EP3870338A1 - Katalysatoradsorbierender filter zur luftreinigung - Google Patents

Katalysatoradsorbierender filter zur luftreinigung

Info

Publication number
EP3870338A1
EP3870338A1 EP19877095.0A EP19877095A EP3870338A1 EP 3870338 A1 EP3870338 A1 EP 3870338A1 EP 19877095 A EP19877095 A EP 19877095A EP 3870338 A1 EP3870338 A1 EP 3870338A1
Authority
EP
European Patent Office
Prior art keywords
adsorbent
catalyst
filter
poly
certain embodiments
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19877095.0A
Other languages
English (en)
French (fr)
Other versions
EP3870338A4 (de
Inventor
Ting GU
Chen Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Corp filed Critical BASF Corp
Priority claimed from PCT/US2019/057348 external-priority patent/WO2020086525A1/en
Publication of EP3870338A1 publication Critical patent/EP3870338A1/de
Publication of EP3870338A4 publication Critical patent/EP3870338A4/de
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407Constructional details of adsorbing systems
    • B01D53/0415Beds in cartridges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/16Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B01D39/1669Cellular material
    • B01D39/1676Cellular material of synthetic origin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042Shaped bodies; Monolithic structures
    • B01J20/28045Honeycomb or cellular structures; Solid foams or sponges
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    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
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    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing
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    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206Organic carriers, supports or substrates
    • B01J20/3208Polymeric carriers, supports or substrates
    • B01J20/3212Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234Inorganic material layers
    • B01J20/3236Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234Inorganic material layers
    • B01J20/3238Inorganic material layers containing any type of zeolite
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234Inorganic material layers
    • B01J20/324Inorganic material layers containing free carbon, e.g. activated carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656Manganese, technetium or rhenium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0407Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2239/00Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04Additives and treatments of the filtering material
    • B01D2239/0471Surface coating material
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2239/10Filtering material manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/102Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2253/106Silica or silicates
    • B01D2253/108Zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/112Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124Metal oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01DSEPARATION
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    • B01D2253/25Coated, impregnated or composite adsorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/207Transition metals
    • B01D2255/2073Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/915Catalyst supported on particulate filters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/92Dimensions
    • B01D2255/9207Specific surface
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • the present disclosure relates to compositions, devices, and methods for air purification. More particularly, the disclosure relates to catalyst-adsorbent compositions, devices, and systems, methods of their preparation, and methods of their use for room
  • Atmospheric pollution is a concern of increasing importance as the level s of various atmospheric pollutants continue to increase.
  • Formaldehyde, nitrogen oxides, sulfur dioxide, and ammonia are regarded as major pollutants for which various sorbent systems and materials are used to remove them from indoor environments.
  • sorbent materials are generally adapted for one type of adsorption application, while being unable to remove other types of pollutants.
  • Current cathode air purification technology for example, requires two separate layers for the removal of basic and acidic chemical contaminants, thus requiring more complex design.
  • nonwoven filter systems that utilize carbon pellets result in high backpressure that has a detrimental effect on performance.
  • a catalyst-adsorbent filter comprises: a filter body comprising a material selected from polymeric foam, polymeric fiber, non-woven fabric, a ceramic, and pulp products (e.g., paper); and a coating formed on the filter body.
  • the coating comprises: a manganese oxide catalyst adapted for converting gaseous pollutants into chemically-benign species; and an adsorbent adapted for adsorbing the chemically-benign species and other gaseous species for which the manganese oxide catalyst is not adapted to convert.
  • the adsorbent is selected from a group consisting of: silica gel, activated carbon, faujasite, chabazite, clinoptilolite, mordenite, silicalite, zeolite X, zeolite Y, ultrastable zeolite Y, ZSM zeolite, offretite, beta zeolite, metal organic frameworks, metal oxide, polymers, resins, and combinations thereof.
  • the adsorbent comprises activated carbon.
  • the activated carbon is synthetic activated carbon or is based on or derived from one or more of wood, peat coal, coconut shell, lignite, petroleum pitch, petroleum coke, coal tar pitch, fruit pits, nuts, shells, sawdust, wood flour, synthetic polymer, or natural polymer.
  • a Brunauer-Emmett-Teller (BET) surface area of the adsorbent is from about 20 m 2 /g to about 3,000 m 2 /g.
  • a wei ght-to- wei ght ratio of the manganese oxide to the adsorbent is from 1 :5 to 7: 1.
  • the coating further comprises a polymeric binder
  • the polymeric binder is selected from a group consisting of: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, poly(vinyl ester), poly(vinyl halide), polyamide, cellulosic polymer, polyimide, acrylic polymer, vinyl acrylic polymer, styrene acrylic polymer, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, po!y(phenylene oxide), poiyfphenylene sulfide), fluorinated polymer, poly(tetrafluoroethylene) polyvinylidene fluoride,
  • the polymeric binder is present from about 5 wt. % to about 30 wt. % with respect to a total weight of the coating.
  • the coating further comprises a dispersant.
  • the dispersant comprises one or more of an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant.
  • the filter body comprises a polymeric foam comprising polyurethane.
  • the filter body is in a form of a honeycomb.
  • a catalyst-adsorbent composition comprises: an adsorbent comprising activated carbon; a catalyst comprising manganese oxide; a polymeric binder; and a surfactant dispersant.
  • a method of forming a catalyst- adsorbent filter comprises: forming a slurry comprising a metal oxide catalyst and an adsorbent; coating the slurry onto a filter body comprising a material selected from polymeric foam, polymeric fiber, non-woven fabric, a ceramic, and pulp products (e.g., paper); and drying the slurry to form the catalyst-adsorbent filter.
  • the drying occurs at a temperature from about 80 °C to about 250 °C.
  • the adsorbent comprises activated carbon, and a BET surface area of the adsorbent is from about 20 m 2 /g to about 3,000 m7g.
  • the metal oxide catalyst comprises manganese oxide, a weight-to-weight ratio of the manganese oxide to the adsorbent is from 1 : 5 to 7: 1.
  • the slurry further comprises a polymeric binder.
  • the polymeric binder is present from about 5 wt. % to about 30 wt. % with respect to a total weight of the coating.
  • the polymeric binder is selected from a group consisting of: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, nitrile rubber, poly chi oroprene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylate,
  • polyacrylonitrile poly (vinyl ester), poly(vinyl halide), polyamide, cellulosic polymer, polyimide, acrylic polymer, vinyl acrylic polymer, styrene acrylic polymer, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, poly(phenylene oxide), poly(phenylene sulfide), fluorinated polymer, polyftetrafluoroethylene) polyvinyl! dene fluoride, poly(vinylfluoride) chloro/fluoro copolymer, ethylene chlorotrifluoroethylene copolymer, polyamide, phenolic resin, epoxy resin, polyurethane, acrylic/styrene acrylic copolymer, latex, silicone polymer, and combinations thereof.
  • the slurry further comprises a dispersant, and the dispersant comprises one or more of an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant.
  • the filter body comprises a polymeric foam comprising polyurethane.
  • a catalyst-adsorbent filter comprises: a filter body comprising a material selected from polymeric foam, polymeric fiber, non-woven fabric, a ceramic, and pulp products (e.g., paper); and a coating formed on the filter body.
  • the coating comprising: a manganese oxide catalyst adapted for converting gaseous pollutants into chemica!ly-benign species; an adsorbent adapted for adsorbing the chemica!ly-benign species together with other gaseous species and volatile organic compounds; a polymeric binder; and a dispersant
  • a volatile organic compound (VOC) scrubbing system comprises any embodi ments of the aforementioned catalyst-adsorbent arranged to contact air received into the VOC scrubbing system.
  • the VOC scrubbing system comprises one or more filtration cartridges having the catalyst-adsorbent disposed therein and arranged to contact a flow of air received into the VOC scaibbing system.
  • Any embodiments of the aforementioned catalyst-adsorbent may be disposed within the one or more filtration cartridges.
  • a method for treating air comprising a pollutant selected from SO 2, NH 3, N0 2 , NO, and formaldehyde, the method comprising flowing a first volume of air into an air treatment chamber that comprises any embodiments of the aforementioned catalyst-adsorbent, the first volume of air having a first concentration of the pollutant, and contacting the sorbent with the first volume of air, wherein a second concentration of the pollutant of the first volume of air is less than or equal to the fi rst concentration after the contacting.
  • the first volume of air comprises recirculated air from an interior of a building.
  • the method further comprises flowing a second volume of air into the air treatment chamber, the second volume of air having a third
  • the second volume of air comprises air from outside of the building.
  • an automobile ventilation system comprises a component (e.g., a filter, filter unit, container, air duct, etc.) that comprises any embodiments of the aforementioned catalyst-adsorbent disposed within the component.
  • a component e.g., a filter, filter unit, container, air duct, etc.
  • an aircraft environmental control system comprises a filter unit that comprises any embodiments of the aforementioned catalyst- adsorbent disposed within the filter unit
  • a cathode air filter for a fuel cell system comprises a filter unit that comprises any embodiments of the aforementioned catalyst- adsorbent disposed within the filter unit.
  • Such cathode air filters system may be incorporated into, for example, fuel cell systems for vehicles, homes, or industrial use
  • an air control system for removing a pollutant from atmospheric air comprises a filter unit that comprises any embodiments of the aforementioned sorbent disposed within the filter unit.
  • the term“adsorbent material” refers to a material that can adhere gas molecules, ions, or other species within its structure (e.g., removal of C0 2 from air).
  • Specific materials include but are not limited to clays, metal organic framework, activated alumina, silica gel, activated carbon, molecular sieve carbon, zeolites (e g., molecular sieve zeolites), polymers, resins, and any of these components or others having a gas-adsorbing material supported thereon (e.g., such as the various embodiments of sorbents described herein). Certain adsorbent materials may preferentially or selectively adhere particular species.
  • the term“catalyst-adsorbent” refers to a material that has dual catalytic and adsorptive properties.
  • a catalyst-adsorbent layer upon contact with a molecular species, may catalyze the conversion of the molecular species into one or more byproducts, and may also be capable of adsorbing the molecular species and/or the one or more byproducts.
  • the catalyst-adsorbent layer may also be capable of adsorbing other molecular species that cannot be reacted cataiytically by the catalyst-adsorbent layer.
  • adsorption capacity refers to a working capacity for an amount of a chemical species that an adsorbent material can adsorb under specific operating conditions (e.g., temperature and pressure).
  • the units of adsorption capacity when given in units of mg/g, correspond to milligrams of adsorbed gas per gra of sorbent.
  • the term“particles” refers to a collection of discrete portions of a material each having a largest dimension ranging from 0.1 mhi to 50 mm.
  • the morphology of particles may be crystalline, semi-crystalline, or amorphous.
  • the size ranges disclosed herein can be mean/average or median size, unless otherwise stated. It is noted also that particles need not be spherical, but may be in a form of cubes, cylinders, discs, or any other suitable shape as W'Ould be appreciated by one of ordinary' skill in the art.
  • “Powders” and“granules” may be types of particles.
  • the terra“monolith” refers to a single unitary block of a particular material.
  • the single unitary block can be in the form of, e g., a brick, a disk, or a rod and can contain channels for increased gas flow/distribution.
  • multiple monoliths can be arranged together to form a desired shape.
  • a monolith may have a honeycomb shape with multiple parallel channels each having a square shape, a hexagonal shape, or another other shape.
  • the term“dispersant” refers to a compound that helps to maintain solid particles in a state of suspension in a fluid medium, and inhibits or reduces agglomeration or settling of the particles in the fluid medium.
  • the terra“binder” refers to a material that, when included in a coating, layer, or film (e.g., a washcoated coating, layer, or film on a substrate), promotes the formation of a continuous or substantially continuous structure from one outer surface of the coating, layer, or film through to the opposite outer surface, is homogeneously or semi- homogeneously distributed in the coating, layer, or film, and promotes adhesion to a surface on which the coating, layer, or film is formed and cohesion between the surface and the coating, layer, or film.
  • a coating, layer, or film e.g., a washcoated coating, layer, or film on a substrate
  • the terms“stream” or“flow” broadly refer to any flowing gas that may contain solids (e.g., particulates), liquids (e.g., vapor), and/or gaseous mixtures.
  • volatile organic compounds or“VOCs” refer to organic chemical molecules having an elevated vapor pressure at room temperature. Such chemical molecules have a low boiling point and a large number of the molecules evaporate and/or sublime at room temperature, thereby transitioning from a liquid or solid phase to a gas phase.
  • VOCs include, but are not limited to, formaldehyde, benzene, toluene, xylene, ethylbenzene, styrene, propane, hexane, cyclohexane, limonene, pinene, acetaldehyde, hexaldehyde, ethyl acetate, butanol, and the like.
  • the terms“unpurified air” or“unpurified air stream” refer to any stream that contains one or more pollutants at a concentration or content at or above a level that is perceived as nuisance, is considered to have adverse effects on human health (including short term and/or long term effects), and/or causes adverse effects in the operation of equipment.
  • Occupational Safety & Health Administration is an unpurified air stream.
  • a stream that contains formaldehyde at a concentration greater than 0.08 part formaldehyde per million parts of air stream calculated as an eight hour time weighted average concentration pursuant to national standards in China is an unpurified air stream.
  • Unpurified air may include, but is not limited to, formaldehyde, ozone, carbon monoxide (CO), VOCs, methyl bromide, water, amine-containing compounds (e.g., ammonia), sulfur oxides, hydrogen sulfide, and nitrogen oxides.
  • purified air or“purified air stream” refer to any stream that contains one or more pollutants at a concentration or content that is lower than the concentration or content of the one or more pollutants in what would be considered an unpurified air stream.
  • the term“substrate” refers to a material (e.g., a metal, semi- metal, semi-metal oxide, metal oxide, polymeric, ceramic, paper, pul p/semi -pulp products, etc.) onto or into which the catalyst is placed.
  • the substrate may be in the form of a solid surface having a washcoat containing a plurality of catalytic particles and/or adsorbent particles.
  • a washcoat may be formed by preparing a slurry containing a specified solids content (e.g., 30-50% by weight) of catalytic particles and/or adsorbent particles, which is then coated onto a substrate and dried to provide a washcoat layer.
  • the substrate may be porous and the washcoat may be deposited outside and/or inside the pores.
  • nitrogen oxide refers to compounds containing nitrogen and oxygen including but not limited to, nitric oxide, nitrogen dioxide, nitrous oxide, nitrosylazide, ozatetrazole, dinitrogen trioxide, dinitrogen tetroxide, dinitrogen pentoxide, trinitramide, nitrite, nitrate, nitronium, nitrosonium, peroxonitrite, or combinations thereof.
  • sulfur compounds refers to compounds containing sulfur including but not limited to sulfur oxides (sulfur monoxide, sulfur dioxide, sulfur trioxide, disulfur monoxide, disulfur dioxide), hydrogen sulfide, or combinations thereof.
  • the term“about,” as used in connection with a measured quantity refers to the normal variations in that measured quantity, as expected by the skilled artisan making the measurement and exercising a level of care commensurate with the objective of measurement and the precision of the measuring equipment. For example, when“about” modifies a value, it may be interpreted to mean that the value can vary by ⁇ 1%.
  • BET BET method according to DIN ISO 9277:2003-05 (which is a revised version of DIN 66131), which is referred to as“BET surface area.”
  • the specific surface area is determined by a multipoint BET measurement in the relative pressure range from 0.05-0.3 p!p .
  • FIG. 1 depicts an illustrative air-flow system in accordance with an embodiment of the disclosure
  • Fig. 2A depicts a cross-section of a filter body having a catalyst-adsorbent coating formed thereon in accordance with an embodiment of the disclosure
  • Fig. 2B depicts a cross-section of a catalyst-adsorbent coating formed on a surface of a filter body in accordance with an embodiment of the disclosure.
  • Fig 3 is a flow diagram illustrating a method of forming a catalyst-adsorbent filter sorbent in accordance with an embodiment of the disclosure.
  • the embodiments described herein relate to catalyst-adsorbent compositions and systems for removing pollutants from air. More specifically, the catalyst-adsorbent compositions may be incorporated into indoor air, cabin air, and cathode air purification systems, which may be designed to remove toxic chemical pollutants such as formaldehyde, ozone, carbon monoxide, nitrogen oxides, sulfur dioxide, amines (including ammonia), sulfur compounds (including thiols), chlorinated hydrocarbons, and other alkali or acidic chemicals.
  • toxic chemical pollutants such as formaldehyde, ozone, carbon monoxide, nitrogen oxides, sulfur dioxide, amines (including ammonia), sulfur compounds (including thiols), chlorinated hydrocarbons, and other alkali or acidic chemicals.
  • a high surface area adsorbent e.g., activated carbon
  • a metal oxide catalyst e.g , manganese oxide
  • the catalyst-adsorbent composition may be coated onto a filter body, such as an open-pored foam, honeycomb, or nonwoven filter body, to increase filtration efficiency and facilitate acceptable backpressure.
  • the embodiments of the present disclosure allow for air purification at low 7 temperatures (e.g., room temperature ranges from 20 °C to 25 °C) without requiring heating of the unpurified air or catalyst-adsorbent filter.
  • low 7 temperatures e.g., room temperature ranges from 20 °C to 25 °C
  • the materials and relatively low temperatures utilized in forming the catalyst-adsorbent composition allow for a broader range of filters, such as polymeric foam materials, that would otherwise be incompatible with higher temperature processes used for coating metallic filters.
  • the embodiments of the present disclosure further allow for effective catalysis without the use of ultra-violet (UV) radiation or electricity, and are free of photo-catalytic chemistry.
  • the embodiments of the present disclosure further allow for the formation of catalyst-adsorbent filters that are free of detectable odors even after long term operation.
  • Fig. 1 depicts an illustrative air-flow system 100 in accordance with an embodiment of the disclosure.
  • the system 100 includes a filter unit 104 and an HVAC system 106 installed as part of a building 102.
  • the filter scrubber unit 104 and the HVAC system 106 are fluidly coupled to each other and to the interior air space of the building 102 such that a recirculation air flow' path 108 is established.
  • various pollutants such as VOCs
  • interior air is recirculated through the filter unit 104 to catalyze and/or adsorb the pollutants using a catalyst-adsorbent filter, as described herein.
  • Purified air then passes through the HVAC system 106, which may be further filtered (e.g., to remove dust and other particulates) and may be heated or cooled before being recirculated back into the building 102.
  • system 100 is merely illustrative, and it is to be understood that the embodiments of catalyst-adsorbent filters described herein may be incorporated into other systems for treating air, such as an automobile ventilation system, and aircraft
  • an air control system for treating atmospheric air an air control system for treating atmospheric air
  • humidifying/dehumidifying systems odor removal systems
  • VGC scrubbing systems treatment systems for cathode air in fuel cell systems for cars, homes, or industrial use, and other systems.
  • Figs. 2A and 2B depict a cross-sections of a catalyst-adsorbent filter 200 formed in accordance with an embodiment of the disclosure.
  • the catalyst-adsorbent filter 200 includes a filter body 210, which is illustrated as being in a form of a honeycomb filter with air
  • the catalyst-adsorbent filter 200 further includes a catalyst-adsorbent composition coated onto interior walls of the filter body 200.
  • the filter body may be in the form of an open-pored foam, a honeycomb, or a nonwoven filter body.
  • a material of the filter body may be ceramic (e.g., porous ceramic), metallic, polymeric foam, plastic, paper, fibrous (e.g., polymeric fiber), or combinations thereof.
  • the filter body may be formed from polyurethane fibers or a polyurethane foam.
  • the filter body may be a metallic monolithic filter body, a ceramic monolithic filter body, a paper filter body, a polymer filter body, or a ceramic fiber monolithic substrate.
  • the filter body may be an HVAC duct, an air filter, or a louver surface in certain embodiments, the filter body may be a portable air filter, or a filter disposed in a vehicle, such as a motor vehicle, railed vehicle, watercraft, aircraft, or space craft.
  • the catalyst-adsorbent composition may be formulated as a slurry and washcoated onto the filter body.
  • a loading of the catalyst- adsorbent composition on the filter body may range from about 0.5 g/in 3 to about 4 g/in 3 with respect to a volume of the filter body.
  • the catalyst-adsorbent composition may be coated onto the filter body and may form a single catalyst-adsorbent layer on the solid substrate or a plurality of catalyst-adsorbent layers. If a plurality of catalyst- adsorbent layers is coated on the solid substrate, the layers may vary in their compositions or alternatively all catalyst-adsorbent layers may have the same composition.
  • the catalyst of the catalyst-adsorbent composition may comprise a catalytic metal oxide.
  • the catalytic metal oxide may include one or more of manganese oxide, cobalt oxide, molybdenum oxide, chromium oxide, copper oxide, or cerium oxide.
  • the metal oxide may be a rare earth metal oxide.
  • the catalytic metal oxide is manganese oxide.
  • the manganese oxide is amorphous or at least partially amorphous.
  • the manganese oxide is semi-crystalline.
  • the manganese oxide may comprise cryptomelane, birnessite, vemadite, manganese oxide polymorph I, poorly crystalline cryptomelane, amorphous manganese oxide, polymorphs thereof, amorphous manganese oxide, or mixtures thereof.
  • the metal oxide catalyst is present from about 10 wt. % to about 90 wt. %, from about 20 wt. % to about 90 wt. %, from about 30 wt. % to about 90 wt. %, from about 30 wt. % to about 80 wt. %, from about 40 wt. % to about 80 wt. %, or from about 40 wt. % to about 70 wt. % based on a total weight of the catalyst-adsorbent composition.
  • the adsorbent of the catalyst-adsorbent composition comprises an adsorbent selected from silica gel, activated carbon, faujasite, chabazite, clinoptilolite, mordenite, siiicaiite, zeolite X, zeolite Y, ultrastable zeolite Y, ZSM zeolite (e.g., ZSM-5, ZSM-l 1), offretite, beta zeolite, metal organic frameworks, metal oxide, polymers, resins, and combinations thereof.
  • an adsorbent selected from silica gel, activated carbon, faujasite, chabazite, clinoptilolite, mordenite, siiicaiite, zeolite X, zeolite Y, ultrastable zeolite Y, ZSM zeolite (e.g., ZSM-5, ZSM-l 1), offretite, beta zeolite, metal organic frameworks, metal oxide,
  • the adsorbent may include an adsorbent material may include a primary adsorbent (such as one or more discussed above) on a supporting material, such as carbon, an oxide (e.g., alumina, silica), or zeolite.
  • a primary adsorbent such as one or more discussed above
  • a supporting material such as carbon, an oxide (e.g., alumina, silica), or zeolite.
  • the adsorbent comprises activated carbon.
  • the activated carbon may be synthetic activated carbon or based on or derived from wood, peat coal, coconut shell, lignite, petroleum pitch, petroleum coke, coal tar pitch, fruit pits, nuts, shells, sawdust, wood flour, synthetic polymer, natural polymer, and combinations thereof.
  • the adsorbent includes a plurality of porous particles in a powder form. In certain embodiments, an average size of the particles/powder ranges from about 1.0 pm to about 100 pm. In certain embodiments, the average size ranges from about 5.0 pm to about 50 pm. In certain embodiments, a BET surface area of the adsorbent is from about 20 m 2 /g to about 3,000 m 2 /g, or greater.
  • the BET surface area of the adsorbent is from about
  • the BET surface area of the adsorbent is from about 100 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 250 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 500 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 600 m 2 /g to about 3,000 m 2 /g.
  • the BET surface area of the adsorbent is from about 700 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 800 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is fro about 900 m 2 /g to about 3,000 m7g. In certain embodiments, the BET surface area of the adsorbent is from about 1,000 m 2 /g to about 3,000 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,000 m 2 /g to about 2,750 m 2 /g.
  • the BET surface area of the adsorbent is from about 1,000 m7g to about 2,500 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,100 m 2 /g to about
  • the BET surface area of the adsorbent is from about 1,200 m 2 /g to about 2,500 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,300 m 2 /g to about 2,500 m7g. In certain embodiments, the BET surface area of the adsorbent is from about 1,400 m 2 /g to about 2,500 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,500 m7g to about 2,500 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,600 m 2 /g to about
  • the BET surface area of the adsorbent is from about 1,700 m 2 /g to about 2,500 m7g. In certain embodiments, the BET surface area of the adsorbent is from about 1,800 m /g to about 2,500 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,800 2 /g to about 2,400 m 2 /g. In certain embodiments, the BET surface area of the adsorbent is from about 1,800 nr/g to about 2,300 m 2 /g
  • the adsorbent is activated carbon having a BET surface area from about 1,000 m7g to about 2,500 m 2 /g. In certain embodiments, the adsorbent is activated carbon having a BET surface area from about 1,800 nT/g to about 2,300 m 2 /g.
  • the adsorbent can be activated.
  • the activation may include subjecting the adsorbent (e g., particles) to various conditions including, but not limited to, ambient temperature, vacuum, an inert gas flow, or any combination thereof, for a sufficient time to activate the adsorbent.
  • the adsorbent may be activated by calcining.
  • a weight-to-weight ratio of the manganese oxide to the adsorbent is from 1 : 1 to 7 : 1. In certain embodiments, the weight-to-weight ratio is from 2: 1 to 5: 1. In certain embodiments, the weight-to-weight ratio may be 1 : 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, or any combination of subranges defined therebetween. In certain embodiments, the weight-to- weight ratio may be 1 : 1 to 1 :5. In certain embodiments, the weight-to-weight ratio may be 1: 1, 1 :2, 1 :3, 1 :4, 1 :5, or any combination of subranges defined therebetween.
  • the catalyst-adsorbent composition may further comprise a binder.
  • suitable binders may include but are not limited to: polyethylene, polypropylene, polyolefin copolymers, polyisoprene, polybutadiene, polybutadiene copolymers, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomers, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, polyfvinyl esters), poly (vinyl halides), polyamides, cellulosic polymers, polyimides, acrylics, vinyl acrylics, styrene acrylics, polyvinyl alcohols, thermoplastic polyesters, thermosetting polyesters, poly(phenylene oxide), polytphenylene sulfide), fluorinated polymers such as poly(tetrafluoroethylene), polyvinylidene fluoride, poly(vinlyfluor
  • chlorotrifluoroethylene copolymer polyamide, phenolic resins, polyurethane, acrylic/styrene acrylic copolymer latex and silicone polymers.
  • the binder is a polymeric binder selected from:
  • the binder comprises an aery lie/ styrene copolymer latex and polyurethane dispersion
  • the binder, or mixture of binders is present from about
  • the polymeric binder is
  • I D present from about 10 wt % to about 30 wt. %, from about 15 wt. % to about 30 wt. %, from about 5 wt. % to about 25 wt. %, from about 5 wt. % to about 20 wt. %, from about 10 wt. % to about 20 wt. %, or from about 15 wt. % to about 20 wt. %.
  • the catalyst-adsorbent composition includes a dispersant.
  • the dispersant may include one or more of an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant.
  • the dispersant is a nonionic acrylic copolymer.
  • Fig. 3 is a flow diagram illustrating a method 300 of forming a catalyst-adsorbent filter sorbent in accordance with an embodiment of the disclosure.
  • the method 300 begins at block 302, where a slum 7 is formed.
  • the slurry 7 comprises a metal oxide catalyst and an adsorbent, which may be formed by dissolving the metal oxide catalyst and adsorbent in an aqueous solution.
  • the slurry further comprises a polymeric binder.
  • the polymeric binder is selected from: polyethylene, polypropylene, polyolefin copolymer, polyisoprene, polybutadiene, polybutadiene copolymer, chlorinated rubber, nitrile rubber, polychloroprene, ethylene-propylene-diene elastomer, polystyrene, polyacrylate, polymethacrylate, polyacrylonitrile, poly(vinyl ester), poly(vinyl halide), polyamide, cellulosic polymer, polyimide, acrylic polymer, vinyl acrylic polymer, styrene acrylic polymer, polyvinyl alcohol, thermoplastic polyester, thermosetting polyester, poly(phenylene oxide), poly(phenylene sulfide), fluorinated polymer, poly(tetrafluoroethylene) polyvinylidene fluoride, poly(vinylfluoride) chloro
  • the slurry further comprises a dispersant.
  • the dispersant may include one or more of an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, or a nonionic surfactant.
  • the slurry further includes an oxidant, which may improve removal efficiency of nitrogen oxides.
  • the oxidant may be selected from nitric acid, hypochlorite, a persulfate, a peroxide, permanganate, or a chlorate.
  • the slurry further includes an alkaline component, such as a hydroxide, ammonia, or a carbonate, which may improve slurry stabilization.
  • an alkaline component such as a hydroxide, ammonia, or a carbonate, which may improve slurry stabilization.
  • a pH of the slurry may be adjusted between 2 and 12, or between 4 and 10.
  • the slurry is coated onto a filter body.
  • the filter body may comprise a material selected from polymeric foam, polymeric fiber, non -woven fabric, a ceramic, or a pulp product (e.g., paper).
  • the filter body comprises a polymeric foam comprising polyurethane.
  • the filter body is in a form of a honeycomb.
  • the slurry is dried to form the catalyst-adsorbent filter.
  • the drying is performed at a temperature from about 80 °C to about 250 °C.
  • the polymeric binder may be present from about 5 wt. % to about 30 wt. % with respect to a total weight of the coating.
  • the blocks of method 300 are not limiting, and that, in certain embodiments, some or all of the blocks of their respective methods may be performed. In certain embodiments, one or more of the blocks may be performed substantially simultaneously. Some blocks may be omitted entirely or repeated.
  • 737 g water was prepared, and 297.6 g MnCfi powder and 59.5 g activated carbon powder were then dispersed into the mixture to form a slurry having a 32 wi. % solid content based on a total weight of the slurry.
  • a final slurry was achieved by adding to the slurry 31.2 g of a polyacrylic latex and 31.2 g polyurethane latex binder. The final slurry had a solids content of about 35 wt.%, a pH of about 10, and a maximum viscosity of 720 centipoise.
  • a test sample was prepared using a polyurethane foam core as a filter body.
  • the polyurethane foam core had a diameter of 1 inch and a length of 40 millimeters.
  • the coated polyurethane foam core was dried at 110 °C and maintained at 110 °C for 1 hour.
  • a washcoat dry gain of the coated polyurethane core was 1.8 g.
  • An additional rectangular polyurethane foam sample having dimensions of 408 by 283 millimeters and a 5-millimeter thickness square polyurethane foam was coated by the same procedure, resulting in a washcoat dry gain of 49.3 g, which was tested using the GB/T 32085 standard.
  • 1127 g water was prepared, and 331 g of activated carbon powder was then dispersed into the mixture to form a slurry having a 26 wt.% solid content based on a total weight of the slurry, a pH of about 8, and a maximum viscosity of 1026 centipoise.
  • a test sample was prepared using a polyurethane foam core as a filter body.
  • the polyurethane foam core had a diameter of 1 inch and a length of 40 millimeter.
  • the coated polyurethane foam core was dried at 110 °C and maintained at 110 °C for 1 hour.
  • Table 1 summarizes the results obtained from placing the coated polyurethane foam cores into a plug-flow reactor.
  • the unpurified air stream included S0 2 , NOx, and NH 3 , each present at 30 ppm.
  • Other parameters of the air stream include a temperature of 25 ⁇ 0.5 °C, relative humidity of 18%, 10% 0 2 , and a space velocity of 150,000 h ⁇ and a total flow time of 1 hour.
  • Table 1 demonstrates that Example 2 is capable of adsorbing more pollutants than Comparative Example 2, with greater SO? adsorption capacity.
  • Example 2 exhibited improved washcoat adhesion than Comparative Example 2.
  • “X includes A or B” is intended to mean any of the natural inclusive permutations. That is, if X includes A; X includes B; or X includes both A and B, then“X includes A or B” is satisfied under any of the foregoing instances.
  • the use of the terms“a,”“an,”“the,” and similar referents in the context of describing the materials and methods discussed herein (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

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TWI799379B (zh) * 2016-06-30 2023-04-21 美商巴斯夫公司 基於氧化錳的催化劑及用於移除甲醛及揮發性有機化合物的催化劑裝置
KR102615619B1 (ko) * 2016-11-03 2023-12-20 콜럼버스 인더스트리즈, 인코포레이티드 가스 오염물질 제거에 있어 개선된 효율을 위한 표면-개질된 탄소 및 흡착제
CN106732755B (zh) * 2016-12-23 2019-03-05 中节能万润股份有限公司 一种分子筛-多元氧化物复合整体挤出式脱硝催化剂的制备方法

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KR20210076011A (ko) 2021-06-23
CA3116764A1 (en) 2020-04-30
EP3870338A4 (de) 2023-05-17
BR112021007686A2 (pt) 2021-07-27
ZA202103375B (en) 2022-10-26

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