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WO2025114104A2 - Matériaux sorbants destinés à la capture de co2, leurs utilisations et leurs procédés de poduction - Google Patents

Matériaux sorbants destinés à la capture de co2, leurs utilisations et leurs procédés de poduction Download PDF

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Publication number
WO2025114104A2
WO2025114104A2 PCT/EP2024/082949 EP2024082949W WO2025114104A2 WO 2025114104 A2 WO2025114104 A2 WO 2025114104A2 EP 2024082949 W EP2024082949 W EP 2024082949W WO 2025114104 A2 WO2025114104 A2 WO 2025114104A2
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building blocks
amino mono
sorbent material
precursors
carbon dioxide
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WO2025114104A3 (fr
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Tomohide Yoshida
Cornelius GROPP
Hanna TRAEGER
Julia Baettig
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Climeworks AG
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Climeworks AG
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    • 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
    • B01J20/28014—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
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • 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
    • 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
    • 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
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    • 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
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/28014—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
    • 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
    • B01J20/28014—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
    • B01J20/28042—Shaped bodies; Monolithic structures
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28054—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 surface properties or porosity
    • B01J20/28078—Pore diameter
    • 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
    • B01J20/34—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
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B01J20/3466—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase with steam
    • 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
    • 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
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/05—Biogas
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • 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
    • B01D53/04—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 with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • B01D53/0476—Vacuum pressure swing adsorption
    • 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 carbon dioxide capture materials with primary and/or secondary amine carbon dioxide capture moieties with good capture and swelling properties, as well as methods for preparing such capture materials, uses of such capture materials and carbon dioxide capture methods involving such materials.
  • Flue gas capture or the capture of CO2 from point sources, such as specific industrial processes and specific CO2 emitters, deals with a wide range of relatively high concentrations of CO2 (3-100 vol %) depending on the process that produces the flue gas.
  • High concentrations make the separation of the CO2 from other gases thermodynamically more favorable and consequently economically favorable as compared to the separation of CO2 from sources with lower concentrations, such as ambient air, where the concentration is in the order of 400 ppm.
  • DAC technologies were described, such as for example, the utilization of alkaline earth oxides to form calcium carbonate as described in US-A-2010034724.
  • Different approaches comprise the utilization of solid CO2 adsorbents, hereafter named sorbents, in the form of packed beds of typically sorbent particles and where CO2 is captured at the gassolid interface.
  • Such sorbents can contain different types of amino functionalisation and polymers, such as immobilized aminosilane-based sorbents as reported in US-B-8834822, and amine-functionalised cellulose as disclosed in WO-A-2012/168346.
  • WO-A-2011/049759 describes the utilization of an ion exchange material comprising an aminoalkylated bead polymer for the removal of carbon dioxide from industrial applications.
  • WO-A-2016/037668 describes a sorbent for reversibly adsorbing CO2 from a gas mixture, where the sorbent is composed of a polymeric adsorbent having a primary amino functionality. The materials can be regenerated by applying pressure or humidity swing.
  • WO2021136744A1 show the functionalisation of polystyrene-divynylbenzen polymers with a high variaty of amines and their use in carbon capture of gas stream with high conentration of CO2.
  • the nitrogen content reported in WO2021136744A1 is between 5-10 mol/kg, which is similar to the amount that can be reached by functionalising PS-DVB with benzylamine as reported by Alesi et al. in Industrial & Engineering Chemistry Research 2012, 51 , 6907-6915.
  • An optimal sorbent ideally should be predominant composed of active phase to be able to intensify the carbon capture process.
  • Amines react with CO2 to form a carbamate moiety, which in a successive step can be regenerated to the original amine, for example by increasing the temperature of the sorbent bed to ca 100°C and therefore releasing the CO2.
  • An economically viable process for carbon capture implies the ability of the sorbent to capture as much CO2 as possible in a very short period of time so that the throughput of the system can be increased. To this end, this feature is of course related to the amount of active amine sites able to bind CO2, thus, it is very important to develop new materials with a high CO2 capture capacity. Some materials show limits to the degree of functionalisation that can be achieved, thus new nontrivial sorbent structures are required to be invented to overcome this limitation.
  • the equilibrium CO2 adsorption capacity for air capture was found to be as high as 7.3 wt%.
  • the proposed “PEI-CFB air capture system” mainly comprises a Circulating Fluidized Bed (CFB) adsorber and a BFB desorber with a CO2 capture capacity of 40 t-CO2/day.
  • a large pressure drop is required to drive the air through the CFB adsorber and also to suspend and circulate the solid adsorbents within the loop, resulting in higher electricity demand than other reported air capture systems.
  • TSA Temperature Swing Adsorption
  • the total energy required is 6.6 GJ/t-CO2 which is comparable to other reference air capture systems.
  • WO-A-2022013197 discloses a method for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air, flue gas and biogas, by cyclic adsorption/desorption using a sorbent material, wherein the method comprises at least the following sequential and in this sequence repeating steps (a) - (e): (a) contacting said gas mixture with the sorbent material to allow gaseous carbon dioxide to adsorb; (b) isolating said sorbent material from said flow-through; (c) inducing an increase of the temperature of the sorbent material; (d) extracting at least the desorbed gaseous carbon dioxide from the unit and separating gaseous carbon dioxide from steam in or downstream of the unit; (e) bringing the sorbent material to ambient atmospheric conditions; wherein said sorbent material comprises primary and/or secondary amine moieties immobilized on a solid support, wherein the amine moieties, in the a -carbon position, are substituted by one
  • HMTA hexamethylentetramine
  • WO-A-2021239748 discloses a method for separating gaseous carbon dioxide from a gas mixture by cyclic adsorption/desorption, using a unit containing an adsorber structure with said sorbent material, wherein the method comprises the following sequential and in this sequence repeating steps: (a) contacting said gas mixture with the sorbent material to allow said gaseous carbon dioxide to adsorb under ambient atmospheric pressure and temperature conditions in an adsorption step, using a speed of the adsorption gas flow; (bO) isolating said sorbent with adsorbed carbon dioxide in said unit from said flow-through of gas mixture; (b1) injecting a stream of saturated steam essentially at ambient atmospheric pressure conditions and thereby inducing an increase of the temperature of the sorbent to a temperature between 60 and 110°C, (b2,b3) extracting at least the desorbed gaseous carbon dioxide while still injecting and/or circulating saturated steam at ambient atmospheric pressure conditions into said unit; (c) bringing the sorbent material to ambient atmospheric
  • GB-A-1296889 discloses how carbon dioxide is separated from mixtures with non-acid gases such as air by sorption on a weakly basic ion exchange resin followed by desorption with steam under conditions such that the steam condenses at the inlet end of the resin bed and a front of condensing steam then progressively passes through the bed displacing the carbon dioxide. Sorption is suitably conducted at 40-90 F and at a relative humidity of 75- 90%.
  • the preferred ion exchanger is a polystyrene-divinylbenzene copolymer containing polyamino functional groups, each of which comprises at least one secondary amino nitrogen atom.
  • an automatically controlled single bed sorption-regeneration system is illustrated.
  • WO-A-2023/152659 discloses polymeric amine sorbents with enhanced stability to moisture and/or oxygen for sorptive gas separation processes.
  • allylamine is reacted with divinylbenzene to form an amine sorbent.
  • the polymeric amine sorbents can be supported on a porous support or integrated into solid porous polymer networks.
  • Sorptive gas separators can employ contactors with such polymeric amine sorbents for separation of a component from a multi-component gas stream.
  • US 11 ,059,024 discloses supported amine polymer adsorbents based on polymers containing only or primarily primary amines sites to be used as regenerable adsorbents for CO, capture from ultradilute gas streams, such as ambient air, or from mixtures of gases containing preferably at least 10% oxygen, and can also be useful for use at the moderate gas pressures found in typical post-combustion capture processes, such as flue gas from large point sources such as coal-fired power plants.
  • Preferred supported solid amine adsorbents are based on poly(allylamine) (“PAA”) and poly(vinylamine) (“PVAm”), both of which are linear polymers, and their derivatives, containing substantially all primary amine groups, supported on substrates.
  • PAA poly(allylamine)
  • PVAm poly(vinylamine)
  • Preferred such substrates include silica mesocellular foam (MCF) and mesoporous-y-alumina, as well on mesoporous-y-alumina coated throughout the pores of MCF, most preferably of monolithic structure.
  • Preferred derivatives include the guanidinylated and cross-linked poly(allylamine) materials.
  • US 9,169,370 discloses an adsorption-desorption material, e.g., crosslinked polyvinylamine material having an Mw from about 500 to about 1x10 A 6, total pore volume from about 0.2 cc/g to about 2.0 cc/g, and a CO2 adsorption capacity of at least about 0.2 millimoles per gram of crosslinked material, and/or linear polyvinyl-amine material having an Mw from about 160 to about 1 x10 A 6, total pore volume from about 0.2 cc/g to about 2.0 cc/g, and a CO2 adsorption capacity of at least about 0.2 millimoles per gram of linear material.
  • adsorption-desorption material e.g., crosslinked polyvinylamine material having an Mw from about 500 to about 1x10 A 6, total pore volume from about 0.2 cc/g to about 2.0 cc/g, and a CO2 adsorption capacity of at least about 0.2 millimoles per gram of
  • This disclosure also involves processes for preparing the crosslinked polyvinyl-amine materials and linear polyvinylamine materials, as well as selective removal of CO2 and/or other acid gases from a gaseous stream using the polyvinylamine materials.
  • Dogan et al. (ChemSusChem 10.1002/cssc.201700190) report chemical tuning of nanoporous, solid sorbents for an ideal CO2 binding requiring unhindered amine functional groups on the pore walls.
  • post-synthetic reduction of nitriles in porous networks often fail due to the insufficient and irreversible metal hydride penetration. They synthesized a nanoporous network with pendant nitrile groups, microsphere morphology and in large scale.
  • the hollow microspheres were easily decorated with primary amines through in situ reduction by widely available boranes.
  • CO2 capture capacity of the modified sorbent was increased up to four times of the starting nanoporous network with a high heat of adsorption (98 kJ/mol).
  • Surface area can be tuned between 1 and 354 m2 /g.
  • Average particle size ( ⁇ 50 pm) is also quite suitable for CO2 capture applications where processes like fluidized bed require spheres of micron sizes.
  • Bachmann DOE-PARC-FE0031951
  • PVAm-DVB polyvinylamine-divinlybenzene system
  • EP-A-0576198 discloses a method for producing carbonaceous resins with superior physical properties that are useful as ion exchange materials, adsorbents, catalysts and catalyst support systems.
  • the carbonaceous resins are produced by heating a polymer obtained by polymerizing a monomer mixture comprising acrylonitrile, crosslinking agent and porogen.
  • WO-A-2022013197 discloses a method for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air, flue gas and biogas, by cyclic adsorption/desorption using a sorbent material, wherein the method comprises at least the following sequential and in this sequence repeating steps (a) - (e): (a) contacting said gas mixture with the sorbent material to allow gaseous carbon dioxide to adsorb; (b) isolating said sorbent material from said flow-through; (c) inducing an increase of the temperature of the sorbent material; (d) extracting at least the desorbed gaseous carbon dioxide from the unit and separating gaseous carbon dioxide from steam in or downstream of the unit; (e) bringing the sorbent material to ambient atmospheric conditions; wherein said sorbent material comprises primary and/or secondary amine moieties immobilized on a solid support, wherein the amine moieties, in the a-carbon position, are substituted by one hydrogen
  • a sorbent material for use in carbon dioxide capture processes.
  • the object is to provide an improved sorbent material having a high CO2 capture capacity and which is stable over a long time, so which resists oxidation and further deterioration mechanisms, and which also allows to be used in particulate form either as a loose bed or embedded in a structure or layer, be it a layered structure or a monolithic structure.
  • the present invention relates to a sorbent material capable of reversibly binding carbon dioxide, for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air, flue gas and biogas, preferably for direct air capture. This in particular using a temperature, vacuum, or temperature/vacuum swing process.
  • Said sorbent material is a particulate copolymeric material based on at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof copolymerized and cross-linked with divinyl building blocks.
  • a particulate material according to the present invention is a material which is solid up to a temperature of at least 80°C, so typically in the range of 0-80°C. It can be a powder material or a granular or bead material, and in any case, it is not a liquid or liquid viscous material in that temperature range.
  • the at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof are non-aromatic monomeric building blocks with 2 - 4 carbon atoms, and the molar proportion of the divinyl building blocks to the sum of the divinyl building blocks and the at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof and, if present, further building blocks (so to the sum of all monomeric building blocks plus the divinyl building blocks), is in the range of 8-30% preferably 10-20%.
  • the molar proportion of the divinyl building blocks to the sum of the divinyl building blocks and the at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof and, if present, further building blocks (so the sum of all monomeric building blocks plus the divinyl building blocks), is preferably more than 10%, 10 - 20% or 10-18% or in the range of 12-17%.
  • the corresponding reaction is preferably carried out in the presence of a low water solubility (radical) initiator, so an initiator that, at room temperature (20°C), normally has a solubility in water of at most 1 g/100g, preferably less than 1 g/100g, more preferably less than 0.5 g/100g.
  • a low water solubility (radical) initiator so an initiator that, at room temperature (20°C) normally has a solubility in water of at most 1 g/100g, preferably less than 1 g/100g, more preferably less than 0.5 g/100g.
  • the proposed material is completely free of aromatic building blocks except for divinyl building blocks which can be aromatic (e.g. DVB) - provides for a high capture capacity and a high oxidation resistance, i.e. high stability under continued capture use.
  • said amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof are selected from the group consisting of wherein X is hydrogen and R can be selected from the group consisting of methyl and halogen, the latter preferably selected as Cl or Br. R can also be CN except for the case where the above rightmost structure is taken. For solubility reasons, it may be preferable if the monomeric building blocks are selected from the above two leftmost and the rightmost structure.
  • said amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof are selected from the group consisting of wherein X is hydrogen and R can be selected from the group consisting of methyl, CN and halogen, the latter preferably selected as Cl or Br.
  • Said sorbent material can be a particulate copolymeric material based exclusively on at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof copolymerized and cross-linked with divinyl building blocks, wherein preferably it is based exclusively on amino mono allyl or precursors thereof copolymerized and cross-linked with divinylbenzene building blocks, or it is based exclusively on amino mono vinyl monomeric building blocks or precursors thereof copolymerized and cross-linked with divinylbenzene building blocks.
  • amino mono vinyl building blocks or precursors thereof are selected as vinylamine and/or the amino mono allyl building blocks or precursors thereof are selected as allylamine or acrylic nitrile or methacrylonitrile.
  • the reaction is carried out in the presence of a porogen to make sure the porosity of the resulting particulate sorbent material provides the functionality of reversibly binding carbon dioxide from the gas phase.
  • Said sorbent material can have a nitrogen content of at least 10% by weight, preferably of at least 14% by weight, preferably in the range of 14-25% by weight.
  • the nitrogen content is determined and calculated according to the description given further below.
  • the sorbent material takes the form of preferably essentially spherical beads with an average particle size in the range of 0.002 - 4 mm, 0.005 - 2 mm, 0.002 - 1.5 mm, 0.005 - 1.6 mm or 0.01-1.5 mm, preferably in the range of 0.25-0.50 mm.
  • the average particle size is determined and calculated according to the description given further below.
  • the sorbent material is preferably in porous form, and has a specific BET surface area, in the range of 0.5-150 m2/g or 10-200, preferably 30-80 m2/g, and/or has an average pore diameter in the range of 1-200 nm, preferably in the range of 10-150 nm, preferably in the range of 50-120 nm.
  • BET Brunauer, Emmett and Teller, also termed SBET
  • surface area analysis values are determined applying the method ISO 9277, and average pore diameters (average pore sizes) were determined using Mercury porosimetry and following the protocol according to ISO 15901-1 :2016 (Evaluation of pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption Part 1).
  • Said divinyl building blocks are preferably selected from the group consisting of divinylbenzene; 1 ,9-decadiene; 1 ,7-octadiene; 2,4,6-triallyloxy-1 ,3,5-triazine; pentaerythritol triacrylate (PETA); ethylene glycol diacrylate; ethylene glycol dimethacrylate; triethylene glycol diacrylate; tetraethylene glycol dimethacrylate; and mixtures thereof, wherein preferably said divinyl building blocks are selected only as divinylbenzene.
  • a carbon dioxide capture adsorber structure More specifically, it relates to an adsorber structure, preferably in the form of a monolith, the form of a layer or a plurality of layers, the form of hollow or solid fibres, including in woven or nonwoven (layer) structures, or the form of hollow or solid particles, comprising a sorbent material as defined above.
  • sorbent material More specifically, it relates to the use of a sorbent material as described above for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air, flue gas and biogas, preferably for direct air capture, in particular using a temperature, vacuum, or temperature/vacuum swing process.
  • it relates to a method for separating carbon dioxide from other gases using such a sorbent material.
  • the method for separating gaseous carbon dioxide from the gas mixture is preferably a method, which comprises at least the following sequential and in this sequence repeating steps (a) - (e):
  • This is e.g. possible by injecting a stream of partially of fully saturated or superheated steam, preferably by flow- through through the unit and over/through the sorbent, and thereby inducing an increase of the temperature of the sorbent material to a temperature between 60 and 110°C, starting the desorption of CO2;
  • the ambient atmospheric temperature established in this step (e) is in the range of the surrounding ambient atmospheric temperature +25°C, preferably +10°C or +5°C).
  • ambient atmospheric pressure and “ambient atmospheric temperature” refer to the pressure and temperature conditions to that a plant that is operated outdoors is exposed to, i.e. typically ambient atmospheric pressure stands for pressures in the range of 0.8 to 1.1 barabs and typically ambient atmospheric temperature refers to temperatures in the range of -40 to 60° C, more typically -30 to 45°C.
  • the gas mixture used as input for the process is preferably ambient atmospheric air, i.e. air at ambient atmospheric pressure and at ambient atmospheric temperature, which normally implies a CO2 concentration in the range of 0.03-0.06% by volume, and a relative humidity in the range of 3-100%. However, also air with lower relative humidity, i.e.
  • ⁇ 3%, or with lower or higher CO2 concentration can be used as input for the process, e.g. with a concentration of 0.1-0.5% CO2 by volume, so generally speaking, preferably the input CO2 concentration of the input gas mixture is in the range of 0.01-0.5% by volume.
  • the pressure in the unit (preferably at the end of this step) is in the range of 500-1000 mbarabs, preferably in the range of 550-1000 mbarabs or 600-950 mbarabs.
  • step (d) may include reduction of the pressure in the unit to values between 20- 500 mbarabs, preferably 50-250 mbarabs by means of evacuation, which causes evaporation of water from the sorbent subsequently both drying and cooling the sorbent.
  • the present invention relates to methods for preparing such a sorbent material.
  • a method for preparing a sorbent material is given, preferably a sorbent material as described above, for separating gaseous carbon dioxide from a gas mixture, preferably from at least one of ambient atmospheric air, flue gas and biogas, containing said gaseous carbon dioxide as well as further gases different from gaseous carbon dioxide, by cyclic adsorption/desorption using said sorbent material capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit, wherein amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof are copolymerized and cross-linked with divinyl building blocks, wherein the at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof are non-aromatic monomeric building blocks with 2-9 or 2 - 4 carbon atoms, and wherein the molar proportion of the divinyl building blocks to the sum of the divinyl building blocks and the at least one of amino mono allyl and amino mono vinyl monomeric building blocks
  • the molar proportion of the divinyl building blocks to the sum of the divinyl building blocks and the at least one of amino mono allyl and amino mono vinyl monomeric building blocks or precursors thereof and, if present, further building blocks, is preferably more than 10%, 10-18% or in the range of 12-17%.
  • acrylic nitrile alone or in combination with further amino mono allyl and/or amino mono vinyl monomeric building blocks or precursors thereof is copolymerized and cross-linked with divinyl building blocks, and in a second step the resulting copolymer is subjected to a reduction to convert the pendant nitrile groups into primary amine groups, wherein preferably in said first step exclusively acrylic nitrile is reacted with divinylbenzene building blocks.
  • the acrylic nitrile can also take the more general structure: with the definition of R as given above.
  • R is selected as methyl, so the acrylic nitrile system is preferably methacrylonitrile.
  • DVB and methacrylonitrile are reacted in this case as monomers.
  • Said reduction in the second step is preferably carried out so as to convert at least 80%, preferably at least 90 or 95 % of the nitrile groups into primary amine groups, wherein preferably for the reduction at least two, preferably at least three reduction cycles are carried out.
  • the reduction is carried out by using at least one of borohydride, lithium aluminium hydride, sodium cyanoborohydride, sodium bis(2-methoxyethoxy)aluminium hydride in an organic solvent, preferably selected from the group consisting of tetrahydrofuran, dioxane, dimethylsulfide, dimethoxymethane, or a mixture thereof, for a time span of at least 14h, preferably at least 18 hours per cycle.
  • an organic solvent preferably selected from the group consisting of tetrahydrofuran, dioxane, dimethylsulfide, dimethoxymethane, or a mixture thereof, for a time span of at least 14h, preferably at least 18 hours per cycle.
  • amino mono vinyl or a precursor thereof alone or in combination with further amino mono allyl and/or amino mono vinyl monomeric building blocks or precursors thereof is copolymerized and cross-linked with divinyl building blocks, wherein said amino mono vinyl or precursor thereof is selected from the group consisting of
  • V R wherein X is selected from the group consisting of tert-butyloxycarbonyl (Boc), phthalimide and R can be selected from the group consisting of methyl and halogen, the latter preferably selected as Cl or Br, in a second step the resulting copolymer is subjected to a deprotection to convert the pendant secondary amine groups into primary amine groups, wherein preferably in said first step exclusively said amino mono vinyl is reacted with divinylbenzene building blocks.
  • Boc tert-butyloxycarbonyl
  • the selection of the specific protecting group on the amine can influence the synthesis significantly. If particle formation is intended, for example formyl protecting groups are not suitable due to the water solubility of the monomer.
  • the copolymerization normally takes place in the presence of radical initiator, wherein preferably the radical initiator is selected from the group consisting of azobisisobutyronitrile, benzoyl peroxide, 2,2 -azobis-2- methyl butyronitrile, 2-2'-azobis(2,4-dimethyl)valeronitrile or 2,2-dimethoxy-2-phenyl-acetophenone of combinations thereof.
  • the radical initiator is selected from the group consisting of azobisisobutyronitrile, benzoyl peroxide, 2,2 -azobis-2- methyl butyronitrile, 2-2'-azobis(2,4-dimethyl)valeronitrile or 2,2-dimethoxy-2-phenyl-acetophenone of combinations thereof.
  • the radical initiator is selected from the group consisting of azobisisobutyronitrile, benzoyl peroxide, 2,2 -azobis-2- methyl butyronitrile, 2-2'-azobis(2,
  • Fig. 1 shows a schematic representation of a direct air capture unit
  • Fig. 2 shows a reaction scheme for PAA-co-DVB
  • Fig. 3 shows a reaction scheme for PVA-co-DVB
  • Fig. 4 shows the carbon dioxide capture capacity as a function of the reduction cycles for the PAA-co-DVB systems in comparison with standard PS-DVB systems;
  • Fig. 5 shows the quantification of conversion of nitriles to amines as a function of the reduction cycles for the PAA-co-DVB systems
  • Fig. 6 shows the carbon dioxide capture capacity as a function of DVB proportion for the PAA-co-DVB systems
  • Fig. 7 shows the influence of aging (convection oven; after 72 h of exposure at 90°C) for the proposed systems as opposed to conventional PS-DVD systems.
  • Solution B was added to Solution A all at once while maintaining the stirring, and the temperature of the reaction solution was set at 65°C. After the reaction solution reached 65°C, the reaction was continued for 18 hours.
  • reaction solution was then allowed to cool down to room temperature and filtered.
  • the solids were then transferred to a 1 L beaker, 1 L of ion-exchanged water was added, stirred with a magnetic stirrer for 30 minutes, and filtered. This was repeated one more time.
  • the desired polymer particles were then dried under reduced pressure at 75°C and 200 torr for 1 hour.
  • the average particle diameter was 330 micrometers (number average), the pore size determined by mercury injection method was 75 nanometers, and the specific surface area determined by the BET method was 62 m2/g.
  • the beads are dried in rotavapor.
  • the proposed synthetic approach allows for control of the morphology (pore size and surface area and cross-linking) as well as of the particle size and the nitrogen content (through the acrylonitrile monomer).
  • Table 1 shows how the properties of the PAN-co-DVB and also of the PAA- co-DVB after the reduction can be tuned as a function of the DVB to monomer ratio, wherein the DVB percentage and the AN percentage in the ratios are given as percentages relative to the total of the acrylonitrile (AN). and DVB.
  • Preferred pore size 50-200nm; preferred surface area: ⁇ 50m2/g.
  • the acrylonitrile-divinylbenzene (PAN-co-DVB) beads are then reacted with a reducing agent to obtain the allylamine-divinylbenzene (PAA-co-DVB) beads.
  • the acrylonitrile-divinylbenzene beads (7g) are added to a three-necked flask, flushed with nitrogen and the three-necked flask was cooled with an ice bath.
  • the borane-THF-solution (1M, 80 mL) was added dropwise under stirring. After complete addition, the reaction temperature is increased to 65°C (reflux) and the mixture is stirred for 24h. The steps can be repeated up to 4 times, and after complete addition, the reaction temperature is increased to 65°C (reflux) and the mixture is stirred for 24h.
  • the mixture is cooled to 0°C, 100 mL of 2M HCI (aqueous) in methanol is added and the mixture is stirred at 40°C for 3h. After that, the beads are filtered off and washed with water. At this stage the amine is protonated and to free the base, the beads are treated with 50 mL of an NaOH solution 2 M and stirred for 1 h at 40°C. The aminated beads are filter off and washed to neutral pH with demineralized water.
  • 2M HCI aqueous
  • the nitrogen content essentially corresponds to the capture capacity properties as illustrated in Fig. 4.
  • Fig. 6 shows the carbon dioxide uptake capacity as a function of the DVB proportion, indicating a clear sweet spot in the range between more than 10 and 18%, with an optimum in the range of 15%.
  • N elemental analysis gives the total nitrogen content (nitriles+primary amines), the N exchange capacity gives exchangeable amine content (primary amines), and the gives the quantitative amount of -CN groups left in the sorbent and hence, the conversion.
  • the average particle diameter was 310 micrometers (number average), the number average pore size determined by mercury porosimetry was 140 nanometers, and the specific surface area determined by the BET method was 49 m2/g.
  • the 10 g beads are placed in a 3-neck flask containing 100mL of ethanol and cooled to OdegC, and stirred at 100rpm for 1 h. Then 80g of 37% HCI was added to the flask, and the temperature of the reaction solution was set at 55degC. After the reaction solution reached 55°C, the reaction was continued for 18 hours.
  • the beads are filtered off and washed with water.
  • the amine is protonated and to free the base, the beads are treated with 50 mL of an NaOH solution 2 M and stirred for 24h at 20degC.
  • the aminated beads are filter off and washed to neutral pH with demineralized water.
  • reaction mixture is stirred and heated up to 70°C maintaining the temperature for 2 h, then the temperature is raised to 80°C and kept it for 16 h. The temperature is then raised 35 to 100°C for 3 h to distill out the porogen.
  • the reaction mixture is cooled down to room temperature and the beads are filtered off using a funnel glass filter and vacuum suction.
  • the beads are dried in rotavapor.
  • the polystyrene-divinylbenzene beads are functionalised using the chloromethylation reaction. 5 g of so obtained beads are added to a 3-neck flask containing 30 mL of chloromethyl methyl ether. 3.5 g of zinc chloride is added to the mixture over 2 h and heated for an additional 4 h to 60°C. After that, the mixture is cooled to room temperature and 25% HCI in water is added to quench chloromethyl methyl ether. The chloromethylated beads are washed until neutral with water, filtered off, and dried.
  • the chloromethylated beads are added to a three-necked flask with 27 g of methylal and the mixture is stirred for 1 h at 25°C (room temperature). To this mixture, 9 g of hexamethylenetetramine and 12 g of water are added and kept under gentle reflux for 6 h. The beads are filtered off and washed with water. To obtain a primary amine, a hydrolysis step followed by a treatment with a base are required. The beads are placed in a 3-neck flask containing 140 mL of a solution of hydrochloric acid (30%) - ethanol (95%) (volume ratio of 1 :3), the reaction mixture is heated to 80°C and kept at this temperature for 20 h.
  • the beads are filtered off and washed with water.
  • the amine is protonated and to free the base, the beads are treated with 50 mL of an NaOH solution 2 M, and stirred for 1 h at 50°C.
  • the aminated beads are filter off and washed to neutral pH with demineralized water.
  • Solution B was added to Solution A all at once while maintaining the stirring, and the temperature of the reaction solution was set at 80°C. After the reaction solution reached 80°C, the reaction was continued for 18 hours.
  • reaction solution was then allowed to cool down to room temperature and filtered.
  • the solids were then transferred to a 1 L beaker, 1 L of ion-exchanged water was added, stirred with a magnetic stirrer for 30 minutes, and filtered. This was repeated one more time.
  • the desired polymer particles were then dried under reduced pressure at 75°C and 200 torr for 1 hour.
  • the average particle diameter was 640 micrometers (number average), the pore size determined by mercury injection method was 60 nanometers, and the specific surface area determined by the BET method was 33 m2/g.
  • Table 2 properties of different PMAN-co-DVB systems
  • the methacrylonitrile-divinylbenzene beads (7g) are added to a three-necked flask, flushed with nitrogen and the three-necked flask was cooled with an ice bath.
  • the borane-THF- solution (1M, 80 mL) was added dropwise under stirring. After complete addition, the reaction temperature is increased to 65°C (reflux) and the mixture is stirred for 24h. The steps can be repeated up to 4 times, and after complete addition, the reaction temperature is increased to 65°C (reflux) and the mixture is stirred for 24h.
  • the mixture is cooled to 0°C, 100 mL of 2M HCI (aqueous) in methanol is added and the mixture is stirred at 40°C for 3h. After that, the beads are filtered off and washed with water. At this stage the amine is protonated and to free the base, the beads are treated with 50 mL of an NaOH solution 2 M and stirred for 1 h at 40°C. The aminated beads are filter off and washed to neutral pH with demineralized water. The eq. CO2 adsorption capacity was 0.98 mmol/g.
  • Solid Content Solid content is measured with a Halogen Moisture Analyzer (Adam Equipment PMB Moisture Analyzer); measurement temperature is 110°C, the measurement stops automatically at constant weight (0.002 g/15 s).
  • Halogen Moisture Analyzer Adam Equipment PMB Moisture Analyzer
  • the beads according to the above examples were tested in an experimental rig in which the beads were contained in a packed-bed reactor or in air permeable layers.
  • the rig is schematically illustrated in Fig. 1.
  • the actual reactor unit 8 comprises a container or wall 7 within which the layers of sorbent material 3 are located.
  • the inflow structure 4 for desorption if for example steam is used for desorption, and there is a reactor outlet 5 for extraction.
  • a vacuum unit 6 for evacuating the reactor.
  • Elemental analysis of the materials was carried out using a LECO CHN-900 combustion furnace. Prior to the measurement, the samples were treated under N2 flow (2 L/min) at 90°C for 2 h. Alternatively, the sample were treated in a vacuum oven at 60°C for 6 h.
  • Nitrogen adsorption measurements were performed at 77 K on a Quantachrome ASiQ.
  • the mass of the sample used was between 0.2-1.0 g. Since the samples contain a significant amount of water, it is important to use a treatment that does not alter their intrinsic porosity and pore structure. Therefore, prior to degassing, the samples were treated using the elutropic row method, which comprises removing water and replacing it with organic solvents with lower boiling point in the following order: methanol, acetone, and n-heptane. 2 g of samples was place in a chromatography column with a frit and flushed with 20 cm3 of each solvent in decreasing polarity order. The sample was then spread out on a petri dish and placed in a vacuum oven at 40°C for 24 hours. After that, the sample was degassed at 70 °C under vacuum for twelve hours before measurement.
  • the average particle size was determined by measuring samples under an optical microscope; a random selection of 100 non-overlapping particles was made.
  • Mercury Porosimetry Measurements Mercury porosimetry measurements were performed to analyze the pore sizes and pore volumes not accessible through N2 adsorption measurements. In order to perform mercury porosimetry measurements the following parameters were used:
  • the samples Prior to Hg porosimetry, the samples were degassed under vacuum at 70°C for 12 h. A sample is placed into a measuring assembly with an empty glass sample cell. Using the Washburn equation, the data set is converted into a cumulative curve of the amount intruded as a function of pore size. The derivative of this curve provides a pore size distribution of the pores accessible via the exterior of the material.
  • the resulting materials were further subjected to a screening oxidation resistance test, using the following conditions: the sorbent was placed in a petri dish and then placed in a convection oven, after 72 h of exposure at 90°C, the petri dish was taken out and the CO2 adsorption capacity of the sample was tested.
  • Sorbent A and B Two different basic primary aminated benzylamine DVB systems (primary amine-functionalized styrene-divinylbenzene resin as synthesized above) designated as Sorbent A and B:
  • Sorbents C-F Data is given for four different acrylonitrile-co-DVB systems designated as Sorbents C-F:
  • the flask was immersed in ice water. The flask was flushed with nitrogen, and then 16.5 g of 36-37% hydrochloric acid and 0.165 g of sodium chloride were added. When the temperature of the contents reached 15 °C, 11 g of allylamine was gradually added (although it generates heat, the rate of allylamine addition was adjusted so that the temperature did not exceed 30 °C). When the temperature dropped to 15°C, 1.75 g of citric acid was slowly added, pH measured was 5.5. After that, 1.8 g of V50 initiator [2,2'-azobis(2- methylpropionamidine) dihydrochloride] and 0.6 g of DVB (80%) were added and the internal temperature raised to 65 °C.
  • the materials of example 1 of EP-A-0 576 198 use 4-methyl-2-pentanol as porogen leading to materials having BET values above 200 m2/g (clear beads). Neither before nor after pyrolysis according to this example the materials of that example show any carbon dioxide binding in the gas phase. The equilibrium CO2 capacity was measured. The capacity was found to be 0 mmol/g. So these materials are not capable of reversibly binding carbon dioxide, for separating gaseous carbon dioxide from a gas mixture.

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Abstract

L'invention concerne un matériau sorbant apte à se lier de manière réversible au dioxyde de carbone, permettant de séparer le dioxyde de carbone gazeux d'un mélange gazeux, de préférence d'au moins l'un parmi l'air atmosphérique ambiant (1), le gaz de combustion et le biogaz, de préférence pour la capture directe d'air, en particulier à l'aide d'un procédé d'oscillation de température, de vide ou de température/vide. Ledit matériau sorbant (3) est un matériau copolymère particulaire à base d'au moins un élément parmi des blocs de construction monomères amino mono-allyliques et amino mono-vinyliques ou des précurseurs de ceux-ci copolymérisés et réticulés avec des blocs de construction divinyle. Ledit au moins un élément parmi les blocs de construction monomères amino mono-allyle et amino mono-vinyle ou des précurseurs de ceux-ci étant des blocs de construction monomères non aromatiques présente de 2 à 4 atomes de carbone, et la proportion molaire des blocs de construction divinyle par rapport à la somme des blocs de construction divinyle et dudit au moins un élément parmi les blocs de construction monomères mono-allyle et amino mono-vinyle amino ou des précurseurs de ceux-ci et, s'il y a lieu, d'autres blocs de construction, s'inscrit dans la plage de 10 à 20 %.
PCT/EP2024/082949 2023-11-27 2024-11-20 Matériaux sorbants destinés à la capture de co2, leurs utilisations et leurs procédés de poduction Pending WO2025114104A2 (fr)

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