Multicomponent gas separation membranes having polyphosphazene coatings

• US 4,728,345 A
• Filed: 12/28/1983
• Issued: 03/01/1988
• Est. Priority Date: 12/28/1983
• Status: Expired due to Fees

• Current Assignee: Permea Incorporated (Linde Plc)
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Murphy, Milton K.
• Primary Examiner(s): Spear, Frank
• Application Number:
  US06/566,132
• Time in Patent Office: 1,525 Days
• Field of Search: 55/16, 55/158, 210/500.2, 210/490, 210/500.27
• US Class Current: 96/13
• CPC Class Codes: B01D 71/72 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
• CPC Class Codes: C08L 85/02 containing phosphorus
• CPC Class Codes: C09D 185/02 containing phosphorus

Abstract

Multicomponent membranes for gas separation having polyphosphazene coatings in occluding contact with a porous separation membrane are disclosed which are effective for separating at least one gas from gaseous mixtures and which exhibit improved stability when exposed to aromatic and aliphatic hydrocarbons contained in the gaseous mixtures. In addition multicomponent membranes for gas separations having a polyphosphazene coating in occluding contact with a porous separation membrane of polar material are disclosed which exhibit relative preferential permeation of polar gases from mixtures containing polar and non-polar gases.

Claims

1. In a multicomponent membrane for gas separation comprising a coating in occluding contact with a porous separation membrane of material, which material exhibits selective permeation of at least one gas of a gaseous mixture over that of one or more remaining gases of a gaseous mixture, said porous separation membrane having a substantial void volume, wherein, with respect to one pair of gases, the material of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the material of said coating, and the multicomponent membrane exhibits a separation factor significantly greater than the determined intrinsic separation factor of material of said coating and greater than the separation factor exhibited by the porous separation membrane;

the improvement comprising a polyphosphazene coating material having the formula;

##STR6## where R and R'"'"' are the same or different organic substituents and n is an integer of two or more, said polyphosphazene coating material swells no more than about 25% by volume when exposed to aliphatic and aromatic hydrocarbons contained in said gaseous mixture.

2. The improved multicomponent membrane for gas separation according to claim 1 wherein the coating material is comprised of polyphosphazenes having a repeating structural unit of the formula:

##STR7## where Y and Y'"'"' can be the same or different and are selected from oxygen, nitrogen or sulfur and R and R'"'"' can be the same or different and are selected from alkyl, aryl, substituted alkyl and substituted aryl with n being an integer of from about 100 to about 70,000.

3. The improved multicomponent membrane for gas separation according to claim 2 wherein the Y and Y'"'"' are both oxygen.

4. The improved multicomponent membrane for gas separation according to claim 3 wherein the polyphosphazene coating material swells no more than about 15% by volume when exposed to aliphatic and aromatic hydrocarbons contained in the gas mixture.

5. The improved multicomponent membrane for gas separation according to claim 3 wherein R and R'"'"' are substituted with halogens.

6. The improved multicomponent membrane according to claim 5 wherein the R and R'"'"' are substituted with fluorine.

7. The improved multicomponent membrane for gas separation according to claim 1 wherein with respect to at least one pair of gases consisting of one of hydrogen, helium, ammonia, carbon dioxide and hydrogen sulfide and one of carbon monoxide, nitrogen, argon, methane, ethane and propane, the multicomponent membrane exhibits a separation factor significantly greater than the determined intrinsic separation factor of the polyphosphazenes and greater than the separation factor exhibited by the porous separation membrane.

8. A multicomponent membrane for polar gas separations comprising a halogenated polyphosphazene coating in occluding contact with a porous separation membrane of polar material, said polar material exhibiting selective permeation for polar gases from gaseous mixtures, said polar porous separation membrane having a substantial void volume, wherein with respect to the polar gases of the porous separation membrane exhibits a determined intrinsic separation factor greater than the determined intrinsic separation factor of the halogenated polyphosphazene coating material, and the multicomponent membrane exhibits a separation factor significantly greater than the determined intrinsic separation factor of the polyphosphazene coating material and greater than the separation factor exhibited by the polar, porous separation membrane for polar gases.

9. The multicomponent membrane for polar gas separations according to claim 8 wherein the porous separation membrane is contacted with a polar solvent prior to or during coating with the polyphosphazenes.

10. The multicomponent membrane for polar gas separations according to claim 8 wherein the material of the porous separation membrane is comprised of polyamides.

11. The multicomponent membrane according to claim 8 wherein the porous separation membrane is comprised of polar material which is crosslinked.

12. The multicomponent membrane for polar gas separations according to claim 8 wherein with respect to polar gases selected from carbon dioxide and hydrogen sulfide in a feed gas mixture with C₁ to C₃ hydrocarbon gases, the multicomponent membrane preferentially permeates the polar gases, carbon dioxide and hydrogen sulfide.

13. The multicomponent membrane for polar gas separations according to claim 8 wherein the polyphosphazene coating material swells no more than about 15% by volume when exposed to aliphatic and aromatic hydrocarbons contained in the feed gas mixture.