# US 10,866,001 B2 · Blended membranes for water vapor transport and methods for preparing same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,866,001 B2 - Document ID: US10866001B2 - Status: Granted - Kind: B2 - Application number: 16/163,312 - Filed: 2018-10-17 - Published: 2019-03-28 - Granted: 2020-12-15 - Earliest claimed: 2014-06-16 - Assignees: CORE Energy Recovery Solutions Inc. - Applicants: CORE Energy Recovery Solutions Inc. - Inventors: Ryan Nicholas Huizing; Hao Chen; Frankie Kin Bong Wong - Web page: https://patentgrep.com/patent/US10866001B2 ## CPC - C08J 7/048: Forming gas barrier coatings - B01D 53/228: {characterised by specific membranes} - B01D 53/268: {by diffusion} - B01D 61/362: {Pervaporation} - B01D 69/02: characterised by their properties - B01D 69/107: {Organic support material} - B01D 69/12: Composite membranes; Ultra-thin membranes - B01D 71/16: Cellulose acetate - B01D 71/82: characterised by the presence of specified groups, e.g. introduced by chemical after-treatment - C08G 65/48: Polymers modified by chemical after-treatment - C08J 7/0427: {with only one layer of a composition containing a polymer binder (with more layers C08J7/042)} - C09D 101/12: Cellulose acetate - C09D 101/14: Mixed esters, e.g. cellulose acetate-butyrate - C09D 101/28: Alkyl ethers - C09D 171/00: Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain (based on polyacetals C09D159/00; based on epoxy resins C09D163/00; based on polythioether-ethers C09D181/02; based on polyethersulfones C09D181/06); Coating compositions based on derivatives of such polymers - D06M 15/07: Cellulose esters - D06M 15/53: Polyethers (polyacetals D06M15/39) - D06N 3/0004: {using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)} - D06N 3/02: with cellulose derivatives - D06N 3/12: with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {, e.g. gelatine proteins} - F24F 3/147: with both heat and humidity transfer between supplied and exhausted air - B01D 2053/222: {with plates} - B01D 2257/80: Water - B01D 2258/06: Polluted air - B01D 2323/39: Electrospinning - B01D 2325/16: Membrane materials having positively charged functional groups - B01D 2325/20: Specific permeability or cut-off range - C08G 2340/00: Filter material - C08G 2650/02: characterized by the type of post-polymerisation functionalisation - C08G 2650/40: containing ketone groups, e.g. polyarylethylketones, PEEK or PEK - C08J 2301/12: Cellulose acetate - C08J 2323/00: Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers - C08J 2371/10: from phenols - C08J 2400/10: Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups - C08J 2401/00: Characterised by the use of cellulose, modified cellulose or cellulose derivatives - C08J 2401/12: Cellulose acetate - C08J 2471/08: Polyethers derived from hydroxy compounds or from their metallic derivatives (C08J2471/02 takes precedence) - C08J 2471/10: from phenols - F24F 2003/1435: {comprising semi-permeable membrane} - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - D06M: TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS - D06N: WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR - F24F: AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING (removing dirt or fumes from areas where they are produced B08B15/00; vertical ducts for carrying away waste gases from buildings E04F17/02; tops for chimneys or ventilating shafts, terminals for flues F23L17/02) ## Abstract Water vapor transport membranes for ERV and other water vapor transport applications are provided. The membranes include a substrate and an air impermeable selective layer coated on the substrate, the selective layer including a cellulose derivative and a sulfonated polyaryletherketone. In some embodiments the sulfonated polyaryletherketone is in a cation form and/or the selective layer includes sPEEK and CA in an sPEEK:CA (wt.:wt.) ratio in the range of about 7:3 to 2:3. Methods for making such membranes are provided. The methods include applying a coating solution/dispersion to a substrate and allowing the coating solution/dispersion to dry to form an air impermeable selective layer on the substrate, the coating solution/dispersion including a cellulose derivative and a sulfonated polyarylether ketone. In some embodiments the sulfonated polyaryletherketone is in a cation form and/or the coating solution/dispersion includes sPEEK and CA in an sPEEK:CA (wt.:wt.) ratio in the range of about 7:3 to 2:3. ## Claims ### Claim 1 A water vapor transport membrane comprising a microporous substrate and an air impermeable selective layer coated on a first surface of the substrate, wherein the selective layer has a thickness of less than about 5 microns and wherein the selective layer comprises at least one cellulose derivative and at least one sulfonated polyaryletherketone, wherein the at least one sulfonated polyaryletherketone comprises a sulfonated polyaryletherketone in a cation form. ### Claim 2 (depends on 1) A water vapor transport membrane according to claim 1, wherein about 80% to about 100% of the at least one sulfonated polyaryletherketone is in the cation form. ### Claim 3 (depends on 1) A water vapor transport membrane according to claim 1, wherein the at least one cellulose derivative has lower water vapor permeability and is less water swellable than the at least one sulfonated polyaryletherketone, and wherein a weight-to-weight ratio of the at least one cellulose derivative and the at least one sulfonated polyaryletherketone in the selective layer results in a level of phase separation in the selective layer that causes swelling of the at least one sulfonated polyaryletherketone, upon exposure of the water vapor transport membrane to moisture, to be constrained by the at least one cellulose acetate derivative. ### Claim 4 (depends on 1) A water vapor transport membrane according to claim 1, wherein the at least one cellulose derivative comprises a cellulose derivative selected from the group consisting of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), and ethyl cellulose (EC). ### Claim 5 (depends on 4) A water vapor transport membrane according to claim 4, wherein the at least one sulfonated polyaryletherketone comprises sulfonated polyether ether ketone (sPEEK). ### Claim 6 (depends on 1) A water vapor transport membrane according to claim 1, wherein the selective layer comprises the at least one sulfonated polyaryletherketone and the at least one cellulose derivative in a sulfonated polyaryletherketone/cellulose derivative (wt.:wt.) ratio in the range of about 7:3 to about 2:3. ### Claim 7 (depends on 1) A water vapor transport membrane according to claim 1 wherein an acetyl content of the at least one cellulose derivative is in the range of about 20% to about 62%, and a degree of sulfonation of the at least one sulfonated polyaryletherketone is in the range of about 23% to about 100%. ### Claim 8 (depends on 1) A water vapor transport membrane according to claim 1, wherein the at least one sulfonated polyaryletherketone is polyether ether ketone (sPEEK), the at least one cellulose derivative is cellulose acetate (CA), a sPEEK:CA (wt.:wt.) ratio is in the range of about 9:1 to about 1:9, the acetyl content of the CA is in the range of about 20% to about 62%, and the degree of sulfonation of the sPEEK is in the range of about 23% to about 100%. ### Claim 9 (depends on 1) A water vapor transport membrane according to claim 1, wherein the selective layer is sufficiently flexible to allow pleating of the membrane without fracturing the selective layer. ### Claim 10 A method for making a water vapor transport membrane, the method comprising: applying a coating solution or dispersion to a first surface of a microporous substrate and allowing the coating solution or dispersion to dry to form an air impermeable selective layer on the substrate, the selective layer having a thickness of less than about 5 microns, wherein the coating solution or dispersion comprises at least one cellulose derivative and at least one sulfonated polyaryletherketone; and exchanging sulfonic acid group protons of the at least one sulfonated polyaryletherketone with cations. ### Claim 11 (depends on 10) A method according to claim 10, wherein about 80% to about 100% of the sulfonic acid group protons of the at least one sulfonated polyaryletherketone are exchanged for cations. ### Claim 12 (depends on 10) A method according to claim 10, wherein the at least one cellulose derivative has lower water vapor permeability and is less water swellable than the at least one sulfonated polyaryletherketone, and wherein a weight-to-weight ratio of the at least one cellulose derivative to the at least one sulfonated polyaryletherketone in the selective layer is selected such that there is a level of phase separation in the selective layer that causes swelling of the at least one sulfonated polyaryletherketone, upon exposure of the water vapor transport membrane to moisture, to be constrained by the at least one cellulose derivative. ### Claim 13 (depends on 10) A method according to claim 10, wherein the at least one cellulose derivative comprises a cellulose derivative selected from the group consisting of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), and ethyl cellulose (EC). ### Claim 14 (depends on 13) A method according to claim 13, wherein the at least one sulfonated polyaryletherketone comprises sulfonated polyether ether ketone (sPEEK). ### Claim 15 (depends on 10) A method according to claim 10, wherein the coating solution or dispersion comprises the at least one sulfonated polyaryletherketone and the at least one cellulose derivative in a sulfonated polyaryletherketone/cellulose derivative (wt.:wt.) ratio in the range of about 7:3 to about 2:3. ### Claim 16 (depends on 10) A method according to claim 10, wherein an acetyl content of the at least one cellulose derivative is in the range of about 20% to about 62%, and the degree of sulfonation of the at least one sulfonated polyaryletherketone is in the range of about 23% to about 100%. ### Claim 17 (depends on 10) A method according to claim 10, wherein the at least one sulfonated polyaryletherketone is sulfonated polyether ether ketone (sPEEK) and the at least one cellulose derivative is cellulose acetate (CA), wherein a sPEEK:CA (wt.:wt.) ratio in the coating solution or dispersion is in the range of about 9:1 to about 1:9, an acetyl content of the CA is in the range of about 20% to about 62%, and a degree of sulfonation of the sPEEK is in the range of about 23% to about 100%. ### Claim 18 An energy recovery ventilation (ERV) core comprising a pleated membrane cartridge, the membrane cartridge comprising a plurality of layers of a water vapor transport membrane, the water vapor transport membrane comprising a microporous substrate and an air impermeable selective layer coated on a first surface of the substrate, wherein the selective layer has a thickness of less than about 5 microns and wherein the selective layer comprises at least one cellulose derivative and at least one sulfonated polyaryletherketone, the ERV core having gas flow pathways in between adjacent ones of the membrane layers.