WO2020039452A1 - An enhanced carbon dioxide sorbent nanofiber membrane and a device thereof - Google Patents

An enhanced carbon dioxide sorbent nanofiber membrane and a device thereof Download PDF

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Publication number
WO2020039452A1
WO2020039452A1 PCT/IN2019/050555 IN2019050555W WO2020039452A1 WO 2020039452 A1 WO2020039452 A1 WO 2020039452A1 IN 2019050555 W IN2019050555 W IN 2019050555W WO 2020039452 A1 WO2020039452 A1 WO 2020039452A1
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Prior art keywords
adsorption
membrane
desorption
minutes
cca
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PCT/IN2019/050555
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French (fr)
Inventor
Pradeep Thalappil
Yatheendran ANAGHA
Kumar Ramesh
Arun Karthik S
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INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras)
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Publication of WO2020039452A1 publication Critical patent/WO2020039452A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/02—Separation 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/14—Separation 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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation 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
    • B01D53/14—Separation 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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0004—Organic membrane manufacture by agglomeration of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0004—Organic membrane manufacture by agglomeration of particles
    • B01D67/00042—Organic membrane manufacture by agglomeration of particles by deposition of fibres, nanofibres or nanofibrils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid 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 physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid 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
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B01J20/28038—Membranes or mats made from fibers or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
    • B01J20/3259—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulfur with at least one silicon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/43—Acrylonitrile series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/39—Electrospinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to the field of air purification or air filtration, more specifically relates to a material that adsorbs C0 2 at ambient room condition and desorbs it at near ambient temperature.
  • C0 2 scavenging materials including calcium oxide, hyper branched amino silica, as well as amines (primary, secondary, and tertiary).
  • C0 2 concentration below 450 ppm, compatible to global average concentration of 300 - 500 ppm (ANSEASHRAE Standard 62.1-2010) in a closed room of 20 cubic meters volume with one occupant for a period of two hours, it is necessary to remove approximately 75 g or 1.704 mol of C0 2 .
  • the present invention provides a new material of composite fiber that adsorbs C0 2 at room temperature and desorbs C0 2 at near ambient temperature.
  • This invention relates to the field of air purification or air filtration, more specifically relates to a material that adsorbs C0 2 at room temperature and desorbs it at near ambient temperature.
  • the invention relates to the fabrication of nanofiber membrane by electrospinning an aminoethyl-aminopropyl trimethoxy silane/polyacrylonitrile (AEAPTMS/PAN) composite, with large surface area, having a 100% recyclable C0 2 adsorption capacity of > 0.77 mmol/g functioning at 24 °C, with complete regeneration at near room temperature of 45 °C, with an adsorption cycle of 120 minutes and desorption cycle of 30 minutes.
  • AEAPTMS/PAN aminoethyl-aminopropyl trimethoxy silane/polyacrylonitrile
  • C0 2 is adsorbed by forming ammonium bicarbonate and ammonium carbamate at room temperature, in the presence and absence of humidity, respectively and desorbed by decomposing the formed ammonium bicarbonate and ammonium carbamate at 55 °C, preferably at 50 °C,more preferably at 45 °C or lower.
  • the invention illustrates the use of the fabricated nanofiber membrane in air purification by integrating it within a device comprising air purifier, air conditioner and heater, with adsorption and desorption cycles.
  • the nanofiber works in a cycle with 40 minutes of adsorption and 20 minute of desorption or preferably 20 minutes of adsorption and 10 minutes of desorption.
  • Figure 1 SEM image of AEAPTMS/PAN composite electrospun material.
  • Figure 2 depicts C0 2 sorption capacity of electrospun AEAPTMS/PAN (composite- 1).
  • Figure 3 depicts cyclic C0 2 sorption capacity of electrospun AEAPTMS/PAN (composite- 1).
  • Figure 4 depicts ambient temperature and relative humidity during C0 2 sorption by electrospunAEAPTMS/PAN (composite- 1 ).
  • Figure 5 depicts % relative humidity dependence of C0 2 adsorption capacity of electrospunAEAPTMS/PAN (composite- 1 ).
  • Figure 6 depicts temperature dependence of C0 2 adsorption capacity of electrospun AEAPTMS/PAN (composite- 1).
  • Figure 7 depicts the rate of desorption at different ambient temperature for AEAPTMS/PAN (composite- 1).
  • Figure 8 depicts the FTIR spectrum of electrospun AEAPTMS/PAN (composite- 1) before adsorption, after C0 2 adsorption and after C0 2 desorption.
  • Figure 9 depicts the Raman spectrum of electrospun AEAPTMS/PAN (composite- 1 ) before adsorption, after C0 2 adsorption and after C0 2 desorption.
  • Figure 10 depicts the schematic diagram of proposed device for C0 2 adsorption and desorption process using electrospun APAETES/PAN membrane.
  • the present invention shows the possibility of using the well-known carbamate and bicarbonate chemistry of amines in scavenging C0 2 by a suitable combination of amines and polyacrylonitrile polymer.
  • the nanofiber membranes of large surface area are produced by electrospinning the composite and this composite material can also be processed into fibrous membrane using melt-spinning process. Due to the inherent curvature and exposed functionalities, large C0 2 uptake is possible resulting in a C0 2 scavenger functioning at room temperature and ambient pressure.Homogeneous distribution of C0 2 scavenging sites leads to the uniformly ordered formation of carbamate and bicarbonates.
  • This invention describes a method for C0 2 control in closed environments to enhance the quality of human life.
  • the present invention relates to the development of electrospun AEAPTMS/PAN fibrous membranewith a high surface area for C0 2 adsorption.
  • the electrospun fiber’s surface contains numerous uniform amine sites for C0 2 capture.
  • Figure 1 shows the SEM images of the surface.
  • the composite- 1 comprises of the electrospun material, N-[3- (Trimethoxysilyl) propyl]ethylenediamine (AEAPTMS) functionalized polyacrylonitrile (PAN/AEAPTMS) as the adsorbent surface which has a higher surface area with a nanofiber diameter of I p , preferably 0.5pm, more preferably 0.1 pm.
  • Figure 1 shows that the fibers are 0.359 ⁇ 0.065pm in diameter.
  • the electrospun polymeric material does effective adsorption of CO 2 at room temperature and desorption at 50 °C enabling complete regeneration of the adsorbent material.
  • this invention demonstrates the CO 2 sorption capacity of the AEAPTMS/PAN and solvent composition.
  • the adsorbent surface was prepared by the electrospinning technique.
  • Amine loaded nano-fibrous material, composite- 1 was prepared by dissolving l2wt% PAN in dimethylformamide (DMF) with 1 ml AEAPTMS in use.
  • amine loaded nano- fibrous material, composite-2 was prepared by dissolving 14 wt% PAN in DMF with 2.0 ml of AEAPTMS.
  • Figure 2 shows an adsorption capacity of 0.77mmol/g CO 2 for composite- 1, nanofiber material in an ambience having 70 % relative humidity, 24 °C temperature and 3400 ppm C0 2 concentration.
  • the adsorption-desorption experiments were performed in an air-tight desiccator having pre-determined humidity and concentration of CO 2 andAEAPTMS/PAN fibrous material sheet and C0 2 measuring meter kept in it. Relative humidity, temperature and C0 2C oncentration in the desiccator were monitored and logged each minute. Adsorption experiments were done at an average temperature of 25°C and desorption tests were performed at 50°C. Desiccator was kept in a hot air oven for high temperature studies and air-conditioned roomfor low temperature studies. Three adsorption - desorption cycles in Figure 3 shows 100% cycling capacity of 0.8 g of composite- 1 material with an initial CO2 concentration of 2304 ppm.
  • the graph shows the uptake of CO2 by the fibers when the composite- 1 fibers were exposed to the gas in an enclosure.
  • the adsorption experiment was repeated after desorption of the adsorbed CO2 at 50 °C.
  • Figure 4 shows the corresponding changes occurred in temperature and % relative humidity during three adsorption-desorption cycles.
  • Electrospuncomposite- 1 shows an average of 0.347mmol/g C0 2 adsorption capacity for initial 30 minutes of adsorption cycle and 100% desorption capacity when the material was heated up to 50 °C.
  • the rate of CO2 desorption increases as the temperature of the material increases.
  • the C0 2 sorption capacity of the developed composite material is dependent on ambient humidity and temperature. The higher value of humidity and lower value of temperature will favor enhanced rate of adsorption.
  • Table 2 shows the amount of C0 2 adsorption for each cycle with a maximum of 0.55mmol/g at 70 % relative humidity and 25 °C.
  • Bicarbonate and carbamate chemistry based CO 2 adsorption capacity is dependent on initial C0 2 concentration, ambient temperature and % relative humidity.
  • CO 2 adsorption capacity increases with increase in initial C0 2 concentration, decrease in ambient temperature and increase in % relative humidity. Presence of water vapor enhances bicarbonate formation and increases the C0 2 adsorption capacity. C0 2 desorption rate increases at higher temperature.
  • FTIR analysis shows the formation of ammonium bicarbonate and ammonium carbamate on composite- 1 after C0 2 adsorption in humid ambience with 60 % relative humidity and 24 °C temperature.
  • Figure 8 A), B) and C) shows the ATR - FTIR spectra of composite- 1 before adsorption, after adsorption and after desorption, respectively.
  • the difference spectrum B-A shows the difference between the spectrum after C02 adsorption and before C0 2 adsorption and C-A difference spectrum shows the difference between the spectrum after C0 2 desorption and before C0 2 adsorption, respectively.
  • the available transmittance peak intensities in the difference spectrum B-A confirms the formation of bicarbonate and carbamate after C0 2 adsorption whereas the absence of corresponding peak intensities in the difference spectrum C-A, suggests reversal of the formed bicarbonate and carbamate and re-availability of homogeneous adsorption sites.
  • the Raman shift in the region 1000-3000cm ' is due to bicarbonate andcarbamte species.
  • Adsorption of C0 2 from humid air on the uniformly distributed homogeneous sites leads to the formation of bicarbonate peak at 1075 cm 1 .
  • Chemisorption of C0 2 on the amine groups present on the surface results in amide peak at 1465 cm 1 and the peak at 1687 cm 'can be attributed to secondary carbamate (CHN group), carbonyl group of acid and antisymmetric CO stretching of bicarbonate.
  • the peak at 2260cm 1 is due to unreacted nitrile which also gets intensified after adsorption of CO 2 due to overlap of NH + group vibration.
  • the peak at 2900 cm 1 is due to CH stretching vibrations, vibrations of O-CH3 group and shift of alkane stretching to higher wave number due to the protonation of amines through C0 2 adsorption.
  • FIG. 10 A schematic diagram of device with AEAPTMS/PAN membrane and inbuilt heater is shown in Figure 10.
  • air enters through particulate filter where suspended &micro-particles are removed. After the particulate filter, air goes through filaments of heater and then subsequently through electrospun AEAPTMS/PAN membrane, where CO 2 from ambient air is removed.
  • Heater is kept on and off for C0 2 adsorption and desorption cycle, respectively. During desorption, temperature of inlet air increases to temperature above 45°C or preferably 55°C.

Abstract

An AEAPTMS (N-[3-(Trimethoxysilyl) propyl] ethylenediamine)/aminoethyl-aminopropyltrimethoxysilanepolyacrylonitrile (PAN) based electrospun nanocomposite materialfor CO2 adsorption and air purification is proposed. The material has CO2 capture capacity of 0.77 mmol/g at 24℃ and 70% relative humidity or in air-conditioned environment with 100% regeneration capacity at near ambient temperature.

Description

DESCRIPTION
TITLE OF THE INVENTION
AN ENHANCED CARBON DIOXIDE SORBENT NANOFIBER MEMBRANE AND A DEVICE THEREOF
FIELD OF THE INVENTION
The present invention relates to the field of air purification or air filtration, more specifically relates to a material that adsorbs C02 at ambient room condition and desorbs it at near ambient temperature.
BACKGROUND OF THE INVENTION
Rapid increase in the CO 2 concentration in the air in the recent past and its alarming consequences such as global warming, are some of the most important environmental issues facing the planet. This significant increase in C02Concentration is caused due to industrial actions, largely from combustion. Increased C02 levels have undesirable consequences on metabolism and neuronal activities. Due to the need to have protection from insects, dust, and such other local disturbances, enclosed environments are desired for living. However, the CO 2 levels in such closed enclosures increase due to biological activities of the inhabitants. Therefore, it is necessary to control the concentration of C02 in such environments for healthy living.
It is well known from the literature that, there are many C02 scavenging materials including calcium oxide, hyper branched amino silica, as well as amines (primary, secondary, and tertiary). In order to maintain the C02 concentration below 450 ppm, compatible to global average concentration of 300 - 500 ppm (ANSEASHRAE Standard 62.1-2010) in a closed room of 20 cubic meters volume with one occupant for a period of two hours, it is necessary to remove approximately 75 g or 1.704 mol of C02. In the ambient condition of 25°C and 90 % relative humidity, removal of such amount of C02 is possible by using 0.1910 kg of the best available C02 removal media such as amino silica monolith (Harshul Thakkar et. ah, ACS Appl. Mater. Interfaces 2017, 9, 7489-7498). Other available media, metal organic frameworks (MOF) -177 (Hussein RasoolAbid et. ah, Journal of Colloid and Interface Science 2012, 120-124), requires 0.051 kg of material to maintain C02 concentration in the above-mentioned case. However, for commercial feasibility, regeneration of silica monolith requires an optimum ambient temperature of 115 °C and, adsorption process of MOF-177 requires an optimum pressure of 4500 kPa. Since, regeneration of the media with best sorption capacity is not possible near ambient conditions, developing a device with a minimum quantity of working sorbent material with efficient cycling capacity near ambient conditions with regeneration is necessary. This will reduces the physical size of the device as well as cost and power requirements.
Though there are many adsorption media for C02 removal in recent years, still there is a need for a better and efficient sorbent material for removing C02 in ambient conditions. Thus the present invention provides a new material of composite fiber that adsorbs C02 at room temperature and desorbs C02 at near ambient temperature.
SUMMARY OF THE INVENTION
This invention relates to the field of air purification or air filtration, more specifically relates to a material that adsorbs C02 at room temperature and desorbs it at near ambient temperature.
In one embodiment the invention relates to the fabrication of nanofiber membrane by electrospinning an aminoethyl-aminopropyl trimethoxy silane/polyacrylonitrile (AEAPTMS/PAN) composite, with large surface area, having a 100% recyclable C02 adsorption capacity of > 0.77 mmol/g functioning at 24 °C, with complete regeneration at near room temperature of 45 °C, with an adsorption cycle of 120 minutes and desorption cycle of 30 minutes. C02 is adsorbed by forming ammonium bicarbonate and ammonium carbamate at room temperature, in the presence and absence of humidity, respectively and desorbed by decomposing the formed ammonium bicarbonate and ammonium carbamate at 55 °C, preferably at 50 °C,more preferably at 45 °C or lower.
In other embodiment, the invention illustrates the use of the fabricated nanofiber membrane in air purification by integrating it within a device comprising air purifier, air conditioner and heater, with adsorption and desorption cycles.Wherein, the nanofiber works in a cycle with 40 minutes of adsorption and 20 minute of desorption or preferably 20 minutes of adsorption and 10 minutes of desorption. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 SEM image of AEAPTMS/PAN composite electrospun material.
Figure 2 depicts C02 sorption capacity of electrospun AEAPTMS/PAN (composite- 1).
Figure 3 depicts cyclic C02 sorption capacity of electrospun AEAPTMS/PAN (composite- 1). Figure 4 depicts ambient temperature and relative humidity during C02 sorption by electrospunAEAPTMS/PAN (composite- 1 ).
Figure 5 depicts % relative humidity dependence of C02 adsorption capacity of electrospunAEAPTMS/PAN (composite- 1 ).
Figure 6 depicts temperature dependence of C02 adsorption capacity of electrospun AEAPTMS/PAN (composite- 1).
Figure 7 depicts the rate of desorption at different ambient temperature for AEAPTMS/PAN (composite- 1).
Figure 8 depicts the FTIR spectrum of electrospun AEAPTMS/PAN (composite- 1) before adsorption, after C02 adsorption and after C02 desorption.
Figure 9 depicts the Raman spectrum of electrospun AEAPTMS/PAN (composite- 1 ) before adsorption, after C02 adsorption and after C02 desorption.
Figure 10 depicts the schematic diagram of proposed device for C02 adsorption and desorption process using electrospun APAETES/PAN membrane.
Referring to the drawings, the embodiments of the present invention are further described. The figures are not necessarily drawn to scale, and in some instances the drawings have been exaggerated or simplified for illustrative purposes only. One of ordinary skill in the art may appreciate the many possible applications and variations of the present invention based on the following examples of possible embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various forms. The figures are not necessary to scale exemplary of the invention that may be embodied in various forms. The figures are not necessary to scale; some features may be exaggerated to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention.
The present invention shows the possibility of using the well-known carbamate and bicarbonate chemistry of amines in scavenging C02 by a suitable combination of amines and polyacrylonitrile polymer. The nanofiber membranes of large surface area are produced by electrospinning the composite and this composite material can also be processed into fibrous membrane using melt-spinning process. Due to the inherent curvature and exposed functionalities, large C02 uptake is possible resulting in a C02 scavenger functioning at room temperature and ambient pressure.Homogeneous distribution of C02 scavenging sites leads to the uniformly ordered formation of carbamate and bicarbonates. This electrospinning induced homogeneity in carbamate and bicarbonate formation on AEAPTMS/PAN structure leads to sharp desorption of C02. The saturated material desorbs C02 in the temperature window of 47- 50°C enabling complete regeneration. This process can be repeated several times. Even with the comparatively poor adsorption capacity of AEAPTMS/PAN material, room temperature adsorption and near complete desorption close to ambient conditions, make it possible to design a system for C02 sequestration with a reduced quantity of the material. A device incorporating such materials with reduced energy input requires 1.64 kg of AEAPTMS/PAN composite material for maintaining C02 concentration below 450 ppm in a room of 20-meter cube volume with one active adult occupant. The adsorption happens at 25 °C, preferably at 22 °C with 60% relative humidity and desorption occurs at 50°C, preferably at 47 °C.
This invention describes a method for C02 control in closed environments to enhance the quality of human life.
Properties of all the best-known materials for C02 sorption as of today and their performances are listed in Table 1.
Table 1 Adsorption capacity of various adsorbents and theiroperational parameters
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
The present invention relates to the development of electrospun AEAPTMS/PAN fibrous membranewith a high surface area for C02 adsorption. The electrospun fiber’s surface contains numerous uniform amine sites for C02 capture. Figure 1 shows the SEM images of the surface. According to the invention, the composite- 1 comprises of the electrospun material, N-[3- (Trimethoxysilyl) propyl]ethylenediamine (AEAPTMS) functionalized polyacrylonitrile (PAN/AEAPTMS) as the adsorbent surface which has a higher surface area with a nanofiber diameter of I p , preferably 0.5pm, more preferably 0.1 pm. Figure 1 shows that the fibers are 0.359±0.065pm in diameter. The electrospun polymeric material does effective adsorption of CO 2 at room temperature and desorption at 50 °C enabling complete regeneration of the adsorbent material.
Further, this invention demonstrates the CO 2 sorption capacity of the AEAPTMS/PAN and solvent composition. The adsorbent surface was prepared by the electrospinning technique. Amine loaded nano-fibrous material, composite- 1 was prepared by dissolving l2wt% PAN in dimethylformamide (DMF) with 1 ml AEAPTMS in use. In another aspect, amine loaded nano- fibrous material, composite-2 was prepared by dissolving 14 wt% PAN in DMF with 2.0 ml of AEAPTMS. Figure 2 shows an adsorption capacity of 0.77mmol/g CO 2 for composite- 1, nanofiber material in an ambience having 70 % relative humidity, 24 °C temperature and 3400 ppm C02 concentration.
The adsorption-desorption experiments were performed in an air-tight desiccator having pre-determined humidity and concentration of CO 2 andAEAPTMS/PAN fibrous material sheet and C02 measuring meter kept in it. Relative humidity, temperature and C02Concentration in the desiccator were monitored and logged each minute. Adsorption experiments were done at an average temperature of 25°C and desorption tests were performed at 50°C. Desiccator was kept in a hot air oven for high temperature studies and air-conditioned roomfor low temperature studies. Three adsorption - desorption cycles in Figure 3 shows 100% cycling capacity of 0.8 g of composite- 1 material with an initial CO2 concentration of 2304 ppm. The graph shows the uptake of CO2 by the fibers when the composite- 1 fibers were exposed to the gas in an enclosure. The adsorption experiment was repeated after desorption of the adsorbed CO2 at 50 °C. Figure 4 shows the corresponding changes occurred in temperature and % relative humidity during three adsorption-desorption cycles. Electrospuncomposite- 1 shows an average of 0.347mmol/g C02 adsorption capacity for initial 30 minutes of adsorption cycle and 100% desorption capacity when the material was heated up to 50 °C. The rate of CO2 desorption increases as the temperature of the material increases. The C02 sorption capacity of the developed composite material is dependent on ambient humidity and temperature. The higher value of humidity and lower value of temperature will favor enhanced rate of adsorption. Table 2 shows the amount of C02 adsorption for each cycle with a maximum of 0.55mmol/g at 70 % relative humidity and 25 °C.
Table 2 C02 concentration in the chamber after each sorption cycle for electrospun AEAPTMS/PAN (composite- 1)
Figure imgf000010_0001
Bicarbonate and carbamate chemistry based CO 2 adsorption capacity is dependent on initial C02 concentration, ambient temperature and % relative humidity. CO 2 adsorption capacity increases with increase in initial C02 concentration, decrease in ambient temperature and increase in % relative humidity. Presence of water vapor enhances bicarbonate formation and increases the C02 adsorption capacity. C02 desorption rate increases at higher temperature.
Increase in C02 adsorption rate with increase in % relative humidity at 25 °C temperature is shown in Figure 5. At ambient temperature, bicarbonate formation is the dominant mechanism for C02 adsorption, than by carbamate formation. As temperature increases, formation rate of bicarbonate decreases and carbamate formation becomes the more dominant mechanism for C02 adsorption. As temperature increases, the C02 adsorption rate further decreases because of an aggregate decrease in the rate of formation of ammonium bicarbonate and ammonium carbamate, hence saturation uptake is delayed. The same phenomenon is shown in Figure 6.
Desorption tests were performed at a fixed temperature of 50 °C, with different temperature ramp rates. To obtain the different temperature rate of 1.11, 1.25 and 1.85 °C/minute, oven temperature was set to 60, 70 and 80 °C, respectively. Once oven temperature reaches 50 °C, it was maintained the same. At three different ramping rates of 1.11, 1.25 and 1.85 °C/minute, composite- 1, takes 45, 40 and 27 minutes, respectively for full desorption of adsorbed 0.308 mmol of C02. The rate of desorption is high with a high-temperature ramp rate. Rate of desorption at different temperature windows is given in Figure 7.
FTIR analysis shows the formation of ammonium bicarbonate and ammonium carbamate on composite- 1 after C02 adsorption in humid ambience with 60 % relative humidity and 24 °C temperature. Figure 8 A), B) and C) shows the ATR - FTIR spectra of composite- 1 before adsorption, after adsorption and after desorption, respectively. The difference spectrum B-A shows the difference between the spectrum after C02 adsorption and before C02 adsorption and C-A difference spectrum shows the difference between the spectrum after C02 desorption and before C02 adsorption, respectively.
Upon C02 adsorption, various surface species are readily formed and the spectrum shows IR features in the range of 1600 to 500 cm 1. The IR bands in the region, 1600-500 cm l are due to carbamate, bicarbonate and carbamic acid species. Adsorption of C02 with H20 molecule present in the humid air on the uniformly distributed homogeneous sites leads to the formation of bicarbonate peaks at 816, 1318 and 691 cm 1. Chemisorption of C02 on amine groups present on the surface results in carbamate and carbamic acid peaks at 1478, 1561 and 593 cm l. The peak at 2245 cm 'can be attributed to unreacted polyacrylonitrile. Assignments are summarized in Table 3. The available transmittance peak intensities in the difference spectrum B-A confirms the formation of bicarbonate and carbamate after C02 adsorption whereas the absence of corresponding peak intensities in the difference spectrum C-A, suggests reversal of the formed bicarbonate and carbamate and re-availability of homogeneous adsorption sites.
The Raman spectrum of AEAPTMS functionalized fiber before C02 adsorption, after C02 adsorption and after C02 desorption are shown in Figure 9. Similar to FTIR, Raman analysis corroborates the formation of ammonium bicarbonate and ammonium carbamate on composite- 1 after C02 adsorption in humid ambience with 60 % relative humidity and 24 °C temperature.
The Raman shift in the region 1000-3000cm ' is due to bicarbonate andcarbamte species. Adsorption of C02 from humid air on the uniformly distributed homogeneous sites leads to the formation of bicarbonate peak at 1075 cm 1. Chemisorption of C02 on the amine groups present on the surface results in amide peak at 1465 cm 1 and the peak at 1687 cm 'can be attributed to secondary carbamate (CHN group), carbonyl group of acid and antisymmetric CO stretching of bicarbonate. The peak at 2260cm 1 is due to unreacted nitrile which also gets intensified after adsorption of CO 2 due to overlap of NH+ group vibration. The peak at 2900 cm 1 is due to CH stretching vibrations, vibrations of O-CH3 group and shift of alkane stretching to higher wave number due to the protonation of amines through C02 adsorption.
Table 3 IR band assignments after C02 adsorption on AEAPTMS/PAN (composite- 1).
Figure imgf000012_0001
A schematic diagram of device with AEAPTMS/PAN membrane and inbuilt heater is shown in Figure 10. During the operation of device, air enters through particulate filter where suspended &micro-particles are removed. After the particulate filter, air goes through filaments of heater and then subsequently through electrospun AEAPTMS/PAN membrane, where CO 2 from ambient air is removed. This provides best efficiency when operated in air-conditioned room without causing any energy inefficiency to existing air-conditioning system. Heater is kept on and off for C02 adsorption and desorption cycle, respectively. During desorption, temperature of inlet air increases to temperature above 45°C or preferably 55°C.
It may be appreciated by those skilled in the art that the drawings, examples and detailed description herein are to be regarded in an illustrative rather than a restrictive manner.

Claims

We Claim:
1. A nanofiber membrane fabricated by electrospinning an aminoethyl-aminopropyl trimethoxy silane/polyacrylonitrile (AEAPTMS/PAN) composite, with large surface area, having a 100% recyclable CCA adsorption capacity of > 0.77 mmol/g functioning at 24 °C, with complete regeneration at near room temperatureof 45 °C, with an adsorption cycle of 120 minutes and desorption cycle of 30 minutes.
2. The membrane as claimed in claim 1 , wherein the nanofiber is fabricated bymelt spinning, or melt electrospinning, or electrospinning.
3. The membrane as claimed in claim 1, wherein the diameter of the nanofiber is in the range of lpm to 0.1 pm.
4. The membrane as claimed in claim 1 , wherein the CO 2 is adsorbed and desorbed in ambient air with adsorption cycle time not greater than 120 minutes and desorption cycle time not greater than 30 minutes.
5. The membrane as claimed in claim 1, wherein the CCA is adsorbed on homogenous uniformly distributed amine sites.
6. The membrane as claimed in claim 1, wherein CCA is adsorbed by forming ammonium bicarbonate and ammonium carbamate at room temperature, both in the presence and absence of humidity.
7. The membrane as claimed in claim 1, wherein CCA is desorbed by decomposing the formed ammonium bicarbonate and ammonium carbamate at 55 °C, preferably at 50 °C, more preferably at 45 °C or lower.
8. The membrane as claimed in claim 1, wherein the CCA adsorption leads to homogenous uniformly distributed bicarbonate and carbamate sites.
9. The membrane as claimed in claim 1, wherein re-adsorption and re-desorption occurs for multiple cycles with 100% regeneration capacity.
10. The membrane as claimed in claim 1, wherein the nanofiber is integrated within a device comprising air purifier, air conditioner and heater, with adsorption and desorption cycles.
11. The membrane as claimed in claim 10, wherein the CCA is adsorbed after particulate removal from ambient air.
12. The membrane as claimed in claim 10, wherein the nanofiber works in a cycle with 40 minutes of adsorption and 20 minute of desorption or preferably 20 minutes of adsorption and 10 minutes of desorption.
PCT/IN2019/050555 2018-08-20 2019-07-29 An enhanced carbon dioxide sorbent nanofiber membrane and a device thereof WO2020039452A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103702740B (en) * 2011-06-06 2016-11-09 瑞士材料试验研究所 For CO absorption from admixture of gas2porous adsorption structure
TWI568491B (en) * 2015-12-31 2017-02-01 財團法人工業技術研究院 Filtration material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103702740B (en) * 2011-06-06 2016-11-09 瑞士材料试验研究所 For CO absorption from admixture of gas2porous adsorption structure
TWI568491B (en) * 2015-12-31 2017-02-01 財團法人工業技術研究院 Filtration material

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