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EP-4741051-A2 - POLYMER COMPOSITIONS CONTAINING ZEOLITE FOR ENHANCED WATER ADSORPTION

EP4741051A2EP 4741051 A2EP4741051 A2EP 4741051A2EP-4741051-A2

Abstract

This invention relates generally to zeolites and polymer compositions with zeolites having enhanced adsorption capacity for adsorption of water, ammonia and other similar compounds. The invention is directed particularly to aluminosilicate zeolites, and methods for preparing zeolite entrained polymer compositions having enhanced water adsorption properties. This invention relates also to improved packaging materials with enhanced water adsorption properties incorporating the polymer compositions containing zeolites.

Inventors

  • TAHRAOUI, Zakaria
  • FORLER, Patrice
  • DAOU, Jean
  • MARICHAL, Claire
  • NOUALI, Habiba

Assignees

  • CSP Technologies, Inc.
  • Le Centre National De La Recherche Scientifique
  • L'Université de Haute Alsace

Dates

Publication Date
20260513
Application Date
20200331

Claims (17)

  1. A process for making a polymer composition for enhanced sorption, the process comprising the steps of: (a) providing a crude sodium zeolite which is a crude sodium aluminosilicate or crude sodium silicoaluminophosphate zeolite; (b) treating the crude sodium zeolite with a solution comprising Mg 2+ , Li + , K + , Ca + , Zn 2+ , Mn 2+ , or Fe 3+ cations, or a combination thereof, to form a treated cation exchanged sodium zeolite; (c) optionally, repeating step (b) one or more times; (d) drying the treated cation exchanged sodium zeolite to provide a dried cation exchanged sodium zeolite, having an absorption or adsorption capacity for one or more of ammonia, nitrogen, oxygen or water that is greater than the absorption or adsorption capacity of the crude sodium zeolite before cation exchange treatment; (e) optionally, repeating step (b) and step (c) one or more times; (f) adding and blending the dried cation exchanged sodium zeolite with a base polymer; and (g) forming the polymer composition.
  2. The process of claim 1, wherein the crude sodium zeolite is an LTA-type or FAU-type.
  3. The process of claim 1 or 2, wherein the solution for cation exchange comprises Mg 2+ cations, Li + cations, or a combination thereof, and the adsorption capacity of the dried cation exchanged sodium zeolite for water is from at least 1% to 33% greater than the water adsorption capacity of the crude sodium zeolite before cation exchange treatment.
  4. The process of any of claims 1 to 3, wherein the solution comprises MgCl2 or LiCl.
  5. The process of any of the previous claims, wherein the dried cation exchanged sodium zeolite is added to the base polymer in powder form.
  6. The process of any of the previous claims, wherein the concentration of the dried cation exchanged sodium zeolite within the polymer composition is in the range of 30 % to 60 % by weight with respect to the total weight of the polymer composition.
  7. The process of any of the previous claims, wherein the base polymer is selected from polypropylene, polyethylene, polyhydroxyalkanoate (PHA), polylactic acid (PLA), polybutylene succinate (PBS), polyisoprene, polyhexene, polybutadiene, polybutene, polysiloxane, polycarbonate, polyamide, ethylene-vinyl acetate copolymer, ethylene-methacrylate copolymer, polyvinyl chloride (PVC), polystyrene, polyester, polyanhydride, polyacrylnitrile, polysulfone, polyacrylic ester, acrylic, polyurethane, polyacetal, polyvinylpyrrolidone (PVP), a copolymer, or a combination thereof.
  8. The process of any of the previous claims, further comprising adding a channeling agent to the base polymer and mixing the channeling agent with the base polymer, thus forming an entrained polymer with channels, wherein the dried cation exchanged sodium zeolite is entrained in the entrained polymer, the channeling agent being a material that is immiscible with the base polymer and able to transport a gas phase substance at a faster rate than the base polymer.
  9. The process of claim 8, wherein the amount of the channeling agent is in a range from 2% to 15% by weight with respect to the total weight of the polymer composition.
  10. The process of claim 8 or 9, wherein the channeling agent is selected from polyethylene glycol (PEG), ethylene-vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane, polycarboxylic acid, propylene oxide polymerisate-monobutyl ether, propylene oxide polymerisate, ethylene vinyl acetate, nylon 6, nylon 66, or a combination thereof.
  11. A polymer composition for enhanced sorption, the polymer composition comprising: (a) a cation exchanged sodium zeolite which is a cation exchanged sodium aluminosilicate or sodium silicoaluminophosphate zeolite, comprising one or more cations selected from Mg 2+ , Li + , K + , Ca + , Zn 2+ , Mn 2+ , or Fe 3+ ; and (b) a base polymer, wherein the cation exchanged sodium aluminosilicate or sodium silicoaluminophosphate zeolite has an absorption or adsorption capacity for one or more of ammonia, nitrogen, oxygen or water that is greater than the absorption or adsorption capacity absent of a cation exchange treatment.
  12. The polymer composition of claim 11, wherein the cation exchanged sodium zeolite comprises magnesium, lithium or both and wherein the adsorption capacity of the cation exchanged sodium zeolite for water is from at least 1% to 33% greater than the adsorption capacity of the sodium zeolite before cation exchange treatment.
  13. The polymer composition of claim 11 or claim 12, wherein the polymer composition is in the form of a powder, a granule, a bead, a pellet, a film, a sheet, a disk, a cover, a plug, a cap, a lid, an insert, a stopper, a gasket, a seal, a washer, a liner, a ring, a container or a package.
  14. The polymer composition of any of claims 11 to 13, prepared by the process of any of the claims 1 to 10.
  15. Use of the polymer composition of any of claims 11 to 14 as a dessicant, preferably in a dehumidifier or in an adsorption heat pump.
  16. Use of the polymer composition of any of claims 11 to 14 to remove, reduce, scavenge, control or modify the amount of water in an environment.
  17. A packaging material comprising the polymer composition of any of claims 11 to 14, wherein the material is selected from plastic, paper, glass, metal, ceramic, synthetic resin or a combination thereof.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. § 119(e) from U.S. Provisional Patent Application No. 62/961,024, entitled "ZEOLITE WITH ENHANCED WATER ADSORPTION", filed January 14, 2020; from U.S. Provisional Patent Application No. 62/961,038, entitled "COMPOSITES CONTAINING ZEOLITE FOR ENHANCED WATER ADSORPTION", filed January 14, 2020; and U.S. Provisional Patent Application 62/827,332, entitled "ZEOLITE WITH ENHANCED WATER ADSORPTION", filed on April 1, 2019; of which the contents of all three applications are incorporated herein by reference in their entirety. FIELD OF THE INVENTION This invention relates generally to zeolites and polymer compositions with zeolites having enhanced adsorption capacity for adsorption of water, ammonia, nitrogen and oxygen. The invention is directed particularly to aluminosilicate zeolites, and methods for preparing zeolite entrained polymer compositions having enhanced water adsorption properties. This invention relates also to improved packaging materials with enhanced water adsorption properties incorporating the polymer compositions containing zeolites. BACKGROUND OF THE INVENTION The adsorption of water by materials is important for many applications which necessitate capture and release of water such as dehumidifiers, adsorption heat pumps, various specialized packaging and others. One of the most promising adsorption heat pump technologies in this context is based on the evaporation and consecutive adsorption of water, under specific conditions. Water content in natural gas is an important concern in adsorption heat pumps because it can cause corrosion and hydrate formation ending in pipeline blockage. Highly humid environments encourage house dust mites and provide favorable environments for the growth of fungi and various harmful bacteria. Atmospheric relative humidity is an important factor affecting health. Dehumidifying materials continue to be needed for home and commercial environments to control moisture conditions and reduce the levels of harmful microorganisms. The need for moisture removal technology and moisture controlled packaging is also important for improving the quality and safe storage of processed foods, drugs and cosmetics. The shipping and storage of moisture sensitive materials such as electronic components and ammunition also require moisture controlled packaging. Environmental decontamination and clean-up efforts also require the use of adsorbent technologies and a need for such clean technologies continues to grow as the number and complexity of industrial processes worldwide increases. Therefore, a demand continues to exist for controlling humidity and development of high efficiency sorbent technology including new and effective adsorbent materials is needed. Several strategies have been used to remove water vapor from gas streams involving the use of a solid or liquid desiccants, membranes, refrigeration, and supersonic methods. One of the most effective strategies remains the use of a solid porous beds incorporating a porous desiccant having effective properties for removing water vapor from a gaseous mixture. A variety of porous materials such as zeolites, metal organic frameworks, clays, carbon based adsorbents, and organic polymers have been explored for various applications. Polymeric membranes for gas separation such as natural gas sweetening, landfill gas recovery, hydrogen recovery and purification, flue gas and air separation is one of the most important applications which uses inorganic porous and nonporous materials dispersed into a polymer matrix. Fillers such as metal organic frameworks (MOFs), activated carbon (AC), mesoporous silica (MS), as well as zeolites have been incorporated into polymers in order to confer certain adsorption, permeability and selectivity to composite materials. Zeolites are compounds that act as molecular sieves and are widely used for their high adsorption properties and their thermal, chemical and mechanical stabilities. Zeolites are known for their hygroscopic properties. They are used for drying solutions, for dehumidifying closed spaces, as well as for drying textiles after the washing process, and as drying components for dishes in dishwashers. US Patent No. 8,904,667 teaches drying solutions based on zeolitic materials with thermal management comprising a titano-alumino-phosphate as adsorbent for energy-improved drying of objects such as textiles, and its production. The first prototypes of adsorption heat or cooling pumps used adsorbent beds made of zeolite loose grains. Zeolite based materials are also used in powder form for the removal of polluting cations present in waste water. The selectivity of zeolites is also particularly used for odors removal due to its ability to adsorb volatile organic compounds at trace levels in the atmosphere. Zeolite based composites for water removal thus present a great area of interest. Zeolites are crystalline al