane at temperatures that may approach the glass transition temperatures of the fluoropolymers in the separation layer. The glass transition temperatures will be dependent on fluoropolymer compositions used in the separation layer. Generally, annealing temperatures for the separation layer are between 50 and 250 C., and preferably between 100 to 200 C. The composite membrane is preferably heated for 0.1 to 60 minutes, more preferably for 1 to 5 minutes. The appropriate annealing temperature and time should not degrade the other components of the composite membrane.

EXAMPLES

Example 1

[0026] Pervaporation separation of an octane/isooctane isomer mixture using a blended Teflon AF 2400/1600 composite membrane: Separate solutions of Teflon AF 2400 and AF 1600 were prepared at 0.50% w/w concentrations with magnetic stirring in Novec FC770. The solutions were separately filtered using 1-m glass fiber prior to preparing blended solutions at different ratios. Single component and blended solutions were separately ring-cast on a microporous PVDF substrate, having an average pore size of approximately 0.2-m, to form the composite membranes. The ring-cast membranes were first air dried and then placed in a 60 C. oven for 1 hour to remove residual solvent. A 47-mm disc was punched from each membrane and separately tested in the pervaporation cell at 80 C. The feed-side of the composite membrane was contacted with a liquid consisting of a 50-50 mixture of octane and isooctane and a helium gas sweep with vacuum was applied on the permeate side. Permeate was collected in a cold trap that was chilled with liquid nitrogen and permeate and feed-liquid compositions were analyzed using a gas chromatograph. The membrane permeance and selectivity for octane and isooctane separation were calculated from the experimental data and are shown in Table 1. The data showed effective separation of the octane/isooctane mixture under pervaporation conditions. Membranes prepared from blends had permeance that was more than 10 times greater than the single component AF1600 membrane and selectivity that was at least 2 times higher than the single component AF2400 membrane.

TABLE-US-00001 TABLE 1 Octane Fluoropolymer Ratio Permeance Selectivity AF 2400 AF 1600 (GPU) (Octane/Isooctane) 100 0 5600 3 90 10 4750 6 50 50 1250 15 0 100 100 17

Example 2

[0027] Pervaporation separation of a pentane/Isopentane isomer mixture using a blended Teflon AF 2400/1600 composite membrane: Separate solutions of Teflon AF 2400 and AF 1600 were prepared at 0.50% w/w concentrations with magnetic stirring in Novec FC770. The solutions were separately filtered using 1-m glass fiber prior to preparing blended solutions at different ratios. Single component and blended solutions were separately cast on a microporous PVDF substrate, having an average pore size of approximately 0.2-m, using a draw-down table and a #15 Mayer rod. A 47-mm disc was punched from each membrane and separately tested in the pervaporation cell at 22 C. The feed-side of the composite membrane was contacted with a liquid consisting of a 50-50 mixture of pentane and isopentane. A helium gas sweep with vacuum was applied on the permeate side. Permeate was collected in a cold trap that was chilled with liquid nitrogen and permeate and feed-liquid compositions were analyzed using a gas chromatograph. The membrane permeance and selectivity for pentane and isopentane separation were calculated from the experimental data and are shown in Table 2.

TABLE-US-00002 TABLE 2 Pentane Fluoropolymer Ratio Permeance Selectivity AF 2400 AF 1600 (GPU) (Pentane/Isopentane) 100 0 8580 1.4 50 50 6330 1.6 10 90 2840 1.7 0 100 2370 2.0

Example 3

[0028] Pervaporation separation of an octane / isooctane isomer mixture using a blended Teflon AF 2400/Hyflon AD 40H composite membrane: Separate solutions of Teflon AF 2400 and Hyflon AD 40H were prepared at 0.50% w/w concentrations with magnetic stirring in Novec FC770. The solutions were separately filtered using 1-m glass fiber prior to preparing blended solutions at different ratios. Single component and blended solutions were separately cast on a microporous PVDF substrate, having an average pore size of approximately 0.2-m, using a draw-down table and a #15 Mayer rod. A 47-mm disc was punched from each membrane and separately tested in the pervaporation cell at 80 C. The feed-side of the composite membrane was contacted with a liquid consisting of a 50-50 mixture of octane and isooctane. A helium gas sweep with vacuum was applied on the permeate side. Permeate was collected in a cold trap that was chilled with liquid nitrogen and permeate and feed-liquid compositions were analyzed using a gas chromatograph. The membrane permeance and selectivity for octane and isooctane separation are shown in Table 3.

TABLE-US-00003 TABLE 3 Octane Fluoropolymer Ratio Permeance Selectivity AF 2400 AD 40H (GPU) (Octane/Isooctane) 100 0 5600 3.0 90 10 4050 3.1 50 50 225 6.6 10 90 155 3.0 0 100 195 2.8

Example 4

[0029] Pervaporation separation of a pentane / isopentane isomer mixture using a blended Teflon AF 2400/Hyflon AD 40H composite membrane: Separate solutions of Teflon AF 2400 and Hyflon AD 40H were prepared at 0.50% w/w concentrations with magnetic stirring in Novec FC770. The solutions were separately filtered using 1-m glass fiber prior to preparing blended solutions at different ratios. Single component and blended solutions were separately cast on a microporous PVDF substrate, having an average pore size of approximately 0.2-m, using a draw-down table and a #15 Mayer rod. A 47-mm disc was punched from each membrane and separately tested in the pervaporation cell at 22 C. The feed-side of the composite membrane was contacted with a liquid consisting of a 50-50 mixture of pentane and isopentane. A helium gas sweep with vacuum was applied on the permeate side. Permeate was collected in a cold trap that was chilled with liquid nitrogen and permeate and feed-liquid compositions were analyzed using a gas chromatograph. The membrane permeance and selectivity for pentane and isopentane separation are shown in Table 4.

TABLE-US-00004 TABLE 4 Pentane Fluoropolymer Ratio Permeance Selectivity AF 2400 AD 40H (GPU) (Pentane/Isopentane) 100 0 8580 1.4 90 10 7930 1.5 50 50 580 2.2 10 90 120 1.7 0 100 160 1.5

Example 5

[0030] Pervaporation separation of a dodecane/Isododecane isomer mixture using a blended Teflon AF 2400/1600 composite membrane: Separate solutions of Teflon AF 2400 and AF 1600 were prepared at 0.50% w/w concentrations with magnetic stirring in Novec FC770. The solutions were separately filtered using 1-.m glass fiber prior to preparing blended solutions at different ratios. Single component and blended solutions were separately cast on a microporous PVDF substrate, having an average pore size of approximately 0.2-m, using a draw-down table and a #15 Mayer rod. A 47-mm disc was punched from each membrane and separately tested in the pervaporation cell at 22 C. The feed-side of the composite membrane is contacted with a liquid consisting of a 50-50 mixture of dodecane and isododecane. A helium gas sweep with vacuum is applied on the permeate side. Permeate is collected in a cold trap that is chilled with liquid nitrogen and permeate and feed-liquid compositions are analyzed using a gas chromatograph. The membrane permeance and selectivity for dodecane and isododecane separation are shown in Table 5.

TABLE-US-00005 TABLE 5 Dodecane Fluoropolymer Ratio Permeance Selectivity AF 2400 AF 1600 (GPU) (Dodecane/Isododecane) 100 0 1800 4 90 10 900 6 50 50 200 7 0 100 50 9