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WO2025008318A1 - Matériaux sorbants destinés à la capture de co2, leurs utilisations et leurs procédés de fabrication - Google Patents

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

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Publication number
WO2025008318A1
WO2025008318A1 PCT/EP2024/068540 EP2024068540W WO2025008318A1 WO 2025008318 A1 WO2025008318 A1 WO 2025008318A1 EP 2024068540 W EP2024068540 W EP 2024068540W WO 2025008318 A1 WO2025008318 A1 WO 2025008318A1
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carbon dioxide
sorbent material
solid support
gaseous carbon
styrene
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Inventor
Cornelius GROPP
Davide Albani
Julian DURRER
Claudio LIMONE
Tomohide Yoshida
Patrick Schneider
Giacomo LAGOMARSINO
Ouassef NAHI
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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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • 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
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • 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
    • B01J20/28026—Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • 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
    • B01J20/28088—Pore-size distribution
    • B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
    • 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
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • 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
    • B01J20/3248—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 type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • 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
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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.
  • US-A-2017259255 discloses a high exchange-capacity anion exchange resin with dual functional-groups and a method of synthesis thereof.
  • the invention relates to the field of environmental function material synthesis and application.
  • the resin is based on chloromethylated polystyrene-divinylbenzene polymer as matrix, and by primary amination and quaternization, yields an anion exchange resin with dual functional-groups having both a weak base anionic group and a strong base anionic group.
  • the anion exchange resin not only has high adsorption capacity for water-born nitrate ions, but also can effectively squelch natural organic acids such as phytic acid in water, thus simultaneously removing nitrate ions and phytic acid organic matter from water. Therefore, the resin has a broad application potential in the fields of drinking water treatment, groundwater remediation, and advanced urban sewage treatment.
  • WO-A-97/31864 relates to anion-exchange compositions comprising anion-exchange functional groups comprising at least a first and a second nitrogen group, wherein the first nitrogen group is a positively charged quaternary amine and the second nitrogen group is selected from the group consisting of primary, secondary, tertiary or quaternary amines. Methods of making and using the compositions are also provided.
  • 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 to perform the cyclic adsorption/desorption of CO2 for hundreds or thousands of cycles over the same sorbent material, where the sorbent shall not undergo any or if at all only insignificant chemical transformations that impedes its reactivity towards 002.
  • Such systems e.g. in particulate form, into materials suitable for carbon dioxide capture
  • they can be chloromethylated in a first step under formation of a chloromethylated styrene-divinylbenzene resin and then aminated to form primary benzylamine groups which are then providing the primary amines for carbon dioxide capture.
  • Amination can e.g. be carried out by reacting the chloromethylated styrene- divinylbenzene resin with hexamethylenetetramine followed by hydrolysis typically under acidic conditions.
  • this object is achieved by a new method of making such materials and methods for separating gaseous carbon dioxide from a gas mixture using a new sorbent material e.g. made according to claim 1.
  • the claimed systems show superior properties compared with the polyamine systems known in the prior art, in particular if the chain length of the diamine system is chosen to have 3-4 carbon atoms.
  • a sorbent material 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 a sorbent material capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit.
  • Said use for separating gaseous carbon dioxide from a gas mixture is correspondingly a use, which entails cyclic adsorption/desorption using this sorbent material capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit.
  • the sorbent material is thus one which is capable of reversibly binding carbon dioxide and adsorbing said gaseous carbon dioxide in a unit in such a process.
  • the method for preparing such a sorbent material includes methods for preparing such sorbent materials ab initio, i.e. using starting solid support precursor material which before has not yet been used in corresponding carbon dioxide capture processes. However, it also includes methods where the solid support precursor starting material has already been used in such a carbon dioxide capture process and where the method is used for regenerating corresponding material, i.e. to regenerate, at least to a certain extent, the initial capture capacity.
  • This regeneration can be carried out with used sorbent material as solid support precursor which previously has never been treated in a method as claimed, but it can also be carried out with material as solid support precursor which previously has been treated in a method as claimed, then has been used in a carbon dioxide capture process until reaching a corresponding level of degradation, and then the method is applied again for regenerating (in this case refunctionalizing) and reestablishing the capture capacity of the corresponding solid support precursor.
  • the corresponding carbon dioxide capture process which the sorbent material has undergone prior to being subjected to such a regeneration process is normally a carbon dioxide capture process involving a heat and/or temperature and/or humidity swing and alternating capture and release steps.
  • the starting material of the proposed method for regeneration is sorbent material which has been used before as adsorbent for carbon dioxide separation from a gas mixture, but which has been oxidised due to having been used in this context and typically having lost at least 30% of the initial carbon dioxide capture capacity.
  • Such regeneration of sorbent material thus is preferably carried out if the carbon dioxide capture capacity has dropped by more than 30%, preferably by more than 20%, more preferably by more than 15% compared with the carbon dioxide capture capacity of pristine sorbent material, or regeneration of the sorbent material is carried out after having cycled the sequence of adsorption/desorption steps at least 500 times, preferably at least 1000 times, more preferably at least 10,000 times, but preferably before having cycled the sequence of steps 50,000 times, preferably before having cycled the sequence of steps 25,000 times.
  • the sorbent material (being the result of the method) comprises: primary amine moieties as well as at least one of secondary amine, and tertiary amine moieties, immobilized on a solid support, preferably it is sorbent material having primary amine functionality as well as secondary amine moieties immobilized on a solid support.
  • a solid support precursor (which, as pointed out above, can be a pristine material or can be a material already having been used in such a carbon dioxide capture process and where the method is used for regenerating corresponding material) is provided, having at least one of a primary amine and secondary amine functionality, preferably it is one having primary amine functionality.
  • this solid support precursor is reacted with at least one reactant selected from the following group: wherein PG is a protecting group, with the proviso that PG may also be a cyclic group with one branch of the cycle replacing the hydrogen bound to the protected secondary amine moiety of the reactant, X is a leaving group, i is in the range of 1-6 for the left structure and 0-5 for the right structure, in particular 1-3, and includes moieties of the type -CH2- as well as of the type -CH(CH3)- (preferably only one of the type -CH(CH3)- is present).
  • the solid support precursor is one which does not comprise any alkyhalide, in particular alkylchloride as pendant groups, or in particular does not comprise any such methylchloride groups, which are available for reaction with the reactant.
  • the proposed approach is a longer synthetic route but avoids cross-linking, with the enormous advantage of providing at least one of a higher carbon dioxide capture capacity, faster kinetics and higher stability.
  • the approach can be summarized as follows, wherein the upper branch shows the route with protecting groups of the covalent type, and the lower branch shows the route with protecting group of the salt type.
  • the starting material illustrated on the left carries corresponding surface accessible structures of the primary amine type, and the corresponding solid support precursor can be structured/porous polymers, silica, but also class II or class III MOF or the like.
  • the protecting group is selected from the group consisting of: hydrogenhalogenide (in particular for precursor material having primary amine functionality), including HCI, HBr, HI, phthalimide (in particular for precursor material having primary amine functionality), tert-butyloxycarbonyl, para-toluenesulfone, benzylidene, acetate/acetamide or trifluoroacetate/trifluoroacetamide.
  • HCI hydrogenhalogenide
  • HBr HBr
  • HI phthalimide
  • tert-butyloxycarbonyl para-toluenesulfone
  • benzylidene acetate/acetamide or trifluoroacetate/trifluoroacetamide.
  • Systems of the type t only -CH2- include systems of the following type: wherein X' is an anion, preferably selected from the group of tosylate, mesylate, or in particular halogens, in particular Cl, I, Br.
  • the general structure of the reagents can be as follows: wherein X is halogen, in particular Cl, Br, or I, i is 1-6, in particular 1-3, and again includes moieties of the type -CH2- as well as of the type -CH(CH3)- (preferably only one of the type -CH(CH3)- is present).
  • the reagent can be provided from well available alkanolamine starting material and can, without further need of purification, directly be used for treatment of the solid support precursor.
  • the conversion into said sorbent material takes place by removing said protecting group using an organic base or an inorganic base or combination thereof, wherein preferably organic bases are selected from the group of pyridine, alkylamines, such as triethylamine, imidazole, tetramethylammonium hydroxide and wherein inorganic bases are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, and a combination thereof.
  • organic bases are selected from the group of pyridine, alkylamines, such as triethylamine, imidazole, tetramethylammonium hydroxide and wherein inorganic bases are preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, and a combination thereof.
  • the reaction with the reactant and/or the step of removal of said protecting group is carried out in an organic or an inorganic solvent or a combination thereof, wherein preferably the solvent is selected from the group consisting of water, methanol, ethanol, di-methoxy methane, tetrahydrofurane, dimethylformamide, or a combination thereof, wherein preferably the solvent is water.
  • the reactant is added to the solid support precursor in an equivalent ratio of 0.1-10, preferably 0.1 -1.0, relative to the primary/secondary amine of the solid support precursor.
  • the solid support precursor is polystyrene based, preferably a polystyrene based benzyl amine, polystyrene based allylamine, preferably it is an amine functionalized styrene-divinylbenzene support, preferably functionalised by primary benzylamine or primary a-methylbenzylamine, or a styrene allylamine support and/or the solid support precursor is a solid styrene-divinylbenzene support functionalised by primary benzylamine or primary a-methylbenzylamine groups as the result of a reaction of halogenmethylated styrene-divinylbenzene, preferably chloromethylated styrene- divinylbenzene, with hexamethylentetramine or through amidomethylation of styrene- divinylbenzene and subsequent hydrolysis.
  • EP 23 212 181.4 is expressly included into this specification as for the manufacturing thereof and the structural characterization and properties.
  • the solid support precursor material preferably in the form of a primary benzylamine based support material or a styrene allylamine support, is in the form of at least one of monolith, layer or sheet, hollow or solid fibres, preferably in woven or nonwoven structures, hollow or solid particles, or extrudates, wherein preferably it takes the form of preferably essentially spherical beads.
  • the solid support material based on primary benzylamine styrene- divinylbenzene support material or a styrene allylamine support, is in the form of at least one of monolith, layer or sheet, hollow or solid fibres, preferably in woven or nonwoven structures, hollow or solid particles, or extrudates, wherein preferably it takes the form of preferably essentially spherical beads.
  • the solid support material preferably in the form of a styrene-divinylbenzene based support material or a styrene allylamine support, can be in the form of solid particles embedded in a porous or non-porous matrix.
  • the sorbent material may take the form of preferably essentially spherical beads with a particle size (D50) 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 0.30-1.25 mm.
  • D50 particle size
  • X of the reactant is selected from the group consisting of halogen, tosylate, mesylate, ester, imide, carbodiimide, pyrazole.
  • 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, in particular using a temperature, vacuum, or temperature/vacuum swing process, wherein said sorbent material is obtainable or obtained using a method as defined above.
  • the sorbent material is one which comprises: primary amine moieties as well as at least one of secondary amine, and tertiary amine moieties, immobilized on a solid support, preferably it is sorbent material having primary amine functionality as well as secondary amine moieties immobilized on a solid support.
  • sorbent material for separating gaseous carbon dioxide from a gas mixture
  • a method of carbon dioxide separation from a gas mixture using such a sorbent material preferably for separating CO2 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, wherein said sorbent material, wherein the sorbent material comprises: primary amine moieties as well as secondary amine and/or ether moieties immobilized on a solid support.
  • such a method for separating gaseous carbon dioxide is a method or a method is used, which comprises at least the following sequential and in this sequence repeating steps (a) - (e):
  • the ambient atmospheric temperature established in tl 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.
  • air with lower or higher CO2 concentration can be used as input for the process, e.g. with a concentration of 0.1 -0.5% 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.
  • a unit for separating gaseous carbon dioxide from a gas mixture preferably from at least one of ambient atmospheric air, flue gas and biogas, preferably direct air capture unit, comprising at least one reactor unit containing sorbent material suitable and adapted for flow-through of said gas mixture, wherein the reactor unit comprises an inlet for said gas mixture, preferably for ambient air, and an outlet for said gas mixture, preferably for ambient air during adsorption, wherein the reactor unit is heatable to a temperature of at least 60°C for the desorption of at least said gaseous carbon dioxide and the reactor unit being openable to flow-through of the gas mixture, preferably of the ambient atmospheric air, and for contacting it with the sorbent material for an adsorption step, wherein preferably the reactor unit is further evacuable to a vacuum pressure of 400 mbar(abs) or less, wherein the sorbent material preferably takes the form of at least part of an adsorber structure comprising an array of individual adsor
  • Fig. 1 shows a schematic representation of a direct air capture unit
  • Fig. 2 shows the increase in carbon dioxide capture capacity through post modification for two different starting benzylamine beads
  • Fig. 3 shows the increase in carbon dioxide capture capacity by way of chloro methylation and amination for different systems
  • Fig.4 compares the increase in carbon dioxide capture capacity by way of chloro methylation and amination to post-functionalization
  • Fig. 5 shows the improvement in kinetics for the materials obtained through post modification for two different solid supports
  • Fig. 6 shows the increase in carbon dioxide capture capacity through post modification for benzylamine beads using 2-methylchloropropylamine HCI and 1- methylchloropropylamine HCI;
  • Fig. 7 shows the increase in carbon dioxide capture capacity through post modification for allylamine systems
  • Fig. 8 shows the increase in carbon dioxide capture capacity through post modification of a structured sorbent (beads or amine sorbent embedded in a structure);
  • Fig. 9 shows the carbon dioxide capture capacity through post modification for regeneration or re-functionalization of beads post degradation.
  • 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.
  • the chloromethyl-functionalized polystyrene-divinylbenzene beads are aminated using the direct amination reaction:
  • the mixture containing chloromethylated beads, methylal and one of the above amine are kept under stirring at 50°C for 12 h.
  • the beads are filtered off and washed with methanol and water.
  • the aminated beads are then dried in the vacuum oven at 60°C for 12h.
  • the framework can be defined as follows:
  • amines on sorbent carrier material examples include polystyrene-based benzylamines; aliphatic amines (e.g. polyallylamines), other functionalities that react favorably with named reagents.
  • solvents that can be used for the synthesis procedure of diamine- functionalized systems: H2O, methanol, ethanol, dimethoxymethane, dimethylformamide, preferably H2O.
  • bases organic bases such as alkylamines, e.g. triethylamine, pyridine, imidazole, tetramethylammonium hydroxide, ; inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, and a combination thereof.
  • Equivalents of amine reagent 0.1 -1.0 compared to e.g. benzylamine styrene- divinylbenzene.
  • the mixture containing the benzylamine beads, DMF and of the above phthalimide- protected amines is kept under stirring at 60°C for 18h.
  • the mixture is then cooled to room temperature, the beads are filtered off and washed with methanol and water.
  • the mixture containing the benzylamine beads, DMF and of the above amines is kept under stirring at 60°C for 18h.
  • the mixture is then cooled to room temperature, the beads are filtered off and washed with water.
  • the beads are then stirred in a 2M aqueous solution of NaOH for 1 h, washed to neutral with water and methanol and dried in the vacuum oven at 60°C for 12h.
  • the calculated conversion from the nitrogen content as measured in the elemental analysis amounts to 13-15% (N content in wit%: 9.8 with Sorbent B as starting materials and 12.4 with Sorbent A as starting material).
  • Chloropropyl ammonium chloride 107.5 g Chloropropyl ammonium chloride are dissolved in a beaker with 250 g of water for 20 min then they are added to the reactor. Rinse the beaker with 50 g of water.
  • Results are given in Fig. 9, showing how the spent material can be recovered in terms of capture capacity.
  • a 1 L round bottom flask is charged with 32 g of amino-2-propanol and 150 mL of dioxane.
  • 150 mL of a solution of 4N HCI in dioxane is added and the mixture is stirred at room temperature for 10 min.
  • 34.5 mL of thionyl chloride is added slowly over 2 min.
  • the reaction is stirred at 80 °C for 18h.
  • the mixture is cooled to room temperature and diluted with 200 mL of Et20.
  • the resulting precipitate is filtered off, washed with 200 mL Et20 and dried under vacuum to give 50 g of 2-chloropropane-1 -amine hydrochloride.
  • a 1 L round bottom flask is charged with 10 g of 2-amino-1 -propanol and 75 mL of dioxane. 75 mL of a solution of 4N HCI in dioxane is added and the mixture is stirred at room temperature for 10 min. 17 mL of thionyl chloride is added slowly over 2 min. The reaction is stirred at 80 °C for 18h. The mixture is cooled to room temperature and diluted with 150 mL of Et20. The resulting precipitate is filtered off, washed with 150 mL Et20 to give 25 g of hygroscopic 1-chloropropane-2-amine hydrochloride, which was used immediately for the next step.
  • Sorbent B was functionalized using the above reagents 2-chloropropane-1 -amine hydrochloride and 1-chloropropane-2-amine hydrochloride to yield post-functionalized material.
  • the calculated conversion from the nitrogen content as measured in the elemental analysis amounts to 13-15% (N content in wt%: 10.7).
  • the calculated conversion from the nitrogen content as measured in the elemental analysis amounts to 13-15% (N content in wt%: 10.4).
  • the 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 solids were then transferred to a 1 L beaker, 1 L of methanol was added, stirred with a magnetic stirrer for 30 minutes, and filtered.
  • 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
  • the pore size determined by the mercury injection method was 75 nanometers
  • the specific surface area determined by the BET method was 62 m 2 /g.
  • the beads are dried in rotavapor.
  • the acrylonitrile-divinylbenzene beads are then reacted with a reducing agent to obtain the allylamine-divinylbenzene 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 (1 M, 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 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
  • Results are given in Fig. 7, showing how the allylamine sorbent material can be boosted in terms of capture capacity.
  • the sheets can be produced from a mixture of 50 wt% (wet, -85% solid content) ion exchange resin (I ER) powder at a mean particle size of 75 microns (D50, volume based) and 50 wt% ultra-high-molecular-weight polyethylene (UHMWPE, molecular weight 4.2 million g/mol) at a mean particle size of 30 microns (D50).
  • the two powders are mixed using a 3D rotational mixer for 15 minutes. Approximately 8 g of powder mixture are filled in an aluminum mold with a cross section of 10x20 mm. The mold is closed and placed in an oven previously pre-heated to 220°C. No pressure is applied.
  • the mold is positioned on small metallic supports to facilitate heating on both sides and kept in the oven at temperature for 40 min. Afterwards, the mold is removed from the oven and left to cool in ambient air to reach room temperature before being opened. Upon opening, a sheet matching the mold inner dimensions is obtained.
  • the sheet density is typically 450-500 kg/m3.
  • Results are given in Fig. 8, showing how the structured sorbent material can be boosted in terms of capture capacity and also how it can be regenerated using the method.
  • haloalkylamine hydrohalide e.g. 3-chloropropylamine hydrochloride
  • 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.
  • 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 (0.002g/15s).
  • Halogen Moisture Analyzer Adam Equipment PMB Moisture Analyzer
  • 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 at40°C for 24 hours. After that, the sample was degassed at 70 °C under vacuum for twelve hours before measurement.
  • 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.
  • the degree of post-functionalization is calculated as the relative number of e.g propylamine monomers per benzylamine or allylamine monomers.
  • %N is the nitrogen content in percent weight as determined by elemental analysis
  • MWmonomer B is the molecular weight in g/mol of the crosslinking monomer (e.g.
  • MWN divinyl benzene
  • MWDVB 130.19 g/mol
  • Fig. 2 shows the increase in carbon dioxide capture capacity through post modification for two different starting benzylamine beads, given relative to 100% benzyl amine as a reference.
  • Data is given for two different basic primary aminated DVB systems designated as Sorbent A, and B, one chloromethylated DVB system designated as Sorbent C in the following table:
  • Fig. 3 shows the corresponding carbon dioxide capture capacity situation for the case where the material is produced not using post-modification according to this invention but using the conventional approach of chloromethylation and subsequent amination.
  • the relative increase is only in the range of 5-30%, so it is significantly lower than when using the proposed post-modification approach.
  • Fig. 4 gives a direct comparison of the carbon dioxide capture capacity situation of Sorbent C, obtained through chloromethylation and amination, with the Sorbent A and B obtained through post-functionalization.
  • Sorbent A and B show superior carbon dioxide capture capacity compared to Sorbent C, which - without being bound to any theoretical explanation - is expected to be due to the higher availability of primary amines.
  • Fig. 5 shows the improvement in kinetics for the post modified systems, the capacity increase is 45-50%. Also, it was found that the corresponding material is able to go through a larger number of capture cycles without deterioration than the benzyl amine systems.

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Abstract

L'invention concerne un procédé de préparation d'un matériau sorbant (3) destiné à séparer le dioxyde de carbone gazeux d'un mélange gazeux, de préférence d'au moins l'un de l'air atmosphérique ambiant (1), du gaz de combustion et du biogaz, contenant ledit dioxyde de carbone gazeux ainsi que d'autres gaz différents du dioxyde de carbone gazeux, par adsorption/désorption cyclique à l'aide d'un matériau sorbant (3) capable de se lier de manière réversible au dioxyde de carbone et d'adsorber ledit dioxyde de carbone gazeux dans une unité (8), le matériau sorbant (3) comprenant : des fractions d'amine primaire ainsi qu'au moins l'une d'une amine secondaire, et des fractions d'amine tertiaire immobilisées sur un support solide, et est réalisée à l'aide d'une voie d'amination évitant une réticulation.
PCT/EP2024/068540 2023-07-05 2024-07-02 Matériaux sorbants destinés à la capture de co2, leurs utilisations et leurs procédés de fabrication Pending WO2025008318A1 (fr)

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