Moisture swing adsorbents and production thereof

Abstract

The invention relates to moisture swing adsorbents based on inorganic porous metal oxide support material treated with quaternary cationic sorbent compound, a method of manufacturing thereof and the use of such adsorbent materials for carbon dioxide capturing from a gas mixture or from air.

Description

[0001]202400128 Foreign Filings 1 MOISTURE SWING ADSORBENTS AND PRODUCTION THEREOF TECHNICAL FIELD OF THE INVENTION The invention relates to moisture swing adsorbents based on treated inorganic porous support materials with quaternary cationic compounds, a method of manufacturing thereof and use of such adsorbent materials for carbon dioxide capturing from a gas mixture, especially from air. BACKGROUND OF THE INVENTION Rising CO2 levels in the atmosphere due to climate change and global warming are widely recognized as some of the most critical environmental issues facing the world today. The main reasoning behind global warming is the release of greenhouse gases into the atmosphere, with carbon dioxide (CO2) being a primary greenhouse gas. The combustion of fossil fuels such as coal, petroleum, and natural gas is the primary source of CO2 emissions. Considering that these fossil fuels still cover most of the world's energy needs, it is essential to address the issue of CO2 emissions to mitigate the impact of global warming. A lot of effort and focus has been placed on reducing CO2 emissions in various industries by looking into alternative energy sources to fossil fuels and through implementing other Negative Emissions Technologies (NETs). In the realm of carbon capture and sequestration most of the implementation has been around systems for point source emissions, however this is not 100% efficient and many other sources of CO2 emissions from smaller or more mobile sources, i.e. automotive, aviation, etc., cannot use these technologies. Technologies for capturing CO2 will need to be sufficient for more efficient capacities and will also need to be retrofitted onto existing plants and also for other smaller application areas. Accordingly, direct air capture (DAC) technologies which remove CO2 directly from the air have been an area of focus. Industrial direct air capture systems (DAC) are available based on porous sorbent systems. By being able to remove CO2directly from air these unavoidable emissions can be mitigated and the desired CO2removal targets can be achieved. However, existing direct air carbon dioxide (CO2) capture processes have limited adoption due to high cost, and high energy consumption of CO2. A major factor with these DAC systems is the sorbent technology, considering treated porous support materials with the sorbent materials. The solid sorbent is proposed to capture CO2 directly from air, while its low energy-cost nature also points capturing CO2 from a variety of other gas streams with larger CO2 concentrations. The key to any DAC system being commercially viable lies in its ability to efficiently and selectively capture the CO2at low atmospheric partial pressures and overall have low energy of capture and regeneration. There are improvements regarding DAC sorbent technologies with the mission of negative emission, and aiming lower energy consumption and simple operating systems. These known systems can be categorized under thermal swing adsorption (TSA), pressure swing adsorption (PSA) or moisture swing adsorption (MSA). Thermal swing adsorption (TSA) requires heat to regenerate, pressure swing adsorption (PSA) requires 202400128 Foreign Filings 2 vacuum to regenerate and moisture swing adsorption (MSA) requires water to evolve off the adsorbed CO2. One mentioned type of direct air capture technology involves the use of temperature swing adsorption (TSA) processes, typically using liquid or solid chemi- or physisorbents. This process has fundamental restrictions and process costs for CO2 capture at dilute ambient concentrations. The high heat of adsorption needed for selective CO2 uptake necessitates large temperature swings. One another mentioned alternative to known solid sorbent DAC systems can be moisture or humidity swing DAC process. The moisture swing adsorbents considered as promising method for capturing industrial process CO2, as they operate at lower temperatures, have longer lifetimes and better oxidation resistance. These moisture swing adsorbents (MSA) includes a porous support material that is functionalized or treated with quaternary groups where the CO2 can interact ionically. MSA typically employs solid sorbents with quaternary ammoniums. Quaternary ammonium can also be referred to as quaternary amine. However, other quaternary species may also be employed, such as, phosphonium species or even other tertiary species may also be employed, such as sulfonium species. However, commercial MSA sorbents are typically resin based and suffer from particle expansion and contraction during the humidity cycling. This can lead to issues in contactor systems and lower uptake rate and efficiencies due to changing pore characteristics. MSA sorbents made with porous supports possessing humidity stable pore structures, improved pore characteristics and high active nitrogen contents may show faster cycle time and improved working capacities. It is known in the art that moisture swing absorption technologies are based on adsorbents based on porous polymeric resin particles. In particular, anion exchange polymer resins possessing quaternized organic moieties such as amines, with a halide based counter ion. These materials are first ion exchanged in to the hydroxide or bicarbonate species to activate them for capturing of CO2 under low humidity conditions. Not to be bound by any specific mechanism, it has been proposed in the literature that under low humidity conditions a bicarbonate counterion associated with a single quaternary ammonium and an available hydroxide counter ion associated to a neighboring quaternary ammonium will dominate. This hydroxide creates an available site for the interaction of CO2to form another bicarbonate counterion. Upon the introduction of high humidity a single carbonate species associated with two quaternary ammonium moieties will form and one molecule of CO2 is evolved. Similarly, porous material supports could be used and functionalized with quaternary and / or tertiary cationic sorbent species. Several factors could impact the final performance of the adsorbent material. Despite capturing capacities of polymeric resin particles, changing in size and volume with moisture uptake and removal can result in slower uptake kinetics. Regarding porous material supports treated with quaternary and / or tertiary cationic sorbent species, preferably quaternary ammonium species, a large amount of treatment would need to be applied to the porous particles to provide sufficient working capacities. At the 202400128 Foreign Filings 3 same time only the hydroxide and bicarbonate species of the sorbent remain active for CO2 capture, hence the sorbent treatment on the particle would need to be ion exchanged to these species. Use of quaternary cationic species, especially quaternary ammonium compounds in MSA sorbents for CO2 capture from air is described in various patents / patent applications as hereby given a selection of those. US 2014 / 356275 A1 describes coextruded sheets of material, where a polymer matrix and an ion- exchange resin material containing quaternary ammonium groups are coextruded. The product is then soaked in carbonate solutions to replace chloride ions by carbonate ions. A comparable system and method of preparation of such a system is described in US 2015 / 004084 A1. US 2023 / 038851 A1 further focusses on polysulfon copolymers (poly(arylene ether sulfon) copolymers) that are modified with ternary amines that are converted to quaternary ammonium compounds using for example methyl iodide (CH3I). The halide counterions are exchanged with OH- or CO3- and the modified polymer is processed into membranes, films or hollow fibers. US 2022 / 323934 A1 discloses compositions of porous crosslinked polymers with quaternary ammonium compounds fixed in the network by crosslinking functions of the quaternary compounds. After polymerization, ion exchange to receive OH- or CO3- counter ions is performed. One article from Advance Functional Materials Journal published in 2013, 23, 4720-4728, and titled as “Three- Dimetionally Ordered Macroporous Polymeric Materials by Colloidal Crystal Templating for Reversible CO2 Capture”, discloses the ion exchange process being conducted before the incorporation of the quaternary ammonium compound to the formation of the anion exchange resin particle. But, within this article an ion exchange is conducted within crosslinked polymerization in order to have maximum pore sizes after polymerization. The major drawback with the known systems is the expansion and contraction of the porous resin particles during the humidity cycling process, which can impact their volume utilization in a contactor system and the accessibility and diffusion rates of the CO2to the internal sorbent, especially quaternary ammonium moieties. This can impact the uptake rate, cycle times and working capacity of these resin based systems. A further drawback is the cost of amine sorbent based DAC systems in the sorbent regeneration and applicability to different application areas. All these known systems in the art are rather applicable on the big productions sites. Seeing as a major cost of DAC systems is in the sorbent regeneration, novel moisture swing sorbents presented within the present invention offer a lower cost solution with improved efficiency on capturing CO2. This novel and inventive moisture swing sorbents can be utilized in different application areas as well. Accordingly, the present invention relates specifically to the moisture swing adsorbents based on porous 202400128 Foreign Filings 4 support materials treated with quaternary cationic sorbent compounds, and having improved pore and surface area characteristics with improved nitrogen content for a better CO2 adsorption capacity. The process for obtaining thereof, and / or capturing CO2from a gas mixture or from air is also a part of the present invention. Present invention further provides a novel method for MSA material production. Compared to known MSA materials obtained with the known methods (such as anion exchange polymer resins), CO2adsorption capacity within the present invention is either improved significantly or comparable to that of solid amine sorbent based DAC systems. Therefore, the technical problem to be solved by the present invention is thus to provide a novel MSA material and production thereof for direct air capturing, that is based on inorganic porous support particles treated with quaternary cationic sorbent compounds. BRIEF SUMMARY OF THE INVENTION It is an object of the present invention to provide moisture swing adsorbents based on treated porous inorganic support materials, having improved Nitrogen (N) content, improved CO2 capacities and avoiding potential hazardous waste streams from active sorbent leaching. Accordingly, a moisture swing adsorbent material (MSA) based on an inorganic porous metal oxide material and process for treating the inorganic porous metal oxide material with a quaternary cationic sorbent compound is provided. The moisture swing adsorbent materials are to be used for direct air capture applications, mainly for CO2 capture from air. According to the present invention, a novel method of treating inorganic porous metal oxide materials with quaternary cationic compounds, preferably with quaternary ammonium hydroxide and / or bicarbonate is provided to obtain MSAs. The inventors have surprisingly found that the MSA material has a Nitrogen content of at least 1 wt% or more based on the adsorbent material itself, as defined in claim 1. This new MSA material solves above mentioned technical problem as it provides relatively high total capacities for CO2 adsorption, high uptake efficiencies for faster cycle times, which does not noticeably expand or contract during humidity cycling, and which allows regeneration with humidity providing a lower energy of regeneration when it is compared to thermal swing materials and / or to be considered as alternative to known moisture swing adsorbents (such as; anion exchange resins) Advantageously, the process of making these adsorbents allows increased flexibility in the quaternary cationic sorbent compound active treatment, regardless of being employed as grafted or impregnated on the porous support material. Advantageously, the process of making these adsorbents allows increased flexibility in the porous support material properties, allowing increased active nitrogen (N) content to be employed regardless of porous support surface area and pore size characteristics. 202400128 Foreign Filings 5 Advantageously, the process of making these adsorbents allows for reduced waste streams from leached quaternary cationic species during the activation / ion exchange process. Advantageously, claimed MSA material based on inorganic porous metal oxide material treated with quaternary cationic sorbent compounds with hydroxide and / or bicarbonate counter-ion(s) provide increased carbon dioxide capturing capability supported with increased active nitrogen (N) content and high CO2uptake rates. Even if preferred quaternary cationic compounds are limited to mainly quaternary ammoniums, some other quaternary or even tertiary cationic species may also suitable as sorbent compounds for treating the inorganic porous metal oxide material, such as quaternary phosphoniums, or tertiary sulfoniums. Moreover, the inorganic porous metal oxide support materials having optimized BET SA, with a sufficient pore volume and pore diameter further provides the advantages of fast CO2 uptake efficiency and improved support stability to these alkaline treatments. By use of such porous support materials, loss of pore volume due to porous support in-stability is prevented and improved hydrothermal stability is obtained. Thus maintaining accessibility to the active N species during repetitive high humidity regeneration. Accordingly, the first aspect of the present invention relates to an MSA material based on inorganic porous metal oxide support material treated with at least one quaternary cationic compound, preferably with ion-exchanged quaternary cationic compound, wherein the MSA material has higher Nitrogen content, such as N ≥ 1 wt%, as defined in claim 1. A second aspect of the invention is the method of production of such MSA material wherein the quaternary cationic sorbent compounds are ion-exchanged to hydroxide and / or bicarbonate before being treated in / on inorganic porous metal oxide support material. A third aspect of the invention is the use of such moisture swing adsorbents (MSA), for carbon dioxide capturing from a gaseous mixture, especially from air. BRIEF DESCRIPTION OF THE DRAWING For the purpose of better illustrating the advantages and properties of the claimed moisture swing adsorbent material and its production thereof, graphs are attached as a non-limiting examples such as; Figure 1: Cumulative CO2 adsorption curve for Comparative Examples 1, 5 and 6 Figure 2: Relative CO2 concentration / CO2 breakthrough curve for Comparative Examples 1, 5 and 6 Figure 3: Cumulative CO2 adsorption curve for Inventive Examples 1 to 4 Figure 4: Relative CO2 concentration / CO2 breakthrough curve for Inventive Examples 1 to 4 Figure 5: Cumulative CO2 adsorption curve for Inventive Examples 5 to 8 Figure 6: Relative CO2 concentration / CO2 breakthrough curve for Inventive Examples 5 to 8 Figure 7: Cumulative CO2 adsorption curve for Inventive Examples 8 to 11 202400128 Foreign Filings 6 Figure 8: Relative CO2 concentration / CO2 breakthrough curve for Inventive Examples 8 to 11 Figure 9: Cumulative CO2 adsorption curve for Inventive Examples 12 to 14 Figure 10: Relative CO2 concentration / CO2breakthrough curve for Inventive Examples 12 to 14 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a moisture swing adsorbent (MSA) material having Nitrogen (N) content of ≥ 1 wt%, preferably more than ≥ 1.5 wt% on a dry basis, provided with increased carbon dioxide absorption capacities. The present invention relates to a moisture swing adsorbent (MSA) material comprising inorganic porous support material(s) treated with quaternary cationic sorbent compound(s); preferably treated with ion-exchanged quaternary cationic sorbent compound(s), more preferably with ion-exchanged quaternary ammonium sorbent compound(s); wherein the MSA material has a Nitrogen (N) content of ≥ 1 wt%, preferably more than ≥ 1.5 wt% on a dry basis. According to a preferred aspect of the present invention, the ion-exchanged quaternary ammonium sorbent compound has at least one quaternary ammonium moiety with an active counter-ion; and the active counter-ion is hydroxide or an ion capable of forming hydroxide upon reaction with water. According to a preferred aspect of the present invention, mentioned active counter-ion is selected from hydroxide, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or combinations thereof, preferably selected from hydroxide, carbonate and / or bicarbonate. According to a preferred aspect of the present invention, the moisture swing adsorbent (MSA) material has a Nitrogen (N) content of more than ≥ 1 wt%, preferably from 1 to 5 wt%, more preferably from 1.5 to 4 wt%, still more preferably from 1.5 to 3.5 wt%, on a dry basis. Within the present invention, “dry basis” means that the free moisture content in the MSA material at 85 to 105 °C is less than 20%, considering that high moisture content may lower the nitrogen content. MSA Material MSA technology is basically based on a membrane sorbent that uses a water swing to absorb and desorb CO2. As already discussed in the background art, most of the known MSA adsorbent materials are based on polymeric resin particles. Although, these materials can have fairly high capacities they can poses other undesirable properties, i.e. changing in size and volume with moisture uptake and removal, and slower uptake kinetics. Similarly, it is known in the art that porous supports could be used and functionalized with quaternary ammonium species, but several factors could impact the final performance of the material, and even not disclosed within the MSA production purposes. In order to have a high N content and corresponding 202400128 Foreign Filings 7 adsorption capacity, a large amount of treatment would need to be applied to the porous particles. At the same time only the hydroxide and bicarbonate species of the quaternary cationic sorbents are active for CO2capture, hence the cationic sorbent treatment on the porous support particle would need to be ion exchanged to hydroxide and bicarbonate species. The present invention provides a method for producing a moisture swing adsorbent (MSA) material that does not employ a polymeric resin support, wherein a high active N content can be obtained using various porosities to for higher adsorption efficiency. Contrary to the traditional manufacturing approach of moisture swing adsorbent materials, wherein the ion exchange process for the quaternary sorbent material followed after porous support material treatment with the quaternary compounds, the inventors have surprisingly found that the ion exchange process can be applied to the quaternary cationic sorbent compounds to exchange the inactive counter ion with an active counter ion capable of forming hydroxide upon reaction with water, before the metal oxide support material is treated with such cationic sorbent material. This new approach provides better CO2 capturing abilities avoids removing a significant portion of the treatment during the ion exchange process and the ability to achieve high active treatments on a variety of support particles with optimized porosities. For such kind of a new approach for obtaining above mentioned MSA materials, without any intention to limit the scope of protection, there has been provided some special type of a metal oxide support materials and / or quaternary cationic sorbent compounds as given below. According to the present invention, the treatment process for obtaining the moisture swing adsorbent material is not limited to grafted quaternary compounds (such as quaternary ammonium) but also enables impregnation of those materials, that still provides high carbon dioxide absorbance efficiency. Quaternary Cationic Sorbent Compounds Present invention relates to a Moisture Swing Adsorbent (MSA) material based on at least one porous support material treated with at least one quaternary cationic sorbent compound, preferably counter-ion exchanged quaternary cationic sorbent compound having an exchanged counter-ion capable of forming hydroxide upon reaction with water (such as; hydroxide or bicarbonate), wherein the MSA material has a Nitrogen (N) content of at least 1 wt% on a dry basis. According to the present invention, cationic compounds can be selected from quaternary ammoniumor any other equivalent cationic compounds without any intention to limit the scope of protection. According to the present invention, quaternary cationic sorbent material is selected for providing examples without any intention to limit the scope of protection. 202400128 Foreign Filings 8 According to the present invention, quaternary cationic species may be employed on porous support materials either by grafting (covalent bonding) or impregnation (non-covalent impregnation) or in combination thereof. According to the present invention, the quaternary ammonium sorbent material may mean a sorbent material having at least one quaternary ammonium cation together with an active counter-ion capable of forming hydroxide upon reaction with water in it. According to the present invention, it is preferred to have a quaternary ammonium cationic sorbent compound together with an active counter-ion capable of forming hydroxide upon reaction with water in it. According to the preferred aspects of the present invention, the quaternary ammonium sorbent material may also mean quaternary ammonium salt, which are salts of quaternary ammonium cations such as; cetyltrimethylammonium ammonium bromide, tetra(ethyl, methyl, propyl, butyl) ammonium hydroxide etc. According to the preferred aspects of the present invention, the quaternary ammonium sorbent material can be selected from a polymer and / or an amino silane having at least one quaternary ammonium moiety together with a counter-ion capable of forming hydroxide upon reaction with water in it. According to the preferred aspects of the present invention, the quaternary ammonium sorbent material can be selected from an amino silane selected from quaternary amino functional silanes or combinations thereof, wherein the amino silane includes at least one quaternary amine moiety and at least one silane moiety. According to the present invention, non-limiting examples of quaternary amino silane compounds, comprising silane moieties, and quaternary amine moieties can be used. The amino silane compound may include one, two, three, or more silane moieties. In some implementations, the silane moiety can include a trialkoxysilane (e.g., -SiR S1 R S2 R S3 , in which each of R S1 , R S2 , and R S3 is, independently, alkoxy; such as trimethoxysilane or triethoxysilane), a dialkoxysilane (e.g., -SiR S1 R S2 R S3 , in which each of R S1 and R S2 is, independently, alkoxy, and R S3 is a leaving group or a reactive group, such as any described herein), a dialkoxysilanol group (e.g., -Si(OR) 2 OH, in which each R is independently alkyl), a hydrosilane group (e.g., -SiH3), a monoalkylsilane group (e.g., -SiR S1 R S2 R S3 , in which R S1 is alkyl, and each of R S2 and R S3 is independently a leaving group or a reactive group, such as any described herein; in which non-limiting examples of monoalkylsilane is alkyldialkoxysilane or alkyldihalosilane), a dialkylsilane group (e.g., -SiR S1 R S2 R S3 , in which each of R S1 and R S2 is independently alkyl, and R S3 is a reactive group or a leaving group, such as any described herein; in which non-limiting examples of dialkylsilane includes dialkylalkoxysilane or dialkylhalosilane), a trihalosilane group (e.g., -SiZ 3 , in which each Z is independently halo, such as 202400128 Foreign Filings 9 trichlorosilane),or a silanetriol (e.g., -Si(OH) 3 ). Examples of quaternary amine silane compounds may also comprise hydrolyzed and / or oligomeric forms of quaternary amine-silanes. Higher numbers (e.g., three or more) of silane moieties in the amino silane compound can increase the covalent bond stability with the substrate as higher numbers of siloxane bonds between the silane moieties and the substrate surface can increase. Additionally, a silane group can form up to three siloxane bonds (Si-O-Si) to the surface, which may increase stability. The number of siloxane bonds that can be formed by silane moiety depends on the composition of the side groups (e.g., one or more of X 1 , X 2 , and / or X 3 ) capable of forming siloxane bonds (e.g., -OMe, -OEt, -Cl, -OH, or a combination of any of these). In a preferred aspect of the present invention, the amino silane compound comprise ate least one quaternary amine moiety. In some implementations, the amine moiety can further include a primary amine (e.g., -NH 2 ), a secondary amine (e.g., -NHR N1 , in which R N1 can be any described herein that is not hydrogen), a tertiary amine (e.g., -NR N1 R N2 , in which each of R N1 and R N2 can be any described herein that is not hydrogen), or an aminoalkyl group (e.g., -Ak-NR N1 R N2 , in which Ak is optionally substituted alkylene and each of R N1 and R N2 can be any described herein). In a preferred aspect of the present invention, the quaternary compounds or preferably quaternary ammonium and / or amine silane compound may covalently bond to the porous support material and without any intention to narrow the scope of the present invention. In a preferred aspect of the present invention, the counter-ion exchanged cationic quaternary sorbent compound is selected from N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM (TMAPTMS) hydroxide or bicarbonate, or Poly-diallyldimethylammonium (Poly-DADMA) hydroxide or bicarbonate, or aminoalkylfunctional silane hydrolysate or aqueous oligomeric aminoalkyl- and ammoniumalkyl-functional silane hydrolysate, Poly(N-methyl-4-vinyl pyridinium hydroxide or bicarbonate, Poly(vinyl benzyl trimethylammonium hydroxide or bicarbonate. In a more preferred aspect of the present invention, the quaternary sorbent compound may be selected from N-Trimethoxysilylpropyl-N,N,N-Trimethylammonium (TMAPTMS ) and / or any hydrolyzed forms thereof, such as VPS 2975 grade (aqueous oligomeric ammoniumalkyl-functional silane hydrolysate) and / or Dynasylan® HYDROSIL 2999 grade (aqueous oligomeric aminoalkyl- and ammoniumalkyl- functional silane hydrolysate) that are commercially available from Evonik Industries AG, or any of its subsidiaries. These quaternary compounds may be counter-ion exchanged with a counter ion capable of forming hydroxide ion when in contact with water, such as the counter ion is selected from hydroxide, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or combinations thereof, preferably selected from hydroxide and / or bicarbonate. According to the present invention, quaternary cationic sorbent compound initially has a quaternary cation, such as a quaternary amine, together with the initial inactive counter ion, wherein the inactive 202400128 Foreign Filings 10 initial counter-ion later exchanged to an active counter-ion species. The inactive initial counter-ion may be selected from halides, selected form chloride, bromide, fluoride iodine etc., and this ion to be replaced with an active counter ion capable of forming hydroxide ion when in contact with water as listed above. According to the present invention, such ion-exchanged quaternary cationic sorbent compound may be used as the sorbent material to treat the porous support particles to obtain MSA material. According to a preferred aspect of the present invention, the sorbent material is selected from quaternary ammonium sorbent materials, that can be selected from a polymer having at least one quaternary ammonium moiety / functional group or a quaternary ammonium salt together with a counter- ion capable of forming hydroxide upon reaction with water in it as well. In some preferred aspects of the present invention the quaternary ammonium sorbent compound is selected from quaternary ammonium compounds comprise moieties that result from polymerization of diallyldimethylammonium, trimethylammonium ion, 2-(Methacryloyloxy)ethyl]trimethylammonium, 2- (Acryloyloxy)ethyl]trimethylammonium, 3-(Methacryloylamino)propyl]trimethylammonium, (3- Acrylamidopropyl)trimethylammonium, or trimethyl-ammonium functional monomers. In some preferred aspects of the present invention the quaternary ammonium compound may comprise diallyldimethylammonium or trimethylammonium ion with a hydroxide, carbonate, bicarbonate, phosphate, hydrogen phosphate, or dihydrogen phosphate counter ion. Any counter ion that is either hydroxide or can react with water to form hydroxide will function within the present invention. In a preferred aspect of the present invention, the quaternary ammonium compound may be selected from a quaternary ammonium / amino silane and / or a quaternary ammonium polymer, such as Poly- diallyldimethylammonium hydroxide and / or bicarbonate (Poly-DADMAC), N,N,N-Trimethyl-3- (Trimethoxysilyl)-1-Propanaminium hydroxide and / or bicarbonate (TMAPTMS), hydrolyzed quaternary ammonium silanes like VPS 2975 or Dynasylan® HYDROSIL 2999 grades from Evonik Industries AG. In a preferred aspect of the present invention, quaternary ammonium compound may be N,N,N- Trimethyl-3-(Trimethoxysilyl)-1-Propanaminium hydroxide and / or bicarbonate, and may be grafted on the silica support material. In a preferred aspect of the present invention, quaternary ammonium compound may be poly- diallyldimethylammonium ((Poly-DADMAC) hydroxide and / or bicarbonate, and may be impregnated on the silica support material. In a preferred aspect of the present invention, quaternary ammonium may be either VPS 2975 and / or Dynasylan® HYDROSIL 2999 and may be grafted or condensed on the silica support material. 202400128 Foreign Filings 11 In a preferred aspect of the present invention, N,N,N-Trimethyl-3-(Trimethoxysilyl)-1-Propanaminium and / or VPS 2975 and / or Dynasylan® Hydrosil 2999 Hydroxide and / or bicarbonate is grafted and poly- diallyldimethylammonium hydroxide and / or bicarbonate is impregnated together on the silica support material. In one aspect of the present invention, the amount of quaternary compound, preferably a quaternary ammonium, quaternary amino polymer and / or an amino silane salts or hydrolysates thereof can be between 20% and 90 %, preferably between 25 and 75 wt%, more preferably 30 and 65 wt%, by weight of the total MSA sorbent compound. Porous Support Materials In recent years, there has been a growing interest in the use of porous support materials as carrier for sorbent materials to obtain MSA sorbent compounds in order to capture CO2, especially capturing CO2 from the air. These support materials are selected from porous materials to absorb CO2 by having large distribution of pore size, such as; silica, alumina or activated carbons and zeolites. Present invention relates to a MSA sorbent material based on at least one inorganic porous metal oxide support material treated with quaternary cationic sorbent compound(s) having a counter-ion capable of forming hydroxide upon reaction with water. A preferred embodiment of MSA sorbents utilizes porous materials treated with quaternary amine / ammonium groups having hydroxide and / or bicarbonate species / ions. In one aspect of the present invention inorganic porous metal oxide support material is defined with the physical characteristics, such as BET SA, with optimized pore size and pore volume. The inorganic porous metal oxide support materials provide a single or plurality of porous solid substrate which primarily serve structural support to sorbent compound. Ideal inorganic porous metal oxide support materials are available in large quantity, and do not drastically decrease the CO2 capture capacity of the sorbents, and further to provide a capability of increasing the structural integrity sorbent material. Additionally, porous metal oxide support materials ideally are able to bond either chemically or physically to the sorbent materials. Exemplary inorganic metal oxide support materials can be selected from ash or clay primarily comprised of silica and / or alumina, ; and oxide materials themselves typically comprising fly ash, namely silicon dioxide, aluminum oxide, calcium oxide and mixed metal oxides for example aluminum-silicon oxides. According to the present invention, inorganic porous metal oxide support materials may also include functional groups on the surfaces of porous particles which promote agglomeration by grafting via chemical bonding or even for impregnation. Exemplary functional groups on the porous metal oxide 202400128 Foreign Filings 12 support material may include hydroxyl groups, carboxylic acid groups, and oxides or even may be functionalized with chemical groups, such as with ammonia or amines to introduce amine groups. In some preferred aspects of the present invention, the porous metal oxide support material is selected from inorganic porous metal oxide materials, may be selected from, without any limitation, SiO2, Al2O3, ZnO, TiO2, MgO, Silica-aluminates, Zeolites), trivalent layered double hydroxides, aluminates of Na and / or K in different Na:K ratios, mixed oxides, zirconia, germania, magnesia, titania, hafnia, composed of those elements, and an organically modified derivatives of each of these. Any of other listed porous materials in US 2013 / 0095999 A1 reference may be used within the present invention. Even if preferred porous materials are limited to inorganic porous metal oxide materials, or specifically to silica or silicate materials, any other listed inorganic materials are suitable for treating with the defined quaternary cationic sorbents. In some preferred aspects of the present invention, the inorganic porous metal oxide support material is selected from substrates in the precipitated form, sol-gel form, semi-gel form, gel form, fumed form, calcined form, agglomerated form, granulated form, powder form or combinations thereof. Within the present invention, precipitated silicas may be in gel, or semi-gel forms based on their structural features and characteristics. In one preferred aspect of the present invention, the inorganic porous metal oxide support material is selected from silica, silicate, zeolite, alumina, ceramic, or combinations thereof, preferably is silica or silicate. In one preferred aspect of the present invention, the inorganic porous metal oxide support material is in the precipitated form, semi-gel form, sol-gel form, fumed form, calcined form, agglomerated form, granulated form, powder from or combinations thereof, In one preferred aspect of the present invention, the inorganic porous metal oxide support material is precipitated silica either in powder or in granule form. In some preferred aspects of the present invention, the inorganic porous support material has a BET Surface Area of 100 m2 / g or more, preferably between 100 and 750 m2 / g, more preferably between 100 and 600 m2 / g. In some preferred aspects of the present invention, the inorganic porous metal oxide support material has a pore volume of 0.6 cm3 / g or more, preferably between 0.8 and 3 cm3 / g, more preferably between 0.8 and 2.5 cm3 / g. In some preferred aspects of the present invention, the inorganic porous metal oxide support material has an average pore diameter of 5 nm or more, preferably in the range between 5 and 50 nm, preferably between 15 and 40 nm. 202400128 Foreign Filings 13 In some preferred aspects of the present invention the inorganic porous metal oxide support material has a BET Surface Area of ≤ 300 m2 / g and pore volume ≥0.6 cm In some preferred aspects of the present invention the inorganic porous metal oxide support material has a BET surface area in the range between 90 and 270 m2 / g, preferably between 90 and 250 m2 / g. In some preferred aspects of the present invention the inorganic porous metal oxide support material has a pore volume in the range between 0.8 and 1.7 cm3 / g, preferably between 0.9 and 1.5 cm3 / g. Method of Production of MSA Materials Another aspect of the present invention is a process for preparing the Moisture Swing Adsorbent (MSA) material according to the previous embodiments or aspects of the present invention. As explained in the background art, the main drawback with the known treatment methods is that, a large amount of treatment is applied on the inorganic porous metal oxide support material; such as polymer treatment first (having quaternary ammonium / amine species), followed with ion-exchange treatment (pre-conversion treatment). Thus, the ion exchange with the hydroxide and / or bicarbonate ions was completed after applying quaternary ammonium / amine sorbent compound on the porous support material. According to the present invention, the initial inactive counter ion on the quaternary cationic sorbent compound is replaced with a counter ion capable of forming hydroxide ion when in contact with water. That is why, the sorbent compound is used as ion-exchanged sorbent compound, and the process of initial counter ion exchange to final counter ion is called as “ion-exchanging step”. The initial counter ion on the quaternary cationic sorbent compound is selected from halides, selected form chloride, bromide, fluoride iodine etc., and this ion is replaced with a counter ion capable of forming hydroxide ion in order to obtain ion-exchanged quaternary cationic sorbent compound. The initial counter ion can also be considered as an inactive ion, to be replaced with an active counter ion. According to the present invention, post-conversion treatment may mean “porous support material treatment with the sorbent compound after ion-exchanging step”, and pre-conversion treatment may mean “porous support material treatment with the sorbent compound before ion-exchanging step”. A traditional pre-conversion treatment process is shown in Scheme 1 and means that the quaternary sorbent compound (e.g: quaternary amine / ammonium salt) was first deposited on the porous support as the halide form (step 1), then these sorbent treated porous support particles were ion- exchanged, possibly done in a column as shown in scheme 1, to remove the initial halide counter-ion and replace it with a final hydroxide and / or bicarbonate species (step 2) and then these particles can be dried to create the active particles (step 3). 202400128 Foreign Filings 14 This pre-conversion treatment limits the treatment to the grafted sorbents only, such as quaternary ammoniums only, without a possibility for impregnated quaternary ammonium treatments. Moreover, such pre-conversion treatment requires higher BET SA for the porous particles for highest stability which then typically have a smaller pore size, which at the end hinders CO2 absorption capacity after treatment. Further drawback relates with the hydroxide and bicarbonate ions as their alkalinity can cause hydrolytic instability of the support and leaching of the support treatment during such further treatment during ion- exchanging. Therefore a stable porous structure and stable treatment is needed with these pre- conversion treatment methods. Nevertheless, lower nitrogen (N) content is obtained after the ion-exchanging applied after porous material treatment, which corresponds to lower CO2absorption data. The inventive post-conversion method of obtaining such MSA materials is shown in Scheme 2 and a quaternary ammonium salt is examplified without any intention to limit the scope of sorbent material. Any other quaternary cationic sorbent materials would also be suitable for the inventive method for obtaining MSA material. The examplified method consists of initially converting the quaternary ammonium salt material from the initial inactive halide form to the final active hydroxide and / or bicarbonate species in an ion exchange column as shown in scheme 2, or by another means (step 1), then this active quaternary ammonium salt is directly deposited onto the porous support (step 2), after which these particles can be dried to create the active particles (step 3). According to the present invention provided inventive method requires only a post-conversion treatment which means that the sorbent material, such as quaternary amine / ammonium material goes through the ion-exchange resin (or via another means) for pre-ion exchanging followed with treatment of the porous support with the ion-exchanged quaternary ammonium sorbents. Thus, the present invention provides a process for preparing the Moisture Swing Adsorbent (MSA) material according to the previous embodiments or aspects of the present invention, comprising the following steps; i) providing a quaternary cationic sorbent compound with an initial in-active counter-ion on it, ii) converting the initial counter-ion from step (i) with hydroxide and / or another counter-ion capable of forming hydroxide upon reaction with water, through a column or any other suitable means enabling ion-exchanging,, to obtain an ion-exchanged cationic sorbent compound, iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the ion-exchanged cationic sorbent compound from step (ii) 202400128 Foreign Filings 15 iv) preferably removing the solvent or liquid from the medium, to obtain dried MSA material, if needed. According to the present invention, solvent can be selected from methanol, ethanol, isopropyl alcohol, water or any other possible solvents, without any intention to limit the scope of protection. According to the present invention, initial counter ion on the sorbent compound is selected from halides, selected form chloride, bromide, fluoride iodine etc., and this ion is replaced with a counter ion capable of forming hydroxide ion in order to obtain ion-exchanged sorbent compound. According to present invention, the quaternary cationic sorbent compounds and / or porous support materials can be selected according to previous aspects and / or embodiments of the present invention. According to the present invention, ion-exchange step (ii) is preferably applied directly to the sorbent compound through the ion exchange resin column (or via other means known in the art) and followed with porous support material treatment with such ion-exchanged sorbent compound. The inventive process would not need a further ion exchange treatment which adversely affects the porous structure and the active sorbent content of the obtained adsorbent material. In some preferred aspects of the process according to invention, the moisture swing adsorbent material obtained according preceding aspects, wherein the ratio of remaining non-exchanged in-active counter ion to N is below than 0.2. In a preferred aspect of the present invention, the process comprises the following steps; i) providing a quaternary ammonium sorbent compound selected from quaternary amino polymer and / or quaternary amino silane compound having at least one quaternary ammonium moiety and an initial in-active counter-ion in it, wherein the initial counter ion is selected from a halide, from chloride, bromide, fluoride or iodine, ii) exchanging the initial counter-ion with hydroxide or bicarbonate, through a column or any other suitable means enabling ion-exchanging, preferably through an ion exchange resin or through a column in a solvent or liquid medium preferably to have a ratio of remaining initial halide counter ion / N content below than 0.2, iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the ion-exchanged quaternary ammonium sorbent material from step (ii) iv) removing the solvent or liquid from the medium to obtain dried MSA material, if needed. In some preferred aspects of the process according to invention, the counter-ion of the quaternary ammonium sorbent compound in step (ii) is chloride and it was exchanged with a counter ion selected from hydroxide, bicarbonate. 202400128 Foreign Filings 16 In some preferred aspects of the process according to invention, the quaternary ammonium sorbent compound in step (i) has a chloride counter ion to be converted with the hydroxide and / or bicarbonate through the ion exchange resin (or via another means known in the art). In some aspects of the process according to invention, the process can be applied for both grafting and / or impregnation of the sorbent compound, preferably quaternary ammonium compounds on the porous support material, as listed within the present invention. Compared to known MSA materials obtained with the known methods, capturing CO2 from the air, the adsorption capacity is either improved significantly or comparable to that of known MSA adsorbents or even comparable to conventional DAC technologies based on aqueous / solid amine sorbents. Further hydrothermal stability is achieved together with higher N content followed with higher CO2 absorption data, by use of above mentioned silicas in the treatment process. In some aspects of the invention, the moisture swing adsorbent material obtained according to preceding aspects, wherein the initial counter ion is chloride and the ratio of remaining non-exchanged chloride ion to N is below than 0.2. In some aspects of the invention, the moisture swing adsorbent material obtained according to preceding aspects, wherein the MSA has a BET SA from 10 m2 / g or more, preferably between 10 and 135 m2 / g, more preferably between 15 and 120 m2 / g. In some aspects of the invention, the moisture swing adsorbent material obtained according to preceding aspects, wherein the MSA has a pore volume from 0.1 to 1.5 cm3 / g, preferably from 0.1 to 1 cm3 / g. In some aspects of the invention, the moisture swing adsorbent material obtained according to preceding aspects, wherein the MSA has a pore diameter from 10 to 50 nm, preferably from 15 to 40 nm. A further aspect of the invention is the use of porous support material based moisture swing adsorbents (MSA) according to the present invention, for moisture swing carbon dioxide capturing from air applications. Preferred Embodiments 1. A moisture swing adsorbent (MSA) material comprising inorganic porous metal oxide support materials treated with at least one quaternary cationic sorbent compound, wherein the MSA material has a Nitrogen (N) content of ≥ 1 wt%, preferably more than ≥ 1.5 wt% on a dry basis. 2. A moisture swing adsorbent (MSA) material according to embodiment 1, 202400128 Foreign Filings 17 wherein the quaternary cationic sorbent compound is a counter-ion exchanged cationic sorbent compound having at least one cationic quaternary moiety with an exchanged counter-ion; and wherein the exchanged counter-ion is hydroxide or an ion capable of forming hydroxide upon reaction with water. 3. A moisture swing adsorbent material according to any preceding embodiment, wherein the cationic sorbent compound is selected from quaternary ammonium compounds. 4. A moisture swing adsorbent material according to any preceding embodiment, wherein the MSA material comprises porous support material(s) treated with at least one counter-ion exchanged quaternary sorbent compound; wherein an initial inactive counter ion is exchanged to an active counter ion to obtain the counter-ion exchanged quaternary sorbent compound. 5. A moisture swing adsorbent material according to embodiment 5, wherein the counter-ion exchanged quaternary sorbent compound has at least one cationic quaternary ammonium moiety with an exchanged counter-ion; and wherein the exchanged counter-ion is hydroxide or an ion capable of forming hydroxide upon reaction with water. 6. A moisture swing adsorbent material according to embodiment 5 or 6, wherein the inactive counter ion is selected from a halide, from chloride, bromide, fluoride or iodine. 7. A moisture swing adsorbent material according to any preceding embodiment, wherein the exchanged counter-ion is hydroxide, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or combinations thereof, preferably hydroxide or bicarbonate. 8. A moisture swing adsorbent material according to any preceding embodiment, wherein the moisture swing adsorbent (MSA) material has a Nitrogen (N) content from 1 to 5 wt%, preferably from 1.5 to 4 wt%, more preferably from 1.5 to 3.5 wt%, on a dry basis. 9. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxide support material is selected from silica, silicate, zeolite, alumina, ceramic, or combinations thereof, preferably is silica or silicate. 10. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxide support material is in the precipitated form, semi-gel form, sol-gel form, gel form, fumed form, calcined form, agglomerated form, granulated form, powder from or combinations thereof. 11. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxide support material is precipitated silica either in powder or in granule form or combinations thereof. 202400128 Foreign Filings 18 12. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxide support material has a BET Surface Area of 100 m2 / g or more, preferably between 100 and 750 m2 / g, more preferably between 100 and 600 m2 / g. 13. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxide support material has a pore volume of 0.6 cm3 / g or more, preferably between 0.8 and 3 cm3 / g, more preferably between 0.8 and 2.5 cm3 / g. 14. The MSA material according to any preceding embodiment, wherein the inorganic porous metal oxdie support material has an average pore diameter of 5 nm or more, preferably in the range between 5 and 50 nm, preferably between 15 and 40 nm. 15. The MSA material according to any preceding embodiment, wherein the counter-ion exchanged cationic sorbent compound is selected form a quaternary ammonium compound, selected from a quaternary amino polymer having at least one quaternary ammonium moiety, or a quaternary amino silane compound comprising at least one silane moiety and at least one quaternary ammonium moiety, their salts, hydrolysed or oligomeric forms or combinations thereof. 16. The MSA material according to embodiment 15, wherein the counter-ion exchanged quaternary sorbent compound or salts thereof is selected form N-TRIMETHOXYSILYLPROPYL-N,N,N- TRIMETHYLAMMONIUM (TMAPTMS) hydroxide or bicarbonate, or Poly- diallyldimethylammonium (Poly-DADMA) hydroxide or bicarbonate, or aminoalkylfunctional silane hydrolysate or aqueous oligomeric aminoalkyl- and ammoniumalkyl-functional silane hydrolysate, Poly(N-methyl-4-vinyl pyridinium hydroxide or bicarbonate, Poly(vinyl benzyl trimethylammonium hydroxide or bicarbonate, or combinations thereof. 17. The MSA material according to any preceding embodiment, wherein the quaternary cationic sorbent compound is grafted and / or impregnated on the porous support material. 18. The MSA material according to any preceding embodiment, wherein the mass fraction of the counter-ion exchanged quaternary cationic sorbent compound in the MSA material is in the range between 20% and 90 %, preferably between 25 and 75 wt%, more preferably 30 and 65 wt% by weight of the total MSA material. 19. A process for preparing the MSA material according to any preceding embodiment, comprising the following steps; (i) providing a quaternary cationic sorbent compound with an initial in-active counter-ion on it, (ii) converting the inactive counter-ion from step (i) with hydroxide and / or another active counter-ion capable of forming hydroxide upon reaction with water, through a column or any other suitable means enabling ion-exchanging, to obtain the counter ion-exchanged cationic sorbent compound,, 202400128 Foreign Filings 19 (iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the counter ion-exchanged cationic sorbent compound from step (ii) and (iv) preferably removing the solvent or liquid to obtain dried MSA material. 20. The process for preparing MSA sorbent material according to embodiment 20, comprising the following steps; (i) providing a quaternary ammonium sorbent compound selected from quaternary amino polymer and / or quaternary amino silane compound having at least one quaternary ammonium moiety and an inactive counter-ion in it, wherein the inactive counter ion is selected from a halide, from chloride, bromide, fluoride or iodine, (ii) exchanging the initial inactive counter-ion with hydroxide or bicarbonate, through a column or any other suitable means enabling ion-exchanging, preferably through an ion exchange resin or through a column in a solvent or liquid medium (iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the counter ion-exchanged quaternary ammonium sorbent material from step (ii) and (iv) preferably removing the solvent or liquid to obtain dried MSA material. 21. A moisture swing adsorbent material obtained according to embodiments 20 or 21, wherein the MSA material has a ratio of remaining initial inactive counter ion / N content of 0.2 or below. 22. A moisture swing adsorbent material according to any preceding embodiments, wherein the MSA material has a BET SA from 10 m2 / g or more, preferably between 10 and 135 m2 / g, more preferably between 15 and 120 m2 / g. 23. A moisture swing adsorbent material according to any preceding embodiment, wherein the MSA material has a pore volume from 0.1 to 1.5 cm3 / g, preferably from 0.1 to 1 cm3 / g. 24. A moisture swing adsorbent material according to any preceding embodiment, wherein the MSA material has a pore diameter from 10 to 50 nm, preferably from 15 to 40 nm. 25. Use of an moisture swing adsorbent material, defined / obtained according to any preceding embodiments, for capturing carbon dioxide from a gas mixture or from air. 202400128 Foreign Filings 20 EXPERIMENTAL PART The invention is further illustrated in detail hereinafter with reference to examples and comparative examples, without any intention to limit the scope of the present invention. Abbreviations MSA: Moisture Swing Adsorbent SA: Surface Area TMAPTMS: N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1-PROPANAMINIUM CHLORIDE Poly-DADMAC : Poly-diallyldimethylammonium chloride Method of Measurements BET SA, Pore volume, Average Pore Diameter Measurements The BET surface areas, pore volumes and average pore diameters disclosed herein were determined on a Micromeritics TriStar II 3020 V1.03 or ASAP 2460. Samples were out gassed at 150-200 °C until the vacuum pressure was about 5 millibar, cooled and run on these automated volumetric analyzers at 77 °K. The BET surface area was determined using the BET nitrogen adsorption method of Brunaur et al., J. Am. Chem. Soc., 60, 309 (1938), and the pore volumes and average pore diameters were determined from the BJH (Barrett-Joiner-Halender) Desorption isotherms with a Halsey Faas Correction, Halsey, G.D., J. Chem. Phys. (1948), 16, pp.931. Such techniques are well known to those skilled in the art. d50 particle size The median particle size (d50) refers to the particle size for which 50% of the sample has a smaller size and 50% of the sample has a larger size. Median particle size (d50) was determined via the laser diffraction method using a Horiba LA 960 instrument or equivalent. Dry particles were submitted to the instrument for analysis where it was dispersed in water. CO2 absorbance capacity (CO2 isotherm) For the CO2 isotherms the samples were outgassed are 90 °C at a target pressure of 1 mmHg for 60 minutes then cooled and loaded onto a micromeritics TriStar 3020. The CO2 Isotherm is generated by measuring the amount of CO2adsorption (mmol / g adsorbed) using 34 points of increasing absolute pressure from ~5 mmHg to 760mmHg. The analysis bath temp is kept at 298.150 K (room temp). The capacity achieved at ~5 mmHg and ~760 mmHg is then recorded and reported to gauge the CO2 adsorption performance. %N Analysis For nitrogen analysis, a LECO FP-828 or similar is used. Samples are weighed into a tin capsule or encapsulated within tin foil. The sample is purged of ambient air and transferred to an oxygen- atmosphere furnace. Upon combustion, gases are swept to a thermoelectric cooler to remove moisture and are collected in a ballast chamber. Upon equilibration in the ballast, a representative aliquot of gas is collected and transferred to an inert gas stream. Upon passing through a heated reduction tube, 202400128 Foreign Filings 21 nitrogen oxide species (NOx) are reduced to N2. Scrubbers remove carbon dioxide (CO2) and additional water vapor. A thermal conductivity cell is used to quantify nitrogen. Chloride Content Analysis The chloride content of the sorbent materials and the final MSA materials are determined using a Orion Cl ion specific electrode. A calibration curve is prepared by making a series of NaCl solutions with known Cl concentrations by adding a desired amount of a 1000ppm NaCl solution to 50 mL of deionized water, mixing in 5 mL of concentrated HNO3 and then diluting to 100 mL prior to reading. Once the calibration curve is generated a given sample is analyzed by adding a known mass of the material to 50mL of deionized and 5 mL of concentrated HNO3. This solution is then covered with a watch glass and stirred for 2 hours while heating at 185 °C. The solution is then cooled down to room temperature and diluted to 100 mL using deionized water. The Cl content of the resulting solution is measured using the Orion Cl ion specific electrode and compared to the standard curve. The Cl content of the sample is then determined by taking this concentration from the solution and correcting for the initial mass of the sample. Inventive Post-Conversion Treatment vs. Traditional Pre-Conversion Treatment According to the present invention, conversion may refer to ion-exchanging step / treatment. According to the present invention, the ion-exchanged quaternary cationic sorbent compound, preferably a quaternary ammonium compound is deposited (grafted or impregnated) on an porous support material. This can be interpreted as the porous support material is treated with the ion- exchanged sorbent compound. According to the present invention, post-conversion treatment may mean “porous support material treatment with the quaternary cationic sorbent compound after ion-exchanging the sorbent compound”, and pre-conversion treatment may mean “porous material treatment with the quaternary cationic sorbent compound before ion exchanging the sorbent compound”. In a preferred aspect of the present invention, inventive post-conversion treatment means that the quaternary ammonium sorbent compound having quaternary ammonium ion with an initial counter ion in it (such as chloride counter ion) goes through the ion-exchange resin (or a column or another means) to exchange the initial counterion with hydroxide, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or combinations thereof; followed with treating the porous support material with that ion-exchanged quaternary ammonium sorbent material. Accordingly, inventive post- conversion treatment means that the quaternary ammonium sorbent material is ion-exchanged, before being deposited (grafted or impregnated) on an porous support material, namely porous support particles are treated with already ion exchanged quaternary ammonium sorbent material. According to the present invention, traditional pre-conversion treatment means that the sorbent material, such as quaternary ammonium sorbent material with an initial counter ion in it (such as chloride counter ion) is used first in treating the porous support material. These treated adsorbent particles are then ion 202400128 Foreign Filings 22 exchanged after this treatment using hydroxide or bicarbonate solution. Within this process, the porous support material is treated with the sorbent material, before ion exchanging process implemented, means that the treated adsorbent particles are ion exchanged with the hydroxide or bicarbonate solution directly. Preparation of MSA sorbents – Traditional Method vs Inventive Method Several samples were made using this traditional synthesis scheme compared to inventive synthesis scheme and several silica particles from fine powders to granular forms were used as inorganic porous metal oxide support materials. The exemplified silica support particles are listed in Table 1. The treatments routes are also shown in Scheme 1 and 2 to better illustrate the traditional and inventive treatment routes. Table 1: Physical Properties of Silica Support Materials Silica Support D50 Particle BET Surface BJH Desorption BJH Desorption Size (µm) Area (m2 / g) Pore Volume Average Pore (cm3 / g) Diameter (nm) Silica A 8.5* 422.8 1.36 10.0 Silica B 300-1000** 371.2 1.37 12.2 Silica C 300-1000** 535.0 0.98 6.1 Silica D 300-1000** 408.4 1.45 12.3 Silica E 300-1000** 231.1 1.28 20.9 Silica F 23.7* 231.7 1.20 20.4 Silica G 14.7* 241.5 1.39 22.0 Silica H 300-1000** 174.5 1.17 26.2 Silica I 300-1000** 120.9 0.82 29.6 *D50 particle size from Horiba LA960 on powder materials **Particle size range from sieving on granular materials As shown in Table 1, several porous silica support materials are tested within traditional and inventive processes. Preparation of Moisture Swing Adsorbents According to the Traditional Method Porous metal oxide support particle is first treated with a commercially available quaternary ammonium sorbent material having at least one quaternary ammonium ion with a chloride counter-ion, followed with counter-ion exchanging via a hydroxide (sodium hydroxide) or bicarbonate (sodium bicarbonate) solution. With this traditional method some limitations arise due to the process steps as expressed below; Within this traditional treatment method, the types of quaternary ammonium sorbent treatments would typically be limited to grafting quaternary ammoniums of which the highest amine density on the market would be N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1-PROPANAMINIUM CHLORIDE with a N 202400128 Foreign Filings 23 content of approximately 5.42%. Accordingly, the traditional treatment method may only enable grafting the polymer sorbent with quaternary ammonium on an porous support material. Despite the fact that an example using a non-covalent impregnation with poly-diallyldimethylammonium chloride (poly- DADMAC) is also provided hereby to show that this example was not properly ion-exchanged and can be considered as an inactive example that does not have enough capacity for CO2 adsorption. According to the present invention, it is important to exchange the inactive counterions to active counterions in order to have enough CO2 adsorption capacity, and accordingly exchanged counter ion ratio to N content becomes important for the final MSA material. Another drawback within the traditional method is the highest stability requirements during the ion exchange process. The sorbent (such as a quaternary amino silane) would need to be grafted directly to the porous metal oxide support surface which would limit the treatment level to about 1.5 - 2 molecules / nm2or about 0.44 % N / g ( about 0.31 mmol / g) for a 100 m2 / g support material. This would mean that the porous metal oxide support materials with higher surface area would be required and these materials typically have smaller pore sizes which limits CO2 diffusion upon functionalization. Moreover, both the bicarbonate or hydroxide exchange solutions are alkaline which is known to cause hydrolytic instability of the sorbent treatment, especially with silane treatments. This can result in a significant portion of the sorbent treatment on the porous metal oxide support material being removed during this ion exchange process as large amounts of these alkaline solutions are required to displace the more preferred chloride counter ion. Comparative MSA Material Examples In order to prepare comparative MSA material examples, 3 steps were followed as explained in traditional method definition above, and also illustrated in scheme 1 provided below. Within the comparative examples 1-4, several silica support materials (Silica A to D) with a variety of pore structures were treated by using N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1- PROPANAMINIUM CHLORIDE sorbent material, and then in a second step these already treated materials were ion exchanged by using a 8 % sodium bicarbonate solution. In a third final step the final ion exchanged sorbent particle was washed with deionized water and dried. Two additional comparative examples 5-6 were made using Silica E, with comparative example 5 being treated using N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1-PROPANAMINIUM CHLORIDE sorbent material, and with comparative example 6 using poly-diallyldimethylammonium chloride (poly- DADMAC). In the second step, both of these already treated materials were ion exchanged using a 4% sodium bicarbonate solution. In a third step the final ion exchanged sorbent particle was washed with deionized water and dried. 202400128 Foreign Filings 24 Sodium bicarbonate solution was chosen as it is less alkaline than sodium hydroxide and has a stronger affinity to the quaternary ammonium to help more efficiently displace the chloride. Scheme 1: Comparative Synthesis route for Preparation of MSA sorbents corresponding to Comparative Examples 1-6 202400128 Foreign Filings 25 Several MSA samples were prepared by using the traditional synthesis scheme, and several silica particles from fine powders to granular forms are also tested as porous support material. The silica support particle physical properties are shown in Table 1 and MSA formulation recipes and procedures for the initial functionalization are shown in Table 2. Table 2: Formulation of Comparative MSA Examples Comparative MSA Material 1 2 3 4 5 6 Examples Silica Silica Silica Silica Silica Silica Silica Support Material A B C D E E Silica Support Mass (g) 50 25 25 25 65 65 (Sorbent) 50% in methanol of N,N,N- TRIMETHYL-3-(TRIMETHOXYSILYL)- 59.82 30.19 22.28 18.00 95.63 0.00 1-PROPANAMINIUM CHLORIDE (g) (Sorbent) 40% in water of 4,000 MW poly-diallyldimethylammonium chloride 0.00 0.00 0.00 0.00 0.00 87.50 (poly-DADMAC) (g) Methanol (g) 9.24 13.59 87.71 30.45 0 0 Theoretical treated mass (g) 71.89 36.05 33.15 31.59 100.00 100.00 Theoretical treatment level (wt%) 30.4 30.7 24.6 20.9 35.0 35.0 Actual treated mass (g) 73.30 37.30 33.99 32.22 103.37 106.12 Actual mass vs Theoretical mass (%) 102.0 103.5 102.5 102.0 103.4 106.1 For the first powder support sample (Silica A),the desired mass of support particles was weighed out to give 50g of dry silica and added to the eirich EL-1 mixer. In a polypropylene bottle the appropriate amount of N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1-PROPANAMINIUM CHLORIDE and any additional methanol was added and mixed. The eirich was turned on to 1500 rpm to fluidize the powder and the silane sorbent solution was sprayed on the silica powder support by using an ultrasonic nozzle at a flow rate of ~8 mL / min. The treated powder was then transferred to an aluminum pan and placed into a forced air convection oven at 80 °C to remove the solvent and facilitate curing of the silane treatment. It remained in the oven for approximately 5 hours and / or no additional mass loss was observed. For the three granular supports (Silica B to D), a wet incipient impregnation followed by solvent removal and curing was employed to create grafted materials. The desired dry mass of support particles was weighed out and added to a mixing vessel where they could be gently tumbled. In a separate container the appropriate amount of N,N,N-TRIMETHYL-3-(TRIMETHOXYSILYL)-1-PROPANAMINIUM CHLORIDE and any additional methanol was added and mixed. The amount of methanol used was to 202400128 Foreign Filings 26 reach ~90-95% of the granules carrying capacity. This silane solution was then added to the silica granules with mixing to get an even distribution of the impregnating solution. The granules were then transferred to an aluminum pan and placed into a forced air convection oven at 80 °C to remove the solvent and facilitate curing of the silane treatment. It remained in the oven for approximately 5 hours and / or no additional mass loss was observed. The actual mass achieved in the treatment and drying process was compared to the theoretical mass calculated from the dry components and any potential solvent loss from the treatment solution or sorbent. In particular the alkoxy silane was presumed to liberate all of the methoxy groups, but due to the high potential degree of self-condensation some additional mass from new siloxane formation was accounted for. Any additional percentage above the theoretical value could be presumed to be residual moisture introduced from the treatment solution or the support particle. This holds true for not only these comparative examples, but for the inventive examples as well. Ion-Exchanging Step: After the silica support materials were treated with the quaternary ammonium sorbent material with chloride counter ion, the samples were subjected to ion exchange using an 8% sodium bicarbonate solution convert it to an active species as explained below; For the powder materials comparative example 1, 5 g of the treated silica support was placed into a beaker. 50 g of 8% sodium bicarbonate solution was added and the suspension was mixed and poured onto a 4 cm buchner funnel to allow the solution to be pulled through with vacuum. An additional 50 g of the 8% sodium bicarbonate solution was then added to the buchner and pulled through the resulting filter cake. 100g of deionized water was then passed through the bed to remove any residual sodium bicarbonate from the material. The material was then transferred to an aluminum pan and dried at 45 °C and ≤10% RH. For the granules of comparative examples 2, 3 and 4, the procedure was quite similar except 5g of the granules were placed into a column and 100g of the 8% sodium bicarbonate solution was passed through the material to exchange the counter ion. This was followed by 100g of water to rinse away any residual bicarbonate and the material was then dried at 45 °C and ≤10% RH. For the granules of comparative examples 5 and 6, 40g of the granules were placed into a 1 inch column and 600g of the 4% sodium bicarbonate solution was passed through the material to exchange the counter ion. This was followed by 100g of water to rinse away any residual bicarbonate and the materials were then dried at 45 °C and 40 mBar in a rotovap. 202400128 Foreign Filings 27 Table 3: The results for %C, %N, Cl-, N2physisorption analysis and CO2isotherms before and after ion exchange applications Comparative 1 2 3 4 5 6 Example %N before ion 2.10 2.32 1.80 1.56 2.54 2.97 exchange N content before 1.50 1.66 1.29 1.11 1.81 2.12 exchange (mmol / g) BET Surface Area 153.1 109.8 205.5 186.2 49.7 48.3 (m2 / g) BJH Desorption Pore 3 0.66 0.63 0.45 0.90 0.52 0.41 Volume (cm / g) BJH Desorption Average Pore 12.5 16.9 5.8 14.6 29.8 27.9 Diameter (nm) CO2 Isotherm 5 0.0035 0.0038 0.0060 0.0062 0.0033 0.0095 mmHg (mmol / g) Comparative 1 2 3 4 5 6 Example % wt N after ion 0.54 0.44 0.53 0.53 0.45 1.20 exchange N content after 0.39 0.31 0.38 0.38 0.32 0.86 exchange (mmol / g) Cl- after ion exchange (mmol / g) 0.0361 0.0353 0.0376 0.0280 0.0089 0.3418 Molar ratio of remaining initial counter ion Cl- / N 0.0935 0.1124 0.0995 0.0741 0.0278 0.3989 BET Surface Area 323.8 113.2 225.1 193.0 174.3 140.1 (m2 / g) BJH Desorption Pore 3 1.11 0.59 0.48 0.91 1.19 0.94 Volume (cm / g) BJH Desorption Average Pore 10.2 16.3 5.8 14.5 22.7 22.6 Diameter (nm) CO2 Isotherm at 5 0.0460 0.0707 0.0033 0.0059 0.0059 0.1238 mmHg (mmol / g) *Theoretical based on N content 202400128 Foreign Filings 28 The bicarbonate ion exchanged materials possessed significantly lower Cl- to N content compared to initially treated materials before ion-exchange, proving that the counterions did exchange to a significant extent. However, this bicarbonate alkaline solution was also found to hydrolytically remove a majority of the sorbent treatment from the silica pores. This is proved with very low CO2 capacities, although the ion-exchanged materials did show a slight improvement over the initial treated materials indicating the quaternary ammoniums did adsorb CO2. This was further confirmed by conducting a humidity activation and CO2breakthrough test on a dry compacted (400-1000 µm) sample of the ion-exchanged Comparative Examples 1, 5 and 6, and the resulting charts being provided in Figure 1 and 2. *CO2 breakthrough curve and cumulative CO2 sorption curve where the relative CO2 concentration is equivalent to the concentration of the incoming stream (395 ppm or 480ppm). In this test a 1cm deep bed of this material was activated by exposing it to a 85% RH N2 stream for 3-5 hours, followed by a 30 °C 0-5% RH N2 dry down phase and finally a CO2 adsorption phase at 25-30 °C, 10-15% RH, 395 or 480 ppm CO2 in N2 at 200 sccm (~20.1 cm / sec linear velocity). Under these conditions comparative example 1, 5 and 6 adsorbed about 0.25 mmol / g, 0.06 mmol / g and 0.13 mmol / g of CO2 respectively, with very steep breakthroughs. A summary of these break through results for the ion exchanged Comparative Examples 1, 5 and 6 can be found in Table 4. As already discussed above, it is important to consider the ion-exchange ratio which is linked with the CO2 adsorption capacity, and accordingly exchanged initial counter ion ratio to N content becomes important for the final MSA material. As seen from above Table 3, the molar ratio of (non-exchanged) initial counter ion (e.g: Cl-) / N for example 6 is quite high which is the proof of lack of proper ion exchanging. Exp.6 is considered as an in-active example, as the inactive counter ions were not properly exchanged to an active hydroxide and / or bicarbonate ion, and even though N content may be high compared to other comparative examples, it does not have enough CO2 adsorption capacity, as it was not fully exchanged to active counter-ion. Comparative example 6 was only provided to indicate that higher BET SA silica may retain some of the cationic polymer after the ion exchanging step but more than 50% is lost due to leaching. What sorbent material does remain is not effectively ion exchanged and it does not work for the required CO2 adsorption capacity. This lack of adequate CO2adsorption capacity holds true for all of the comparative examples wherein ion exchange was conducted after treating the support material with the sorbent material. Within the present invention, it is preferred to have a ratio of remaining initial / inactive counter ion (such as a halide) to N below than 0.2 in the MSA material. 202400128 Foreign Filings 29 Within the present invention, it is preferred to reach out a CO2 Isotherm capacity at 5 mmHg of equal or higher than 0.14 mmol / g. Table 4: CO2 capacities at 50% breakthrough, 90% breakthrough and saturation of Comparative Examples 1, 5 and 6 Comparative MSA Example 1 5 6 Break through CO2 Challenge 480 480 395 Concentration (ppm) CO2 capacity at 50% breakthrough 0.03 0.10 0.20 (mmol / g) CO2 capacity at 90% breakthrough 0.04 0.11 0.24 (mmol / g) CO2 capacity at saturation (mmol / g) 0.25 0.06 0.13 These initial treated MSA materials and final treatment levels and the resulting CO2 capture performance was used as a baseline of comparison for the inventive MSA materials and synthesis process described below. Preparation of MSA materials according to the Inventive Method In the inventive synthesis method, the commercially available polymer sorbent material is examplified, having quaternary ammonium ions with chloride counter-ions, and is first converted to hydroxide or bicarbonate species by ion exchanging the counter-ions. This can be done by using commercially available anion exchange columns which can then be repeatedly regenerated using sodium or potassium hydroxide or sodium or potassium bicarbonate. After the ion-exchanging the sorbent material, it can then be directly deposited to the silica support particle in the second step and is immediately ready for use as an MSA, after curing or solvent removal is complete in the third step. Inventive Moisture Swing Adsorbent Examples Prepared According the Inventive Method In order to prepare inventive MSA examples, 3 steps were followed as explained above in the method of MSA material preparation part, and as shown in below Scheme 2. 202400128 Foreign Filings 30 Scheme 2: Inventive Synthesis route for Preparation of MSA sorbents corresponding to Inventive Examples 1-14 202400128 Foreign Filings 31 Producing the MSA materials with this new ion-exchanging approach has several advantages as expressed below; Firstly, since there is no need for further activation of the treated material through ion exchange after sorbent treatment on the support material, the types of sorbent treatment agents are not limited to grafted sorbents with quaternary ammoniums and can be extended to non-covalently impregnated molecules like poly-diallyldimethylammonium chloride (poly-DADMAC). For this same reason, one does not need to be limited to direct grafting to the surface for stability, and higher treatment levels can be employed to increase N content of the MSA material. These higher treatment levels can be through the formation of poly-silanes (grafted / class 2 sorbent), use of non- covalent impregnations (impregnated / class 1 sorbent) and combinations of both (grafted and impregnated / class 4 sorbent). Secondly, this would also mean that higher surface area silica supports would not be required for a sorbent treatment for obtaining an MSA material, which would allow for the use of supports with larger pores for improved CO2 diffusion and mechanical / hydrothermal stability. Inventive MSA Examples In the case of a quaternary ammonium silane is used as the sorbent, enabling covalent attachment care may need to be taken during ion exchanging, during the initial activation step as the ion exchange column may need to be flushed with methanol or another solvent to prevent hydrolysis. This adds a step as the regeneration of the column is done under aqueous conditions with the hydroxide and bicarbonate solutions. With regards to the sorbents having quaternary ammonium species enabling non-covalent attachment, these are converted in an aqueous solution so this additional step is not needed. Inventive Examples 1, 2, 3 and 4 In inventive Examples 1, 2, 3 and 4, 550 g of a 7.3% poly-DADMAC solution, having approximately 4,000 MW average was passed through an Amberlite A26 (OH-) resin column. The effluent solution was found to have a pH >12 with pH paper and a Cl- content of ~1,300 ppm by an ion selective electrode, versus the theoretical 16,000 ppm for the original poly-DADMAC solution. This solution was then concentrated at 45 °C and 50 mBar on the rotovap. It was then rediluted to ~34% by using water. This poly-diallyldimethyl ammonium hydroxide solution was then used to wet incipient impregnate on to Silica E to produce the solid MSAs. These four examples were wet incipient impregnation followed by solvent removal. The desired mass of support particles was weighed out and added to a mixing vessel where they could be gently tumbled. In a separate container the appropriate amount of poly-DADMA OH- solution and any additional water was added and mixed. The amount of water used was to reach ~90-95% of the granules carrying capacity. This solution was then quickly added to the granules, which were mixed to get an even 202400128 Foreign Filings 32 distribution of the impregnating solution. The granules were then dried on roto-vap. A summary of the formulation recipes for inventive Examples 1 through 7 are shown in Table 5 and the resulting material properties are shown in Table 6. Table 5: Formulation of Inventive Examples 1 to 7 Inventive MSA Examples 1 2 3 4 5 6 7 Silica Silica Silica Silica Silica Silica Silica Silica Support Material E E E E H I D Silica Support Mass (g) 14.3 14.3 5.7 9.55 9.00 9.00 10.50 Sorbent concentration (wt%) 34 34 34 45 40 40 40 (Sorbent) aqueous solution of 4,000 MW poly- diallyldimethylammonium 20 13.3 10.7 17.36 15.00 15.00 11.25 hydroxide (poly-DADMA OH-) (g) H2O (g) 0.00 4.3 0.00 0.00 0.00 0.00 2.01 Theoretical treated mass (g) 21.10 18.82 9.34 17.36 15.00 15.00 15.00 Theoretical treatment level 32 24 39 45 40 40 30 (wt%) Actual treated mass (g) 21.8 19.1 9.10 16.80 15.52 15.53 15.60 Actual mass vs Theoretical 103.3 101.5 97.4 96.8 103.5 103.5 104.0 mass (%) Inventive Example 1 20g of the ~34% poly-DADMA OH- solution was impregnated onto 15g (4.55% H2O - 14.3g dry) of Silica E using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and 40 mBar on the rotovap. This should provide 21.1g of dry supportedsorbent at ~32 wt% poly-DADMA OH-. Actual final mass – 21.8 g. Inventive Example 2 13.3g of the ~34% poly-DADMA OH- solution was impregnated onto 15g (4.55% H2O - 14.3g dry) of Silica E using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and 40 mBar on the rotovap. This should provide 18.82g of dry supported sorbent at ~24 wt% poly-DADMA OH-. Actual final mass – 19.1g. Inventive Example 3 10.7g of the ~34% poly-DADMA OH- solution was impregnated onto 6g (4.55% H2O – 5.7g dry) of Silica E using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and 40 mBar on the rotovap. This should provide 9.34g of dry supported sorbent at ~39 wt% poly-DADMA OH-. Actual final mass – 9.1g. 202400128 Foreign Filings 33 Inventive Example 4 For this sample some of the original poly-DADMA OH- solution was increased in concentration at 45 °C and 50 mBar on the rotovap. The final concentration was set at ~45% to allow for a higher treatment level.17.36g of the ~45% poly-DADMA OH- solution was impregnated onto 10g (4.55% H2O – 9.55g dry) of Silica F using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and 40 mBar on the rotovap. This should provide 17.36g of dry supported sorbent at ~45 wt% poly-DADMA OH-. Actual final mass – 16.8g. Inventive Examples 5, 6, and 7 (Silica H, I and D were used as porous support materials with poly- DADMAC impregnation): In inventive Examples 5, 6 and 7, a 20% poly-DADMAC solution, having approximately 4,000 MW average was passed through a hydroxide exchanged IRA-900 (OH-) resin column. The effluent solution was found to have a pH >12 with pH paper and a Cl- content of <1500 by an ion selective electrode, versus the theoretical ~44,000 ppm for the original poly-DADMAC solution. This solution was then concentrated at 45 °C and 50 mBar on the rotovap. It was then rediluted to ~40% by using water. This poly-diallyldimethyl ammonium hydroxide solution was then used to wet incipient impregnate on to Silica D and Silica E to produce the solid MSAs. These three examples were wet incipient impregnation followed by solvent removal. The desired mass of support particles was weighed out and added to a mixing vessel where they could be gently tumbled. In a separate container the appropriate amount of poly-DADMA OH- solution and any additional water was added and mixed. The amount of water used was to reach ~90-95% of the granules carrying capacity. This solution was then quickly added to the granules, which were mixed to get an even distribution of the impregnating solution. The granules were then dried in an environmental chamber and the water was removed at 45 °C and ≤10 %RH. Inventive Example 5 15.0g of the ~40% poly-DADMA OH- solution was impregnated onto 9.76g (7.80% H2O – 9.00g dry) of Silica H using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~40wt% poly-DADMA OH-. Actual final mass was 15.52g Inventive Example 6 15.0g of the ~40% poly-DADMA OH- solution was impregnated onto 9.46g (4.90% H2O – 9.00g dry) of Silica I using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~40wt% poly-DADMA OH-. Actual final mass was 15.53g Inventive Example 7 11.25g of the ~40% poly-DADMA OH- solution was impregnated onto 11.05g (5.00% H2O – 10.50g dry) of Silica D using some extra water if needed to fully wet out the granules and help distribute. The water 202400128 Foreign Filings 34 was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~30wt% poly-DADMA OH-. Actual final mass was 15.60g. Table 6: The results for %C & %N of the resulting Inventive MSA Examples 1 to 7 and the N2physisorption analysis and CO2 isotherms for the Example 4 with the highest treatment level. Inventive MSA 5 6 7 1 2 3 4 Example Silica Support Silica Silica Silica Silica Silica Silica I Silica Material E E E E H D % wt N 2.18 1.61 2.46 2.75 2.61 2.61 1.96 N content 1.86 1.86 1.40 1.56 1.15 1.76 1.96 (mmol / g) Cl- after exchange (mmol / g) 0.1507 0.1048 0.1585 0.0064 0.1932 0.1782 0.1673 Molar ratio of remaining initial counter ion Cl- / N 0.0968 0.0912 0.0902 0.0033 0.1037 0.0956 0.1195 BET Surface 27.5 20.1 84.9 57.6 102.8 52.2 68.9 Area (m2 / g) BJH Desorption 0.25 0.20 0.46 Pore Volume 0.41 0.72 0.40 0.64 (cm3 / g) BJH Desorption 30.5 35.9 18.3 Average Pore 24.5 23.6 24.6 28.8 Diameter (nm) CO2 Isotherm 5 0.1886 0.1634 0.2054 0.3774 0.4562 0.3428 0.3429 mmHg (mmol / g) The performance of these materials was further assessed by conducting a humidity activation and CO2 breakthrough test. In this test a 1cm deep bed (~0.1g) of each material was activated by exposing it to a 85-90% RH N2 stream for 3 hours, followed by a 3 hour 30 °C 0-5% RH N2 dry down phase and finally a CO2 adsorption phase at 25-30 °C, 10-15% RH, 395 or 480 ppm CO2 in N2 at 200 sccm (~20.1 cm / sec linear velocity). Under these conditions these sorbents adsorbed anywhere from 0.33 to 0.53 mmol / g of CO2 with a very sharp breakthrough. The resulting breakthrough curves and cumulative CO2 sorption curves for Inventive Examples 1 to 4 can be seen in Figures 3 and 4 and for Inventive Examples 5 to 7 in Figures 5 and 6, along with a table of the capacities at 50% breakthrough, 90% breakthrough and saturation given in Tabel 7. 202400128 Foreign Filings 35 Table 7: CO2 capacities at 50% breakthrough, 90% breakthrough and saturation of Inventive Examples 1 to 7 Inventive MSA Example 1 2 3 4 5 6 7 Break through CO2 Challenge 480 480 480 395 395 395 395 Concentration (ppm) CO2 capacity at 50% breakthrough 0.44 0.31 0.20 0.36 0.28 0.44 0.38 (mmol / g) CO2 capacity at 90% breakthrough 0.50 0.41 0.24 0.43 0.30 0.51 0.51 (mmol / g) CO2 capacity at saturation (mmol / g) 0.46 0.33 0.52 0.53 0.52 0.43 0.28 Table 8: Formulation of Inventive Examples 8 to 11 Inventive MSA Examples 8 9 10 11 Silica Silica Silica Silica Silica Support Material E E F G Silica Support Mass (g) 9.55 10.00 200.00 150.00 Sorbent concentration (wt%) 40 50 45 50 (Sorbent) 50% in methanol of N,N,N-TRIMETHYL-3- (TRIMETHOXYSILYL)-1-PROPANAMINIUM OH- or 0.00 18.87 0.00 297.78 HCO3- (g) (Sorbent) aqueous solution of 4,000 MW or 9,000 MW poly-diallyldimethylammonium hydroxide (poly-DADMA 13.46 0.00 296.30 0.00 HCO3-) (g) H2O (g) 0.00 0.00 87.59 0.00 Theoretical treated mass (g) 14.93 16.71 333.33 262.59 Theoretical treatment level (wt%) 36 42.57 40.0 42.88 Actual treated mass (g) 15.10 15.98 307.29 252.20 Actual mass vs Theoretical mass (%) 101.1 95.6 92.2 96.0 The formulations and procedures for Inventive Examples 8 through 11 are given in Table 8 and the resulting material properties are shown in Table 9. Inventive Example 8 (Silica E was used with poly-DADMA HCO3- impregnation): In inventive Example 5, 100g of a 7.3% ~4,000 MW poly-dadmac solution was passed through an IRA- 900 resin column that was pre-exchanged with 8% sodium bicarbonate solution. This allowed the poly- DADMAC to be converted directly to poly-DADMA HCO3- or the active form for MSA applications. The effluent from the column was found to have a pH ~8.5-9.0 by pH paper and a Cl- content of ~250-500 ppm by an ion selective electrode, versus the theoretical 16,000 ppm of the original poly-DADMAC solution. This solution was then concentrated at 45 °C and 40 mBar on the rotovap. It was then rediluted to ~40% using water. 202400128 Foreign Filings 36 13.46g of the 40% ion exchanged poly-DADMA HCO3- solution was impregnated onto 10g (4.55% H2O - 9.55g dry) of Silica E using some extra water if needed to fully wet out the granules and help distribute. This was done in an evaporating flask and after the impregnation was complete the water was then removed at 45 °C and 40 mBar on the rotovap. This should provide 14.93g at ~36 wt% poly-DADMA HCO3- on a dry basis on the final sorbent. Actual final mass - 15.1g. Inventive Example 9 (Silica E was used with TMAPTMS grafting): For this example 50g of a 50% N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM CHLORIDE (TMAPTMS) solution in methanol was passed through an Amberlite A26 (OH-) resin column that was previously flushed with methanol to remove water from the system. The column discharge was found to have a pH >12 by pH paper and a Cl- content of <1000 ppm by an ion selective electrode, versus the theoretical 68,000 ppm for the original solution. If the column capacity was utilized it could be regenerated using a 5-10% NaOH solution, re-exchanged with methanol and reused. This resulting solution was then concentrated at 45 °C and 100 mBar on the rotovap. It was then diluted to ~50% using methanol. 18.87g of the ~50% N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM hydroxide solution was impregnated onto 10.48g (4.55% H2O - 10.00g dry) of Silica E using no extra methanol was needed as the granules were near saturation. The impregnation was done by tumbling the particles and spraying the solution in with a nozzle. The methanol was then removed at 45 °C in a convection oven and the silane was allowed to cure for 7 hours. This should provide ~42.57 wt% SILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM hydroxide on a dry basis on the final granules and a theoretical final cured mass around 16.71g. Actual final mass - 15.98g. Inventive Example 10 (Silica F was used with poly-DADMA HCO3- impregnation): In inventive Example 10, ~3 kg of a 20wt% ~9,000 MW poly-dadmac solution was passed through an IRA-900 resin column that was pre-exchanged with 8% sodium bicarbonate solution. This allowed the poly-dadmac to be converted directly to poly-DADMA HCO3- or the active form for MSA applications. The effluent from the column was found to have a pH ~8.5-9.0 by pH paper and a Cl- content of ~<500 ppm by an ion selective electrode, versus the theoretical 44,000 ppm of the original poly-DADMAC solution. Once the column capacity was reached the discharge Cl- content would start to rise so this portion >500ppm was set aside. The column was then regenerated and it was repassed through and this was repeated until all 3 kg was converted. These low Cl- portions were then combined and then concentrated at 45 °C and 40 mBar on the rotovap. It was then rediluted to ~45% using water. 296.30g of the 45% ion exchanged poly-DADMA HCO3- solution was impregnated onto 216.33g (7.55% H2O – 200.0g dry) of Silica F using some extra water if needed (87.59g). For this powder sample the desired mass of support particles was weighed out and added to the eirich EL-1 mixer. In a polypropylene bottle the desired amount of poly-DADMA HCO3- solution was mixed with any additional water. The eirich was turned on to 1500 rpm to fluidize the powder and the silane solution was sprayed on using a ultrasonic nozzle at a flow rate of ~8 mL / min. The powder was then transferred to an aluminum pan and placed into an environmental chamber and the water was removed at 45 °C and 0- 202400128 Foreign Filings 37 5%RH. This should provide 333.33 g at ~40 wt% poly-DADMA HCO3- on a dry basis on the final sorbent. Actual final mass – 307.29g Inventive Example 11 (Silica G was used with TMAPTMS grafting): For this example 2kg of a 50% N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM CHLORIDE (TMAPTMS) solution in methanol was passed through a column of IRA-900 resin previously exchanged using sodium bicarbonate and flushed with methanol. The column discharge was found to have a pH of 8.5-9.0 by pH paper and a Cl- content of <500 ppm by an ion selective electrode, versus the theoretical 68,000 ppm for the original solution. If the column capacity was utilized it was regenerated using 8% sodium bicarbonate solution, flushed with methanol and reused until all portions of the silane were fully exchanged and <500 ppm in Cl-. This resulting solution was then concentrated at 45 °C and 100 mBar on the rotovap. It was then diluted to ~50% using methanol. 297.78g of the ~50% N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM HCO3- solution was impregnated onto 157.15g (4.55% H2O - 150g dry) of silica G using no extra methanol as the volume was already >80% of the powders carrying capacity. For this powder sample the desired mass of support particles was weighed and added to an eirich EL-1 mixer. In a polypropylene bottle the desired amount of N-TRIMETHOXYSILYLPROPYL-N,N,N-TRIMETHYLAMMONIUM HCO3- solution was added. The eirich was turned on to 1500 rpm to fluidize the powder and the silane solution was sprayed onto the particles using a ultrasonic nozzle at a flow rate of ~12 mL / min. The powder was then transferred to an aluminum pan and the methanol was then removed at 45 °C in a convection oven and the silane was allowed to cure overnight. This should provide ~42.88 wt% SILYLPROPYL-N,N,N- TRIMETHYLAMMONIUM HCO3- on a dry basis on the final granules and a final cured mass around 262.59g. Actual final masses - 250.94g, 254.25 and 251.42. Table 8: The results for %C, %N, N2 physisorption analysis and CO2 isotherms for the sorbents corresponding to Inventive Examples 8-11 Inventive Example 8 9 10 11 % wt C 16.7 15.2 16.2 16.1 % wt N 2.40 2.86 2.10 2.58 N content (mmol / g) 1.71 2.04 1.50 1.84 Cl- content (ppm) 2,323 1,053 753 1,520 Cl- after exchange (%) 0.2323 0.1053 0.0753 0.1520 Cl- after exchange (mmol / g) 0.0655 0.0297 0.0212 0.0429 Molar ratio of Cl- / N 0.0382 0.0145 0.0142 0.0233 BET Surface Area (m2 / g) 58.7 36.8 60.0 56.9 BJH Desorption Pore Volume (cm3 / g) 0.40 0.36 0.47 0.47 BJH Desorption Average Pore 24.5 33.1 27.1 28.4 Diameter (nm) CO2 Isotherm 5 mmHg (mmol / g) 0.1455 0.2604 0.1477 0.2574 202400128 Foreign Filings 38 The performance of these materials was further assessed by conducting a humidity activation and CO2 breakthrough test. For this test the powder samples (Inventive examples 10 and 11) the particles were lightly compacted using a lab scale roller compactor at , broken and screened to 300-1000 µm to allow them to be tested on the breakthrough analyzer. In this test a 1cm deep bed (~0.1g) of each material was activated by exposing it to a 85-90% RH N2 stream for 3 hours, followed by a 3 hour 30 °C 0-5% RH N2 dry down phase and finally a CO2 adsorption phase at 25-30 °C, 10-15% RH, 395 ppm CO2 in N2 at 200 sccm (~20.1 cm / sec linear velocity). Under these conditions these sorbents adsorbed anywhere from 0.43 to 0.81 mmol / g of CO2 with most exhibiting very sharp breakthroughs. The resulting breakthrough curves and cumulative CO2 sorption curves can be seen in Figures 7 and 8 along with a Table 10 of the capacities at 50% breakthrough, 90% breakthrough and saturation. Table 10: CO2 capacities at 50% breakthrough, 90% breakthrough and saturation Inventive Example 8 9 10 11 CO2 capacity at 50% breakthrough (mmol / g) 0.43 0.36 0.38 0.74 CO2 capacity at 90% breakthrough (mmol / g) 0.50 0.50 0.41 0.78 CO2 capacity at saturation (mmol / g) 0.52 0.53 0.43 0.81 N efficiency at 90% breaktrough 0.29 0.25 0.27 0.42 (mmol CO2 / mmol N) Table 11: Formulation of Inventive Examples 12 to 14 Inventive MSA Examples 12 13 14 Silica Silica Silica Silica Support Material H H D Silica Support Mass (g) 9.75 9.75 9.75 Sorbent concentration (wt%) 46 48 46 (Sorbent) aqueous VPS 2975 OH- (g) 11.41 0.00 11.41 (Sorbent) aqueous Dynasylan® HYDROSIL 2999 OH- (g) 0.00 10.94 0.00 H2O (g) 1.28 1.75 0.90 Theoretical treated mass (g) 15.00 15.00 15.00 Theoretical treatment level (wt%) 35 35 35 Actual treated mass (g) 15.43 14.74 14.87 Actual mass vs Theoretical mass (%) 102.9 98.3 99.1 The formulations and procedures for Inventive Examples 12 through 14 are given in Table 11 and the resulting material properties are shown in Table 12. Inventive Examples 12, 13 and 14 (Silica H and D were used as porous support materials with the hydroxide form of VPS 2975 and Dynasylan® HYDROSIL 2999): In inventive Examples 12, 13 and 14, either VPS 2975 (46 wt% hydrolyzed quaternary ammonium silane in water) or VPS 2999 (48 wt% hydrolyzed silane in water), were passed through a hydroxide exchanged IRA-900 (OH-) resin column. The effluent solution was found to have a pH >12 with pH 202400128 Foreign Filings 39 paper and a Cl- content of <1500 by an ion selective electrode, versus the theoretical ~75,000 ppm for the original VPS 2975 solution and ~66,000 ppm for the original Dynasylan® HYDROSIL 2999 solution. These solutions were then concentrated at 45 °C and 40 mBar on the rotovap back to the original concentrations by removing any dilution water. These aqueous solutions of sorbents in the hydroxide form were then used to wet incipient impregnate on to Silica H and Silica D to produce the supported MSA sorbents. It was found that these hydrolyzed forms of silanes had several advantages over the alkoxy versions. Firstly, as the hydrolyzed silanes were in the aqueous form they could simply be passed through the ion exchange resin without any laborious solvent exchange to prevent condensation. In addition, since the viscosity of these solutions are quite low they could be exchanged at their full concentration. Lastly, this low viscosity also aided in more easily achieving more uniform treatment onto the solid support. These three examples were wet incipient impregnation followed by solvent removal. The desired mass of support particles was weighed out and added to a mixing vessel where they could be gently tumbled. In a separate container the appropriate amount of VPS 2975 or Dynasylan® HYDROSIL 2999 hydroxide solution and any additional water was added and mixed. The amount of water used was to reach ~90-95% of the granules carrying capacity. This solution was then quickly added to the granules, which were mixed to get an even distribution of the impregnating solution. The granules were then dried in an environmental chamber and the water was removed at 45 °C and ≤10 %RH this drying could also be conducted on the roto-vap between 45-85 °C at 40 mBar. Inventive Example 12. 11.41g of the ~46% VPS 2975 OH- solution was impregnated onto 10.57g (7.80% H2O – 9.75g dry) of Silica H using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~35wt% VPS 2975 OH-. Actual final mass – 15.43g Inventive Example 13. 10.94g of the ~48% VPS 2999 OH- solution was impregnated onto 10.57g (7.80% H2O – 9.75g dry) of Silica H using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~35wt% VPS 2999 OH-. Actual final mass – 14.74g Inventive Example 14. 11.41g of the ~46% VPS 2975 OH- solution was impregnated onto 10.26g (5.00% H2O – 9.75g dry) of Silica D using some extra water if needed to fully wet out the granules and help distribute. The water was then removed at 45 °C and ≤10 %RH in an environmental chamber. This should provide 15.00g of dry supported sorbent at ~35wt% VPS 2975 OH-. Actual final mass – 14.87g. 202400128 Foreign Filings 40 Table 12: The results for %C, %N, N2physisorption analysis and CO2isotherms for the sorbents corresponding to Inventive Examples 12-14 Inventive Example 12 13 14 % wt N 2.10 2.94 2.47 N content (mmol / g) 1.50 2.10 1.76 Cl- after exchange (mmol / g) 0.0210 0.0096 0.0286 Molar ratio of counter ion after exchange Cl- / N 0.0140 0.0046 0.0162 BET Surface Area (m2 / g) 50.6 56.2 109.5 BJH Desorption Pore Volume (cm3 / g) 0.37 0.49 0.61 BJH Desorption Average Pore Diameter (nm) 24.8 27.5 17.9 CO2 Isotherm 5 mmHg (mmol / g) 0.2256 0.1778 0.3342 The performance of these materials was further assessed by conducting a humidity activation and CO2 breakthrough test. In this test a 1cm deep bed (~0.1g) of each material was activated by exposing it to a 85-90% RH N2 stream for 3 hours, followed by a 3 hour 30 °C 0-5% RH N2 dry down phase and finally a CO2 adsorption phase at 25-30 °C, 10-15% RH, 480 ppm CO2 in N2 at 200 sccm (~20.1 cm / sec linear velocity). Under these conditions these sorbents adsorbed anywhere from 0.37 to 0.52 mmol / g of CO2 with most exhibiting very sharp breakthroughs. The resulting breakthrough curves and cumulative CO2 sorption curves can be seen in Figures 9 and 10 along with a Table 13 for the capacities at 50% breakthrough, 90% breakthrough and saturation. Table 13: CO2 capacities at 50% breakthrough, 90% breakthrough and saturation Inventive Example 12 13 14 CO2 capacity at 50% breakthrough (mmol / g) 0.40 0.45 0.33 CO2 capacity at 90% breakthrough (mmol / g) 0.47 0.50 0.36 CO2 capacity at saturation (mmol / g) 0.49 0.52 0.37 N efficiency at 90% breaktrough 0.31 0.24 0.20 (mmol CO2 / mmol N) Results and Conclusion With the present invention it was proved that effective moisture swing sorbents can be obtained, based on porous supports treated with cationic sorbent compounds or combinations thereof. Examplified quaternary ammonium silanes, or quaternary ammonium polymer or hydrolyzed forms thereof provide MSA materials proved with their increased CO2 adsorption capacities. This was enabled by employing a novel process where the cationic sorbent compounds, such as quaternary ammonium with the halide counter-ion was initially converted to the active hydroxide and / or bicarbonate species prior to silica support material treatment / functionalization. 202400128 Foreign Filings 41 This novel process avoids typical post functionalization ion exchange step. Such kind of a traditional making processes was found to hydrolytically remove grafted sorbent treatments from the support surface in a. It was also found that this new process provides flexibility in the porous support properties, in particular allowing for support particles with lower BET surface area to pore volume ratios to be employed and still provide sorbents with increased active sorbent content, such as quaternary ammonium content. This provides an advantage as these types of supports are typically more stable and have larger mesopores which leads to improved diffusion characteristics.

Claims

202400128 Foreign Filings 42 CLAIMS 1. A moisture swing adsorbent (MSA) material comprising inorganic porous metal oxide support materials treated with at least one quaternary cationic sorbent compound, wherein the MSA material has a Nitrogen (N) content of ≥ 1 wt%, preferably more than ≥ 1.5 wt% on a dry basis.

2. A moisture swing adsorbent (MSA) material according to claim 1, wherein the quaternary cationic sorbent compound is a counter-ion exchanged cationic sorbent compound having at least one cationic quaternary moiety with an exchanged counter-ion; and wherein the exchanged counter-ion is hydroxide or an ion capable of forming hydroxide upon reaction with water.

3. A moisture swing adsorbent material according to claim 1 or 2, wherein the cationic sorbent compound is selected from quaternary ammonium compounds salts or combinations thereof.

4. A moisture swing adsorbent material according to claim 2 or 3, wherein the MSA material comprises inorganic porous metal oxide support material(s) treated with at least one counter-ion exchanged quaternary sorbent compound; wherein an initial inactive counter ion is exchanged to an active counter ion to obtain the ion exchanged quaternary sorbent compound.

5. A moisture swing adsorbent material according to claim 4, wherein the counter-ion exchanged quaternary sorbent compound has at least one cationic quaternary ammonium moiety with an exchanged counter-ion; and wherein the inactive counter ion is selected from a halide, preferably from chloride, bromide, fluoride or iodine, and exchanged to an active counter-ion selected from hydroxide or an ion capable of forming hydroxide upon reaction with water.

6. A moisture swing adsorbent material according to claims 2 to 5, wherein the exchanged counter-ion is hydroxide, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or combinations thereof, preferably hydroxide or bicarbonate.

7. A moisture swing adsorbent material according to preceding claims, wherein the moisture swing adsorbent (MSA) material has a Nitrogen (N) content from 1 to 5 wt%.

8. The MSA material according to preceding claims, wherein the inorganic porous metal oxide support material is selected from silica, silicate, zeolite, alumina, ceramic and combinations thereof.202400128 Foreign Filings 43 9. The MSA material according to claim 9, wherein the inorganic porous metal oxide support material is in the precipitated form, semi-gel form, sol-gel form, gel form, fumed form, calcined form, agglomerated form, granulated form, powder from or combinations thereof.

10. The MSA material according to preceding claims, wherein the inorganic porous metal oxide support material has a BET Surface Area of 100 m2 / g or more, preferably between 100 and 750 m2 / g, more preferably between 100 and 600 m2 / g.

11. The MSA material according to preceding claims, wherein the inorganic porous metal oxide support material has a pore volume of 0.6 cm3 / g or more, preferably between 0.8 and 3 cm3 / g, more preferably between 0.8 and 2.5 cm3 / g.

12. The MSA material according to preceding claims, wherein the inorganic porous metal oxide support material has an average pore diameter of 5 nm or more, preferably in the range between 5 and 50 nm, preferably between 15 and 40 nm.

13. The MSA material according to preceding claims, wherein the counter-ion exchanged cationic sorbent compound is selected from a quaternary amino polymer having at least one quaternary ammonium moiety, or selected from a quaternary amino silane compound having at least one silane moiety and at least one quaternary ammonium moiety, salts thereof hydrolyzed or oligomeric forms or combinations thereof.

14. A process for preparing the MSA material according to any preceding claims, comprising the following steps; (i) providing a quaternary cationic sorbent compound with an initial inactive counter-ion on it, (ii) converting the initial counter-ion from step (i) with hydroxide and / or another active counter- ion capable of forming hydroxide upon reaction with water, through a column or any other suitable means enabling ion-exchanging, to obtain the counter ion-exchanged cationic sorbent compound, (iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the ion-exchanged cationic sorbent compound from step (ii), and (iv) optionallyremoving any solvent or liquid from the medium to obtain dried MSA material.

15. The process for preparing MSA sorbent material according claim 14, comprising the following steps; (i) providing a quaternary ammonium sorbent compound selected from quaternary amino polymer and / or quaternary amino silane compound having at least one quaternary ammonium moiety and an initial inactive counter-ion in it, wherein the initial inactive counter ion is selected from a halide, from chloride, bromide, fluoride or iodine,202400128 Foreign Filings 44 (ii) exchanging the initial counter-ion with hydroxide or bicarbonate, through a column or any other suitable means enabling ion-exchanging, preferably through an ion exchange resin or through a column in a solvent or liquid medium. (iii) providing inorganic porous metal oxide support material and treating the inorganic porous metal oxide support material with the counter-ion exchanged quaternary ammonium sorbent material from step (ii) (iv) preferably removing the solvent or liquid from the medium to obtain dried MSA material.

16. The MSA material obtained according to claims 14 or 15, wherein the MSA material has a ratio of remaining initial inactive counter ion / N content of 0.2 or below, 17. Use of an moisture swing adsorbent material, defined or obtained according to any preceding clams, for capturing carbon dioxide from a gas mixture or from air.

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