Method for producing and recycling functionalized aggregated silica

Abstract

This specification discloses functionalized granules comprising a plurality of microparticles and a coating, and systems configured for using such functionalized granules. This specification also includes collecting a plurality of microparticles and using the plurality of microparticles to produce a plurality of functionalized granules having an average dimension or average dimension greater than the average dimension or average dimension of the plurality of microparticles.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefits of U.S. Provisional Application No. 63 / 468,443, filed on 23 May 2023, the disclosures of which are incorporated herein by reference.

[0002] This disclosure relates to functionalized granules, and more specifically to functionalized granules that may include porous silica and can be used for the reversible recovery of gases (e.g., carbon dioxide). [Background technology]

[0003] Atmospheric carbon concentrations have risen over the decades in correlation with industrialization. Carbon dioxide is the main contributor to total carbon concentration. Three-dimensional porous structures can be used to remove carbon dioxide from the gaseous environment. [Overview of the project]

[0004] Generally, this disclosure relates to a method for collecting particulate matter and then further processing such particulate matter (for example, by agglomerating the fine powder and regenerating it into larger particles such as granules). Particulate sorbents can be used in carbon recovery systems, in which particulate matter may be generated by the movement of the sorbent within the system or other processing equipment. Depending on the composition of the sorbent, various levels of particle abrasion may occur to generate particulate matter (or fine powder).

[0005] The fine powder may originate from larger functionalized silica particles, which in turn may be processed to provide larger particles (e.g., functionalized granules as described herein). In some embodiments, the granules are functionalized granules having a coating and / or matrix configured for gas recovery (e.g., CO2 recovery). In certain embodiments, the granules may be produced for the purpose of reversibly recovering low concentrations (e.g., <400 ppm, atmospheric concentration) of carbon dioxide from a gas (e.g., ambient air).

[0006] For larger particles such as granules, functionalization may be included. In some embodiments, fine powder may be agglomerated to form granules, which may then be functionalized to include a coating or matrix. In other embodiments, fine powder may be processed to form functionalized fine powder having a coating or matrix, which may then be agglomerated to form granules (e.g., functionalized granules). The coating or matrix may be present on the surface (e.g., at least a portion of the surface of the fine powder or granules) or between surfaces (e.g., between at least a portion of multiple fine powders or multiple granules).

[0007] Functionalization may involve the use of amine-containing compounds (e.g., polymeramines and / or aminosilanes) in coatings and / or within the matrix. Functionalization may be used in fine powders or granules. In some embodiments, porous silica fine powders or porous silica granules may be functionalized with polymeramines such as polyethyleneimine (PEI) and aminosilanes containing at least one silane moiety and at least one amine moiety. Non-limiting examples of aminosilanes include aminoalkyl-substituted trialkoxysilanes (e.g., N-(2-aminoethyl)-3-aminopropyltrimethoxysilane). In some embodiments, porous silica fine powders or porous silica granules may be characterized by large pore diameters and high surface-to-volume ratios. In some examples, by recoating the fine particles constituting the granules with a functionalization mixture (e.g., a mixture of polymeramines and aminosilanes), the granules can obtain a CO2 recovery capacity comparable to or exceeding that of the "new" adsorbent on which the fine particles were formed. In many cases, the granules may have mechanical strength comparable to or even greater than that of the "new" adsorbents, depending on various factors (e.g., the stage in which the functionalized mixture is applied to the fine particles during aggregation or the stage in which the fine powder is applied to the granules as it aggregates, the type of amine-containing compound and / or binder used during aggregation, the shear force applied during aggregation, etc.).

[0008] While not desired to be limited by the mechanism, the combination of polymer amines and aminosilanes can increase the number of amine moieties available for carbon recovery. In some embodiments, this flocculation and coating method can reduce long-term manufacturing costs by facilitating the regeneration and recycling of scaled-up sorbents for several reagents. In some embodiments, this regeneration method reduces the energy, materials, and time required to produce new sorbents to replace those lost due to wear. In yet other embodiments, this regeneration method produces enhanced sorbents and reduces damage to the regenerated silica particles.

[0009] Generally, this disclosure relates to methods for recycling degraded sorbents. The adsorption capacity of an sorbent can be reduced to below an effective threshold after multiple adsorption and desorption cycles. Recycling degraded sorbents reduces the environmental impact of degraded sorbents produced by carbon capture treatments. This recycling method can be implemented on a large scale to reduce long-term recycling costs. Exemplary methods for recycling degraded sorbents include regeneration, reuse, or passivation.

[0010] The regeneration method reduces the energy, material, and time costs associated with producing new sorbents from degraded sorbents. This regeneration method includes calcination, amine regeneration, or amine reduction. Each regeneration method produces raw materials for new sorbents for further functionalization.

[0011] By integrating degraded sorbents into different industrial processes through reuse methods, the environmental impact of degraded sorbents is reduced. Therefore, by diverting degraded sorbents from waste flows and directing them towards manufacturing processes, the overall waste generated by carbon capture processes is reduced.

[0012] Passivation methods reduce the environmental impact of degraded sorbents by chemically equilibrating the amine groups present in the degraded sorbent. Chemical passivation also reduces the reactivity of the degraded sorbent, thereby reducing the costs and energy associated with the special handling and disposal of the degraded sorbent.

[0013] Generally, one embodiment disclosed herein is a functionalized granule comprising a plurality of fine particles, at least one of which comprises a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion, and a coating comprising an optional second silane portion and a second amine portion, and optionally configured to be bonded to the plurality of fine particles, and disposed on at least a portion of the surface of at least one of the plurality of fine particles.

[0014] In some embodiments, at least one of the plurality of fine particles comprises a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion.

[0015] In some embodiments, the coating includes an optional second silane portion and a second amine portion. In some embodiments, the coating is configured to bond the plurality of microparticles. In some embodiments, the coating includes the second silane portion, and the second amine portion is bonded to the second silane portion. In some embodiments, the coating is placed on the surface of the plurality of microparticles. In some embodiments, the first and second silane portions may be the same or different. In some embodiments, the first and second amine portions may be the same or different.

[0016] In some embodiments, the functionalized granules further include a matrix. In some embodiments, the matrix is ​​arranged between at least some of the plurality of microparticles. In some embodiments, the matrix includes the second silane moiety and the second amine moiety.

[0017] In some embodiments, the coating and / or matrix further comprises a polymer (e.g., a polymer amine), if present.

[0018] In another embodiment, the Disclosure comprises collecting a plurality of fine particles, at least one of which comprises a first porous silica, a first silane moiety bonded to the surface of the first porous silica, and a first amine moiety bonded to the first silane moiety; and using the plurality of fine particles to produce a plurality of functionalized granules having an average dimension or average dimension (e.g., diameter) greater than the average dimension or average dimension (e.g., diameter) of the plurality of fine particles, wherein optionally, at least one of the plurality of functionalized granules comprises a second porous silica, a second silane moiety bonded to the surface of the second porous silica, and a second amine moiety bonded to the second silane moiety.

[0019] In some embodiments (for example, any aspect of this specification), the average or average dimension (e.g., diameter) of the plurality of functionalized granules is greater than the average or average dimension (e.g., diameter) of the plurality of fine particles.

[0020] In some embodiments (for example, any aspect of this specification), at least one of the plurality of fine particles comprises a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion.

[0021] In some embodiments (for example, any aspect of this specification), at least one of the plurality of functionalized granules comprises a second porous silica, a second silane moiety bonded to the surface of the second porous silica, and a second amine moiety bonded to the second silane moiety.

[0022] In some embodiments, the generation includes aggregating the plurality of microparticles to provide a plurality of granules, and generating the plurality of functionalized granules by forming a coating on at least a portion of the surface of at least one of the plurality of granules and / or forming a matrix between at least a portion of the plurality of microparticles or between at least a portion of the plurality of granules.

[0023] In some embodiments, the generation includes providing a plurality of functionalized microparticles by forming a coating on at least a portion of the surface of at least one of the plurality of microparticles and / or forming a matrix between at least a portion of the plurality of microparticles, and generating a plurality of functionalized granules by agglomerating the plurality of functionalized microparticles.

[0024] In some embodiments, the generation includes exposing the plurality of microparticles, the plurality of granules (if present), or the plurality of functionalized microparticles (if present) to a liquid binder.

[0025] In some embodiments, the generation includes spraying a liquid binder onto the plurality of microparticles, the plurality of granules (if present), or the plurality of functionalized microparticles (if present).

[0026] In some embodiments, the generation includes shearing the plurality of microparticles, the plurality of granules (if present), or the plurality of functionalized microparticles (if present).

[0027] In some embodiments, the collection involves obtaining the plurality of fine particles from an inlet to a reactor containing the powder adsorbent, or from an outlet to a reactor containing the powder adsorbent (e.g., an adsorption reactor, a desorption reactor, or another reactor). In some embodiments, the powder adsorbent comprises the first porous silica, the first silane portion bonded to the surface of the first porous silica, and / or the first amine portion bonded to the first silane portion.

[0028] In some embodiments, at least one of the plurality of functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica.

[0029] In some embodiments, the method further includes drying the plurality of functionalized granules (for example, drying them in a vacuum oven at 80°C until the hydration threshold of water for the coated silica substrate reaches less than 5% wt / wt).

[0030] In another embodiment, the Disclosure encompasses a direct air recovery (DAC) system configured to use functionalized granules. In some embodiments, the system includes a first inlet configured to receive a first powder adsorbent; a second inlet configured to receive recycled powder adsorbent obtained by recycling at least a portion of the first powder adsorbent; an adsorbent system configured to adsorb CO2 from ambient air using the first powder adsorbent and the recycled powder adsorbent; a desorbent system configured to desorb CO2 from the first powder adsorbent and the recycled powder adsorbent; and an outlet configured to deliver a plurality of fine particles from the amount of air that has entered, passed through, or exited the adsorbent system.

[0031] In some embodiments, the first powder adsorbent comprises a plurality of first functionalized granules, at least one of which comprises a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion.

[0032] In some embodiments, at least one of the plurality of fine particles comprises the first porous silica from at least one of the plurality of first functionalized granules, the first silane moiety bonded to the surface of the first porous silica, and / or the first amine moiety bonded to the first silane moiety.

[0033] In some embodiments, the recycled powder adsorbent comprises a plurality of second functionalized granules, at least one of which comprises a second porous silica, a second silane portion bonded to the surface of the second porous silica, and a second amine portion bonded to the second silane portion.

[0034] In some embodiments, at least one of the plurality of second functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica, or at least one of the plurality of first functionalized granules of the first porous silica.

[0035] In some embodiments, the system further includes one or more blowers, each receiving ambient air and arranged to blow air into the adsorbent system, and one or more exhaust ports, each configured to remove air from the adsorbent system and / or the desorbent system. In some embodiments, the outlet is in fluid communication with at least one of the one or more exhaust ports.

[0036] In yet another embodiment, the Disclosure encompasses an aggregation system configured to provide functionalized granules. In some embodiments, the system includes a first inlet configured to receive a plurality of fine particles, at least one of which comprises a first porous silica, a first silane moiety bonded to the surface of the first porous silica, and a first amine moiety bonded to the first silane moiety; a second inlet configured to receive a liquid binder; a reactor configured to use the plurality of fine particles to produce a plurality of functionalized granules having an average size or average dimension (e.g., diameter) greater than the average size or average dimension (e.g., diameter) of the plurality of fine particles; and an outlet configured to deliver the plurality of functionalized granules outside the reactor.

[0037] In some embodiments, at least one of the plurality of functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica.

[0038] In some embodiments, the reactor includes a liquid handler (e.g., a sprayer) configured to expose the plurality of fine particles to a liquid binder (e.g., any of those described herein).

[0039] In some embodiments, the reactor includes a mixer configured to apply shear to the plurality of fine particles. Non-limiting mixers include pin mixers, paddle mixers, and / or ribbon blenders.

[0040] In any embodiment of this specification, the plurality of microparticles have an average or average dimension (e.g., diameter) of about 25 microns to about 500 microns.

[0041] In any embodiment of this specification, at least one of the plurality of particles comprises a plurality of pores. In some embodiments, the plurality of pores have an average or mean size (e.g., diameter) of about 60 angstroms to about 600 angstroms and / or a pore volume of about 0.1 mL / g to about 2.0 mL / g (e.g., about 0.5 mL / g).

[0042] In any embodiment of this specification, the functionalized granules have an average or average dimension (e.g., diameter) of about 500 microns to about 2 millimeters.

[0043] In any embodiment of this specification, the functionalized granules include a plurality of pores.

[0044] In any embodiment of this specification, the functionalized granules have a bulk density of approximately 10 lb / ft 3 ~40 lbs / ft 3 (For example, about 15 lb / ft 3 Or approximately 30 lb / ft 3 The material is characterized by having an average pore diameter of approximately 60 angstroms to approximately 600 angstroms, and / or a pore volume of approximately 0.1 mL / g to approximately 2.0 mL / g (for example, approximately 0.5 mL / g).

[0045] Generally, one embodiment disclosed herein is a method for producing calcined particles. The method comprises collecting a plurality of degraded functionalized particles which may include porous silica, a silane portion bonded to the surface of the porous silica, and an amine portion bonded to the silane portion, and heating the plurality of degraded functionalized particles to a temperature sufficient to thermally decompose the silane portion and the amine portion to produce a plurality of calcined particles.

[0046] For example, it may include one or more of the following characteristics:

[0047] In any embodiment of this specification, the plurality of degraded functionalized particles may have a CO2 absorption capacity of less than 0.5 mol CO2 / kg.

[0048] In any embodiment of this specification, the above temperature may be sufficient to prevent crystallization of the plurality of degraded functionalized particles.

[0049] In any embodiment of this specification, the method may include maintaining the temperature for a duration sufficient to thermally decompose the silane and amine portions.

[0050] In any embodiment of this specification, the method may include cooling the calcined particles after the duration at a rate sufficient to prevent crystallization of the calcined particles.

[0051] In any embodiment of this specification, the heating, cooling, or both are performed independently for a duration not exceeding one hour.

[0052] In any embodiment of this specification, the method may include providing at least a portion of the calcined particles as the plurality of fine particles in the method.

[0053] Generally, one aspect disclosed herein is a method comprising collecting a plurality of degraded functionalized particles which may comprise porous silica, a silane portion bonded to the surface of the porous silica, and an amine portion bonded to the silane portion, and exposing the plurality of degraded functionalized particles to a sedative so that the plurality of degraded functionalized particles are no longer reactive.

[0054] For example, it may include one or more of the following characteristics:

[0055] In any embodiment of this specification, the above method may include exposing the plurality of degraded functionalized particles to a reducing agent that chemically reduces the amine moiety.

[0056] In any embodiment of this specification, the method may include providing at least a portion of the porous silica as the plurality of fine particles in the method.

[0057] In any embodiment of this specification, the exposure may include exposing the plurality of degraded functionalized particles to an oxidizing agent that chemically reduces the amine moiety and the silane moiety.

[0058] In any embodiment of this specification, the exposure may include exposing the plurality of degraded functionalized particles to a converter so that the amine moiety can be converted into a nitrogen source.

[0059] In any embodiment of this specification, the nitrogen source may be a urea-containing nitrogen source.

[0060] In any embodiment of this specification, the conversion agent may be carbon dioxide or formaldehyde.

[0061] In any embodiment of this specification, the method may include drying the plurality of degraded functionalized particles before exposure until their moisture content is 5% wt / wt or less.

[0062] In any embodiment of this specification, the exposure may include exposing the plurality of degraded functionalized particles to one or more polar solvents sufficient to remove the amine and silane portions from the porous silica.

[0063] In any embodiment of this specification, the exposure may include exposing the plurality of degraded functionalized particles to a first aqueous solution with a pH of about 2 or less and a second aqueous solution with a pH of 12 or more, the pH of which may be sufficient to remove the amine and silane portions from the porous silica.

[0064] Certain non-limiting embodiments of the subject matter described herein can be implemented to achieve one or more of the following technical advantages:

[0065] By producing recycled silica in an aqueous single-pot reaction at ambient pressure and temperature on a short-time scale, manufacturing costs can be reduced, dependence on industrial solvents can be decreased, and / or the environmental impact of the product can be reduced.

[0066] Recycled silica can adsorb CO2 at concentrations similar to newly manufactured silica sorbents, enabling efficient recovery at atmospheric levels using recycled products. Recovering CO2 from atmospheric conditions facilitates the use of recycled silica in a wide range of applications.

[0067] By desorbing CO2 from regenerated silica at laboratory temperatures, the energy required to remove the recovered CO2 can be reduced, improving the applicability of regenerated silica to a wider range of industries and the environment, and / or increasing the CO2 desorption rate.

[0068] The regenerated silica achieves a high number of adsorption / desorption cycles, thereby reducing the operating costs of the carbon capture system.

[0069] By manufacturing recycled silica using industrially available components, manufacturing costs can be reduced and manufacturing scalability can be improved.

[0070] By regenerating silica fine powder with polymer compounds, the bonding stability and mechanical strength of aggregated particles can be increased, thereby extending the effective lifespan of the regenerated silica.

[0071] Details of one or more embodiments are described in the accompanying drawings and the description below. Other features and advantages will become apparent from the specification, drawings and the scope of the patent. [Brief explanation of the drawing]

[0072] [Figure 1] This is a schematic diagram of functionalized granules. [Figure 2A]This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2B] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2C] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2D] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2E] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2F] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2G] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2H] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2I] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2J] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 2K] This is a chemical diagram of exemplary compounds containing silane groups, amine groups, and polymer amine groups. [Figure 3A] This flowchart illustrates a non-limiting process for producing functionalized granules from microparticles. [Figure 3B] This is another flowchart illustrating a non-limiting process for producing functionalized granules from microparticles. [Figure 4] This is a schematic diagram of a non-restrictive aggregation process. [Figure 5] This is a schematic diagram of an exemplary paddle dryer for producing functionalized granules from fine particles. [Figure 6] This is a schematic diagram of an exemplary ribbon dryer used for producing functionalized granules from microparticles. [Figure 7A]This is a schematic diagram of an exemplary integrated system for silica functionalization, carbon dioxide extraction, and fine powder regeneration. [Figure 7B] This is a schematic diagram of an exemplary embodiment of a direct carbon dioxide air recovery system. [Figure 8] This is a schematic diagram of an exemplary embodiment of a carbon dioxide extraction system. [Figure 9] This is a schematic diagram of an exemplary embodiment of an integrated powdered carbon dioxide extraction system. [Figure 10A] These are schematic diagrams of the exploded view and assembled view of a sample holder for testing CO2 adsorption of a sample. [Figure 10B] This is a schematic diagram of an experimental apparatus for testing the absorption of CO2 from a sample.

[0073] In drawings, similar references indicate similar elements. [Modes for carrying out the invention]

[0074] Amorphous silica can be used as a porous structure for functionalization to achieve carbon recovery. Amine-functionalized silica substrates, for example, using one or more amine-containing groups covalently bonded on the surface, can be used to reversibly recover carbon dioxide from gaseous mixtures (e.g., air).

[0075] The movement of sorbents within carbon recovery process equipment can cause particle abrasion, potentially generating "fine particles." These fine particles typically end up in dust collectors rather than being recycled through the carbon recovery process.

[0076] In some embodiments, the fines are distinguished by their size compared to particles that can be used as sorbents. In some embodiments, the fines have an average dimension or average value dimension that is less than the average dimension or average value dimension of the particles used within the sorbent used in the gas recovery process. In some embodiments, the fines are characterized by an average dimension or average value dimension (e.g., diameter) of less than 500 microns (e.g., from about 25 microns to about 500 microns). Further, the size (e.g., diameter, radius, length, etc.) distribution of a plurality of fines (or a population of fines) can vary between systems, between batches of particles collected within the same system, and / or between different processing conditions. Thus, in some non-limiting embodiments, a population of fines having any size distribution and / or any average dimension or average value dimension can be used to generate functionalized particles (e.g., any of those described herein).

[0077] As used herein, the term "moiety" is used to describe a characteristic portion of an organic molecule. For example, an amine moiety is a molecule, compound, or portion of a compound that contains an amine group (e.g., -NR N1 R N2 ) as described herein, and a silane moiety is a molecule, compound, or portion of a compound that contains a silane group (e.g., -SiR S1 R S2 R S3 ) as described herein. In a non-limiting example, an amine moiety can include an aminoalkyl group (e.g., -Ak-NR N1 R N2 ) as described herein that can be present in an amino silane compound or a polymeric amine compound. The term "moiety" can be used to describe the larger molecule containing the group or to describe the group itself.

[0078] As used herein, “interaction” is used to describe covalent or non-covalent interactions between chemical substances, including physical adsorption, ionic interactions, hydrogen bonding, halogen bonding, electrostatic interactions, π-bond interactions, hydrophobic interactions, inclusion complexes, inclusion formation, van der Waals interactions, and combinations thereof.

[0079] As used interchangeably herein, “acyl” or “alkanoyl” means an aliphatic group or alkyl group, as defined herein, attached to a parent group through a carbonyl group. In certain embodiments, the alkanoyl is -C(O)-Ak, where Ak is an aliphatic group or alkyl group, as defined herein. In some embodiments, the unsubstituted alkanoyl is C 2~7 This is an alkanoyl group. An example of an alkanoyl group is acetyl.

[0080] As used interchangeably herein, “acyloxy” or “alkanoyloxy” means an acyl group or alkanoyl group, as defined herein, attached to a parent group through an oxy group. In certain embodiments, the alkanoyloxy is -OC(O)-Ak, where Ak is an aliphatic group or alkyl group, as defined herein. In some embodiments, the unsubstituted alkanoyloxy is C 2~7 This is an alkanoyloxy group. An example of an alkanoyloxy group is acetoxy.

[0081] "Aliphatic" refers to a molecule with at least one carbon atom to 50 carbon atoms (C) 1~50 ), for example, 1 to 25 carbon atoms (C 1~25 ) or 1 to 10 carbon atoms (C 1~10This refers to a hydrocarbon group having ), which includes alkanes (or alkyls, e.g., as described herein), alkenes (or alkenyls), and alkynes (or alkynyls), including their cyclic forms, as well as linear and branched structures, and all stereoisomers and positional isomers. Such hydrocarbons may be unsubstituted or substituted with one or more groups, such as alkyl groups as described herein.

[0082] "Alkyl" and the prefix "alky" refer to branched or unbranched saturated hydrocarbon groups with 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (t-Bu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, and tetracosyl. Alkyl groups are cyclic (for example, C 3~24 Alkyl groups may be cycloalkyl or acyclic. Alkyl groups may be branched or unbranched. Alkyl groups may be substituted or unsubstituted. For example, an alkyl group may be substituted with one or more alkenyl, alkoxy, alkynyl, amino, aryl, carboxyaldehyde (e.g., -C(O)H), carboxyl (e.g., -CO2H), cyano (e.g., -CN), halo, nitro (e.g., -NO2), oxo (e.g., =O), etc. An alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halos or alkoxys). In some embodiments, the unsubstituted alkyl group is C 1~3 , C 1~4 , C 1~6 , C 1~8 , C 1~10 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~6 , C 2~8 , C 2~10, C 2~12 , C 2~16 , C 2~18 , C 2~20 , C 2~24 , C 3~8 , C 3~10 , C 3~12 , C 3~16 , C 3~18 , C 3~20 or C 3~24 It is an alkyl group.

[0083] "Alkylene" means a polyvalent (e.g., divalent) form of an aliphatic group or alkyl group as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, and butylene. In some embodiments, the alkylene group is C 1~3 , C 1~4 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , C 1~24 , C 2~3 , C 2~6 , C 2~12 , C 2~16 , C 2~18 , C 2~20 or C 2~24 It is an alkylene group. The alkylene group may be branched or unbranched. The alkylene group may be substituted or unsubstituted. For example, the alkylene group may be substituted with one or more substituents, as described herein for alkyl groups.

[0084] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group or alkyl group, as described herein. Examples of alkoxy groups include trihaloalkoxys such as methoxy, ethoxy, butoxy, and trifluoromethoxy. Alkoxy groups may be substituted or unsubstituted. For example, an alkoxy group may be substituted with one or more substituents, as described herein for alkyl groups. An example of an unsubstituted alkoxy group is C 1~3 , C 1~6 , C 1~12 , C 1~16, C 1~18 , C 1~20 or C 1~24 An example is an alkoxy group.

[0085] "Amine" or "amino" means -NR N1 R N2 , -NR N1 -, or a compound having such a group, where R N1 and R N2 Each of them independently is H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl, or, where R N1 and R N2 These atoms, together with the nitrogen atoms to which they are bonded, form a heterocycline group.

[0086] "Aminoalkyl" means an aliphatic group or alkyl group as described herein, substituted with one, two, three or more amine groups. Aminoalkyls may include internal or terminal amine groups. Aminoalkyls may be further substituted. For example, an aminoalkyl may be substituted with one or more substituents as described herein for alkyl. An example of an unsubstituted aminoalkyl group is C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 or C 1~24 Examples include aminoalkyl groups.

[0087] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5 to 15 ring atoms having a monocycle (e.g., phenyl) or a plurality of fused rings (e.g., naphthyl, indolyl, or pyrazolopyridinyl) in which at least one ring is aromatic, i.e., at least one ring, and any plurality of fused rings, have a continuous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Hückel's rule (4n+2). Bonding to the parent structure is typically via the aromatic moiety of the fused ring system.

[0088] "Aryl" means an aromatic carbocyclic group having at least 5 to 15 carbon atoms (C 5~15 ), for example, 5 to 10 carbon atoms (C 5-10 ), having a monocyclic or multiple fused rings, which fused rings may or may not be aromatic, provided that the point of attachment to the remaining positions of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, for example, alkyl, and any substituent described herein for alkyl. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, etc. The term "aryl" also includes heteroaryl, which is defined as a group containing an aromatic group in which at least one heteroatom is incorporated into the ring. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl", which is also included in the term "aryl", defines a group containing an aromatic group that does not contain a heteroatom. In certain embodiments, the unsubstituted aryl group is a C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 or C 6~10 aryl group.

[0089] "Arylene" means a polyvalent (e.g., divalent) form of an aromatic group or aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthylene, anthrylene or phenanthrylene. In some embodiments, the arylene group is a C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 or C 6~10It is an arylene group. The arylene group can be branched or unbranched. The arylene group can be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substituents as described herein for alkyl or aryl.

[0090] "Aryloxy" means -OR, where R is an optionally substituted aromatic group or aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is C 4~18 or C 6~18 aryloxy group.

[0091] "Carbonyl" means a -C(O)- group.

[0092] "Halo" means F, Cl, Br or I.

[0093] "Heteroaliphatic" means an aliphatic group as defined herein that contains at least one heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms or 1 to 5 heteroatoms, and this aliphatic group is selected from, but not limited to, boron, halo, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms where applicable within the group.

[0094] "Heteroalkyl" means an aliphatic or alkyl group containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of boron, halo, nitrogen (e.g., those present in imino), oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms where applicable) as defined herein.

[0095] "Heteroalkylene" means a polyvalent (e.g., divalent) form of a heteroaliphatic group or heteroalkyl group as described herein. The heteroalkylene group can be substituted or unsubstituted. For example, the heteroalkylene group can be substituted with one or more substituents as described herein for alkyl.

[0096] "Heteroaromatic" means an aromatic group as defined herein, comprising at least one heteroatom to 20 heteroatoms, for example, 1 to 15 heteroatoms or 1 to 5 heteroatoms, the aromatic group being selected from, but not limited to, boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms within the group.

[0097] "Heteroaryl" means an aryl group containing at least one to six heteroatoms, for example, one to four heteroatoms, where the aryl group is selected from, but not limited to, boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and their oxidized forms within the ring. Such heteroaryl groups may have a monocyclic or multiple fused rings, where the fused rings may or may not be aromatic, and may or may not contain heteroatoms, provided that the bonding sites are mediated by atoms of an aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, for example, alkyls, and any substituents for alkyls as described herein. Exemplary heteroaryls include some heterocyclyl groups as defined herein that are aromatic, i.e., they contain 4n+2pi electrons within a monocyclic or polycyclic ring system.

[0098] "Heteroarylene" means a polyvalent (e.g., divalent) form of a heteroaromatic group or heteroaryl group as described herein. Exemplary heteroarylene groups include pyridinylene. In some embodiments, the heteroarylene group is C 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 or C 6~10The heteroarylene group is a heteroarylene group. The heteroarylene group may be branched or unbranched. The heteroarylene group may be substituted or unsubstituted. For example, the heteroarylene group may be substituted with one or more substituents, as described herein for alkyl or aryl groups.

[0099] Unless otherwise specified, "heterocyclyl" means a three-, four-, five-, six-, or seven-membered ring (e.g., a five-, six-, or seven-membered ring) containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, selenium, silicon, or sulfur). For example, a three-membered ring has 0 to 1 double bonds, four- and five-membered rings have 0 to 2 double bonds, and six- and seven-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, tetracyclic, or other polycyclic groups.

[0100] "Hydroxyl" means -OH.

[0101] "Imino" means -NR-, where R can be H, an optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl.

[0102] "Oxy" means -O-.

[0103] "Silan" is -SiR S1 R S2 R S3 , or a compound having such a group, where R 31 , R S2 and R S3 Each of these independently may be H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine or other as described herein, or R S1 and R S2 These atoms, together with the silicon atoms to which they are bonded, form a heterocycline group.

[0104] "Thioh" means -S-.

[0105] This specification discloses agglomerated functionalized porous silica for reversible recovery (e.g., adsorption) of carbon dioxide (CO2), a method for producing agglomerated silica from recovered fine powder, and a method for recycling degraded functionalized porous silica (e.g., sorbents or adsorbents). Generally, functionalized silica is a layer of beads or powder through which a gaseous mixture containing CO2 flows. The gas exiting the functionalized silica layer has a lower CO2 concentration than the gas entering it. During the adsorption and desorption processes of carbon recovery, the functionalized silica is handled through recovery and regeneration processes and is mechanically abraded during transport. Abrasion generates fine powder, which can be re-functionalized and agglomerated to produce functionalized granules suitable for reintroduction into carbon recovery process equipment.

[0106] Figure 1 shows an exemplary unit of functionalized granules 100. Functionalized granules 100 can reversibly adsorb CO2 over multiple cycles, for example, multiple adsorption and desorption steps. When used in CO2 recovery applications, a higher number of cycles results in a longer product life. In some embodiments, functionalized granules 100 reversibly adsorb CO2 over 100 cycles (e.g., over 500 cycles, over 1000 cycles, over 2000 cycles, over 3000 cycles). Here and throughout this specification, references to measurable values ​​such as quantity, duration over time, etc., and enumerations of such values ​​include exact values, approximations of such values, and values ​​within ±10% of such values. For example, here, 100 cycles includes exact 100 cycles, about 100 cycles, and within ±10% of 100 cycles.

[0107] CO2 adsorbed on the functionalized granules 100 is released (e.g., desorbed) under several conditions. For example, reducing the gas pressure surrounding the functionalized granules 100 causes the recovered CO2 to desorb. This facilitates the re-recovery of the adsorbed CO2 in the secondary environment. In some embodiments, the functionalized granules 100 are exposed to a reduced gas pressure of less than 5 psi (e.g., less than 3 psi, less than 1.5 psi, less than 1 psi, or less than 0.1 psi).

[0108] As a second example, increasing the temperature of the functionalized granules 100 desorbs CO2 from the functionalized granules 100 by destabilizing the bond between the amine moiety and CO2. In some embodiments, the functionalized granules 100 desorb CO2 at temperatures above 40°C (e.g., above 50°C, above 60°C, above 70°C, above 80°C, or above 90°C). By increasing the temperature and decreasing the gas pressure, the rate at which CO2 is desorbed from the functionalized granules 100 can be improved.

[0109] The fine particles 102 are generally a portion or aggregate of porous silica (e.g., silicon dioxide) beads or silica powder (e.g., from micrometer size to less than 0.5 millimeters in size) generated during the abrasion of a silica sorbent (e.g., during a carbon recovery process). In some embodiments, the fine particles 102 may consist of amorphous silica, e.g., noncrystalline silica. While the illustrated fine particles 102 are substantially spherical, the overall structure of the fine particles 102 may be any shape suitable for manufacturing. Furthermore, within such particles, pores may have any effective shape, composition, distribution, and arrangement (e.g., a hexagonal arrangement of pores in MCM-41, which may also be spherical or any other shape). In other words, the fine particles 102 may be bead-like, but are not limited to these.

[0110] The diameter or maximum dimensions of the particulate matter 102 may vary depending on the application and / or source. Generally, the particulate matter 102 has a diameter distribution with an average (e.g., mean) diameter that can range from 25 micrometers (μm) to 0.5 millimeters (mm) (e.g., 45 μm to 500 μm, 50 μm to 500 μm, 60 μm to 300 μm, 45 μm to 150 μm, 70 μm to 80 μm, 50 μm to 0.5 mm, or 200 μm to 0.5 mm). In some embodiments, the average diameter of the particulate matter 102 is less than 500 μm (e.g., less than 400 μm, less than 350 μm, less than 300 μm, less than 200 μm, or less than 100 μm).

[0111] The width of the distribution centered on the average diameter affects the adsorption performance of the fine particles 102. In some embodiments, the width of the distribution is 5 μm to 50 μm (e.g., 10 μm to 40 μm or 20 μm to 30 μm) centered on the average value. In some embodiments, the width of the distribution is 50 μm to 0.2 mm (e.g., 75 μm to 0.2 mm, 100 μm to 0.1 mm, 80 μm to 0.15 mm) centered on the average value.

[0112] The width of the distribution can be alternatively described using D90, D50, or D10 values. Such values ​​can be determined by any effective method, such as sieving. These values ​​indicate the proportion of the total distribution of material diameters in the sample up to and within that value. For example, a D90 of 500 μm indicates that 90% of the sample has a size of 500 μm or less. In some embodiments, the functionalized granules 100 have a D10 value of 30 μm or a D90 value of 150 μm. In some examples, the functionalized granules 100 have a D10 value of 100 μm or a D90 value of 500 μm, a D10 value of 150 μm or a D90 value of 400 μm, or a D10 value of 200 μm or a D90 value of 300 μm. In some embodiments, the functionalized granules have D50 values ​​of 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1400 μm, or 1500 μm.

[0113] Generally, while we do not wish to be bound by theory, smaller particle sizes 102 can facilitate better functionalization before aggregation and / or allow for higher CO2 recovery capacity. In some embodiments, smaller particle sizes 102 can lead to higher gas flow capacity and faster adsorption because the interparticle volume is larger, shortening the gas diffusion pathway throughout the functionalized granules 100. In other embodiments, smaller particle sizes 102 can lead to higher amine coating concentrations because the total surface area of ​​the functionalized granules 100 is relatively larger. In some embodiments, using smaller particle sizes 102 with a liquid binder can provide a granular core with increased strength (e.g., crushing strength) compared to particles with a porous silica core lacking a liquid binder. In other embodiments, smaller particle sizes 102, such as average radius or average width, can reduce the energy cost of the adsorption process for the fluidization process.

[0114] The microparticles 102 contain pores, which are openings extending from the outer surface of the microparticles 102 into their internal volume. The pores increase the surface area of ​​the microparticles 102. The dimensions of the pores vary from pore to pore and may vary within individual pores. Generally, the diameter of the pores is between 60 angstroms (Å) and 700 Å (e.g., 60 Å to 300 Å, 60 Å to 400 Å, 60 Å to 600 Å, 80 Å to 300 Å, 100 Å to 200 Å, 150 Å to 250 Å, 60 Å to 300 Å, 100 Å to 700 Å, 200 Å to 700 Å, 300 Å to 700 Å, 500 Å to 700 Å, 100 Å to 500 Å, or 300 Å to 500 Å). In some embodiments, the pores have an average or average size (e.g., diameter) of about 60 angstroms to about 600 angstroms. In some embodiments, the pore diameter is greater than 90 Å (e.g., greater than 100 Å, greater than 120 Å, greater than 150 Å). Larger pore diameters increase the adsorption and desorption rates and facilitate the filling of the pores by the amine moiety without pore blockage, which can reduce adsorption and desorption efficiency.

[0115] Pores extend within the central volume of the microparticles 102 and form interconnection channels. The pores create a volume through which gas can flow within the microparticles 102, resulting in additional surface area for functionalization. The volume of the pores is greater than 0.5 mL / g, preferably greater than 0.8 mL / g (e.g., greater than 1 mL / g, greater than 1.2 mL / g, greater than 1.5 mL / g, or greater than 1.8 mL / g). The increased total volume of pores increases the adsorption potential of the functionalized granules 100. The pores may have, but are not limited to, irregularly circular or hexagonal cross-sectional shapes. The total surface area of ​​the microparticles 102 includes the outer surface and the surface area within the pores. In some embodiments, the total surface area of ​​the microparticles 102 is 100 m² per dry gram. 2 (m 2 It is greater than ( / g). In some embodiments, the total surface area is 300 m². 2 / g or more (for example, 200m 2 / g, 400m 2 / g over 500m 2 / g or more, or 800m 2 The value is greater than / g. The larger the total surface area, the greater the area available for functionalization, and the greater the adsorption potential of the functionalized granules 100.

[0116] The surfaces of the functionalized granules 100 and / or fine particles 102 are functionalized with a CO2 adsorption compound 106 containing aminosilane 108 and polymeramine 110. In some examples, the functionalized granules 100 are functionalized as granules 100, while in other examples, the fine particles 102 are functionalized before agglomerating into the granules 100 (e.g., forming functionalized fine particles). In further examples, the fine particles 102 are functionalized during the agglomeration process such that a subgroup of fine particles 102 is functionalized on the exposed surface before agglomerating into the functionalized granules 100.

[0117] In some embodiments, the functionalized granules 100 have an average radius of 0.5 mm to 2.0 mm (e.g., 0.5 mm to 1.5 mm, 0.5 mm to 1.0 mm, 1.0 mm to 2.0 mm, or 1.5 to 2.0 mm). In some embodiments, the functionalized granules 100 have an average diameter of 0.5 mm to 2.0 mm (e.g., 0.5 mm to 1.5 mm, 0.5 mm to 1.0 mm, 1.0 mm to 2.0 mm, or 1.5 to 2.0 mm).

[0118] Generally, fine particles may be characterized by a larger surface area-to-volume ratio compared to larger particles. For example, but not limited to, larger particles tend to have a more spherical shape, increasing the overall surface area provided by pores, which in turn may provide additional surface area to be functionalized. Furthermore, a population of larger particles with a narrow size distribution (e.g., a population with a diameter or average diameter of about 0.5 to about 2 mm) may have a lower overall bulk density. Subsequently, a lower bulk density results in a smaller pressure drop across the adsorbent, which in turn may result in less energy being used to capture CO2. In contrast, finer particles with a wider particle size distribution (e.g., smaller particles with a diameter or average diameter of less than about 0.5 mm) are characterized by a higher bulk density, which in turn may result in a larger pressure drop across the adsorbent.

[0119] In many cases, the functionalized granules 100 are characterized by mechanical properties including crushing strength, shear strength, density (e.g., bulk density), pore size (e.g., average pore size), porosity, and / or pore volume (e.g., to provide a desired CO2 recovery capacity). Non-limiting properties include approximately 10 lb / ft 3 ~40 lbs / ft 3 (For example, about 15 lb / ft 3 , about 22lb / ft 3 , or approximately 25 lb / ft 3 , about 30lb / ft 3 , about 35lb / ft 3One or more of the following may be considered: bulk density of approximately 60 angstroms to approximately 600 angstroms, and / or pore volume of approximately 0.1 mL / g to approximately 2.0 mL / g (e.g., approximately 0.5 mL / g or approximately 1.5 mL / g), fracture strength in the range of approximately 1 MPa to approximately 4 MPa (e.g., approximately 2 MPa to approximately 3 MPa), e.g., stress at 50% compressive strain, and abrasion loss rate of 0 wt% to approximately 4 wt% (e.g., approximately 1.5 wt% or approximately 3 wt%) as measured by the ASTM D4058 test (e.g., loss measured over a duration of approximately 30 minutes at a rolling speed of approximately 60 rpm).

[0120] The aminosilane 108 and polymeramine 110 can together form a network, which can then provide a stable CO2 adsorption function. The network may include any effective combination of covalent and / or non-covalent interactions, and the network may feature a coating, a matrix, or both. The aminosilane 108 comprises at least one silane group (e.g., one, two, three or more silane groups) and at least one amine group. In some embodiments, the aminosilane 108 is covalently bonded to the outer surface and interior of the pores of the fine particles 102. The aminosilane 108 may contain one to three or more silane groups, e.g., silane group 208. In some embodiments, the silane groups may include dialkoxysilanol groups (e.g., -Si(OR)2OH, where each R is independently alkyl), hydrosilane groups (e.g., -SiH3), dialkylsilanes (e.g., -SiR S1 R S2 R S3 , here, R S1 and R S2 Each of them is independently alkyl, and R S3 (wherein is a reactive group or a leaving group, for example, any of those described herein, and non-limiting examples of dialkylsilanes are dialkylalkoxysilanes or dialkylhalosilanes), monoalkylsilane groups (e.g., -SiR) S1 R S2 R S3 , here, R S1is alkyl, and R S2 and R S3 Each of these is independently a leaving group or a reactive group, and includes, for example, any of those described herein (non-limiting examples of monoalkylsilanes are alkyldialkoxysilanes or alkyldihalosilanes), trihalosilane groups (e.g., -SiZ3, where each Z is independently a halo such as trichlorosilane), or silanetriol groups (e.g., -Si(OH)3), as well as others described herein. The greater the number of silane moieties in aminosilane 108 (e.g., three or more), the greater the number of siloxane bonds between the silane moieties and the surface of the microparticles 102, thus increasing the stability of the covalent bond with the microparticles 102. When there are more than three silane groups, the silane moieties refer to molecules such as, but not limited to, bis(3-trimethoxysilylpropyl)amine. Additionally, the silane moieties can form up to three siloxane bonds (Si-O-Si) on the silica surface, thus improving stability. The number of siloxane bonds that can be formed by the silane moiety is determined by the number of groups (X) that can form siloxane bonds. 1 ~X 3 It depends on the composition of (e.g., -OMe, -OEt, -CI, -OH, or any combination thereof).

[0121] Aminosilane compounds can have any valid structure. In a non-limiting example, aminosilanes include structures having formula (I). [R A ] a Si[X] 4-a (I) In the formula, each R A X is independently an amine moiety containing at least one amine group, each X is independently a side group, a reactive group, or a leaving group, and a is an integer from 1 to 4.

[0122] Amine portion (for example, R A ) may contain one or more amine groups. For example, the amine group may be -NR N1 R N2 or -NR N1 -This is possible, and here, R N1 and RN2 Each of these is independently hydrogen (H), halo (e.g., F, CI, Br, or I), hydroxyl (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted alkoxy (e.g., -OR, where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, where each R is independently optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, where each R is independently optionally substituted alkyl). In some embodiments, R N1 , R N2 Each of R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic.

[0123] In some embodiments, the amine portion (for example, R A ) comprises one, two, three or more amine groups. In other embodiments, the amine moiety has terminal amine groups (e.g., -NR N1 R N2 ) and internal amine groups (e.g., -NR) N1 -)

[0124] Amine portion (for example, R A A non-restrictive example of ) is -NR N1 R N2 , -L-NR N1 R N2 , -NR N3 -L-NR N1 R N2 , -L 2 -NR N3 -L-NR N1 R N2 , -L 3 -NR S4 -L 2 -NR N3 -L 1 -NR N1 R N2, -L 2 -SiR S1 R S2 -L 1 -NR N1 R N2 and -L 3 -SiR S1 R S2 -L 2 -NR N3 -L 1 -NR N1 R N2 These are listed, and here, R N1 , R N2 , R S1 , and R S2 Each of these may be any of those described herein, R N3 and R N4 Each of these is R N1 and N2 This may be any of the terms described herein, each L, L 1 , L 2 or L 3 R is independently a linker. Examples of linkers include, for example, covalent bonds, atoms (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylenes, optionally substituted heteroalkylenes, optionally substituted arylenes, or optionally substituted heteroarylenes. In some non-limiting embodiments, R N1 , R N2 , R N3 , R N4 , R S1 and R S2 Each of these is independently H, an optionally substituted aliphatic, or an optionally substituted alkyl.

[0125] An aminosilane may contain a reactive group, a leaving group, or another group (e.g., X). Non-limiting examples of such groups include H, a halo (e.g., F, CI, Br, or I), a hydroxyl (e.g., -OH), an optionally substituted alkyl, an optionally substituted aminoalkyl, an optionally substituted alkoxy (e.g., -OR, where R is an optionally substituted alkyl), an optionally substituted aryl, an optionally substituted aryloxy (e.g., -OR, where R is an optionally substituted aryl), or an optionally substituted alkanoyloxy. In some embodiments, X is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic.

[0126] In a non-limiting example, aminosilanes include structures having formula (Ia). R A1 SiX 1 X 2 X 3 (Ia) In the formula, R A1 is an amine moiety containing at least one amine group, and X 1 , X 2 and X 3 Each of these is independently a side group, a reactive group, or a leaving group. A1 , X 1 , X 2 and X 3 Each of these is R A And X may be any of those described herein.

[0127] In another non-restrictive example, aminosilanes include structures having the formula (lb)~(le). R A1 -L 1 -SiX 1 X 2 X 3 (Ib) R N1 R N2 NL 1 -SiX 1 X 2 X 3(I C), R A1 -L 1 -R A2 -L 2 -SiX 1 X 2 X 3 (Id), or R N1 R N2 NL 1 -N(R N3 )-L 2 -SiX 1 X 2 X 3 (le) In the formula, R A1 or R A2 Each of them is independently an amine moiety containing at least one amine group, R N1 , R N2 and R N3 Each of these may be any of those described herein, X 1 , X 2 and X 3 Each of these is independently a side group, a reactive group, or a leaving group, L 1 and L 2 Each of these is a linker. A1 , R A2 , X 1 , X 2 , X 3 , L 1 and L 2 Each of these is R A , X and L may be any of those described herein. In some embodiments, X 1 , X 2 and X 3 Each of these independently consists of H, halo, and optionally substituted alkyl (e.g., optionally substituted C). 1~3 Alkyl) or optionally substituted alkoxy (e.g., optionally substituted C) 1~3 In other embodiments, X 1 , X 2 and X 3 Each of them independently has an arbitrarily substituted alkoxy (e.g., an arbitrarily substituted C 1~3(is an alkoxy). In yet another embodiment, L is optionally substituted alkylene (e.g., optionally substituted C 1~12 , C 1~10 , C 1~8 or C 1~6 alkylene).

[0128] In yet another non-limiting example, the aminosilane comprises a structure having the formula (If). R A1 R A2 R A3 SiX 1 (If) wherein each of R A1 , R A2 or R A3 is independently an amine moiety containing at least one amine group, and X 1 is a side group, a reactive group or a leaving group. Each of R A1 , R A2 , R A3 and X 1 can each be any of those described herein for R A and X.

[0129] In some examples, the aminosilane comprises a structure of formula (II). [R B b N[Y] 3-b (II) wherein each R B is independently a silane moiety containing at least one silane group, each Y is independently H, optionally substituted alkyl, or optionally substituted aryl, and b is an integer from 1 to 3. In some embodiments, each Y is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.

[0130] The silane moiety (e.g., R B ) can contain one or more silane groups. In one example, the silane group is -SiR S1 R S2 R S3 or -SiR​S1 R S2 -This is possible, and here, R S1 , R S2 and R S3 Each of these is independently hydrogen (H), halo (e.g., F, CI, Br, or I), hydroxyl (e.g., -OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted alkoxy (e.g., -OR, where R is optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., -OR, where R is optionally substituted aryl), trialkylsilyloxy (e.g., -OSiR3, where each R is independently optionally substituted alkyl), or trialkoxylsilyloxy (e.g., -OSi[OR]3, where each R is independently optionally substituted alkyl). In some embodiments, R S1 , R S2 , R S3 Each of R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic.

[0131] In some embodiments, the silane portion (for example, R B ) comprises one, two, three or more silane groups. In other embodiments, the silane moiety is a terminal silane group (e.g., -SiR S1 R S2 R S3 ) and internal silane groups (e.g., -SiR S1 R S2 -)

[0132] Silane portion (for example, R B A non-restrictive example of ) is -SiR S1 R S2 R S3 , -Si(OR S1 )(R S2 )(R S3 ), -Si(OR S1 )(OR S2 )(R S3 ), -Si(ORS1 )(OR S2 )(OR S3 ), -L-SiR S1 R S2 R S3 , -L-Si(OR S1 )(R S2 )(R S3 ), -L-Si(OR S1 )(oR S2 )(R S3 )-,-L-Si(OR S1 )(OR S2 )(OR S3 ), -SiR S4 R S5 -L-SiR S1 R S2 R S3 and -SiR S1 R S2 -NR N1 R N2 These are listed, and here, R S1 , R S2 , R S3 , R N1 and R N2 Each of these may be any of those described herein, R S4 and R S5 Each of these is R S1 , R S2 and R S3 R may be any of those described herein, where L is a linker. Examples of linkers include, for example, covalent bonds, atoms (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylenes, optionally substituted heteroalkylenes, optionally substituted arylenes, or optionally substituted heteroarylenes. In some non-limiting embodiments, R S1 , R S2 , R S3 , R S4 R S5 , R N1 and R N2 Each of these is independently H, an optionally substituted aliphatic, or an optionally substituted alkyl.

[0133] In a non-limiting example, aminosilanes include structures having formula (IIa). R B1 NY 1 Y 2 (IIa) In the formula, R B1 is a silane moiety containing at least one silane group, Y 1 and Y 2 Each of these is one of the terms described herein for Y. B1 R B This may be any of the terms described herein.

[0134] In another non-limiting example, aminosilanes include structures having formulas (IIb) to (IId). R B1 R B2 NY 1 (IIb) [R S1 R S2 R S3 Si-L 1 -]NY 1 Y 2 (IIc), or [R S1 R S2 R S3 Si-L 1 -]NY 1 [-L 2 -SiR S1 R S2 R S3 ](IId) In the formula, R B1 or R B2 Each of them is independently a silane moiety containing at least one silane group, Y 1 and Y 2 Each of these is independently a side group, a reactive group, or a leaving group, R S1 , R S2 and R S3 Each of these may be any of those described herein, L 1 and L 2 Each of these is a linker. B1 , R B2 , Y 1 , Y 2 , L 1 and L 2 Each of these is R BY and L may be any of those described herein.

[0135] Figures 2A-2C illustrate examples of aminosilanes with non-restrictive silane groups (Figure 2A) and examples of amine moieties (Figures 2B and 2C). Figure 2A illustrates an example of aminosilane 206 having silane group 208 with three potential interaction sites. Aminosilane 206 is an example of a chemical that can provide aminosilane 108. Aminosilane 206 has an amine group 210 represented by RA and three silane groups 208 X 1 ~X 3 It has a silane group 208 X 1 ~X 3 This includes a methoxy group (-OMe), an ethoxy group (-OEt), a chloro group (-Cl), a hydroxyl group (-OH), a hydrogen group (-H), or an alkyl group (e.g., -(CH2)). n X may be substituted with functional groups including, but not limited to, linear alkyl groups (where n is an integer between 0 and 10) such as (CH3), or branched alkyl groups. Further examples of functional groups may include any of the reactive or leaving groups described herein. Non-limiting examples of functional groups of X may include halos, and optionally substituted aliphatic, alkyl, alkoxy, alkanoyloxy, heteroaliphatic, heteroalkyl, aromatic, aryl, and aryloxy groups.

[0136] The aminosilane 206 used as aminosilane 108 can be any combination of these functional groups, for example, amine group 210 and silane group 208 (e.g., X 1 ~X 3The group may have at least one amine group 210 and at least one silane group 208 (e.g., -OMe, -OEt, -Cl, -OH, or other groups described herein) that can form a siloxane bond (e.g., Si-O or Si-O-Si bond). Figure 2B is a non-limiting example of the 3-aminopropyl group, which in some examples functions as one or more silane groups 208 or amine groups. Figure 2C is a non-limiting example of the N-(2-aminoethyl)-3-aminopropyl group, which in some examples functions as one or more amine groups 210.

[0137] As a non-limiting example, Figures 2D-2G show an example of aminosilane 206 functionalized with silane group 208 and amine group 210 suitable for this application, for example, functioning as aminosilane 108. Figures 2D and 2E are R A (CH3) c Si(OEt) d Examples of alkylalkoxyaminosilanes of type (for example, where each of c and d can be 1 or 2 in 3-aminopropyl(diethoxy)methylsilane and 3-(ethoxydimethylsilyl)propylamine) are shown, which in some examples function as aminosilane 108 or 206. Generally, although we do not wish to be bound by theory, the amine group 210 (e.g., the amine moiety) of one aminosilane 206 interacts with one or more of the silane groups 208 of adjacent aminosilanes 206. Figure 2F shows (OH)3SiR A An example of a type aminosilanetriol (e.g., (3-((2-aminoethyl)amino)propyl)silanetriol) is shown, which in some cases functions as aminosilane 108 or 206. Figure 2G shows (R A ) is an example of a 3SiCl type chloroaminosilane (e.g., tris(dimethylamino)chlorosilane, tris(ethylmethylamino)chlorosilane, etc.), which in some cases functions as aminosilane 108 or 206.

[0138] The amine portion of aminosilane 108 is X of the adjacent aminosilane 108. 1 ~X 3 It may interact with one or more of the moieties or with polymer amine 110. The amine moiety is or may contain amine groups such as the amine groups in Figures 2B and 2C, which illustrate exemplary aminopropyl and N-(2-aminoethyl)-3-aminopropyl groups, respectively. In some embodiments, the amine moiety is a primary, secondary, or tertiary amine group. For example, the amine moiety includes one or more aminopropyl or diethylenetriamine groups. In some embodiments, the amine moiety includes two or more amine groups linked via various alkyl groups. For example, the amine moiety may include a terminal amine group, an internal amine group, and a linker positioned between the terminal and internal amine groups. Optionally, a further linker may be present between the amine and silane moieties of the aminosilane compound.

[0139] In some embodiments, aminosilane 108 includes (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N-(2-aminoethyl)-3-aminopropylsilanetriol, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-aminopropylsilanetriol, N-(2-aminoethyl)-3-aminopropylsilanetriol, tris(ethylmethylamino)chlorosilane or tris(dimethylamino)chlorosilane, or aminosilane oligomers, such as Evonik's VPS SIVO 280.

[0140] The amine moiety of aminosilane 108 and polymer amine compounds interact with the silanol group (or other group) of aminosilane 108 through hydrogen bonding and ionic interactions to form a network across the silica surface. In some examples, polymer amine 110 is a polymer / oligomeric amine such as polyethyleneimine (PEI), poly(propyleneimine) (PPI), or other polymer amine mixtures (e.g., Amix 1000, as produced by BASF, Ludwigshafen, DE). In some examples, polymer amine 110 is a small molecule containing an amine moiety such as tetraethylenepentamine (TEPA), triethylenetetramine (TETA), ethanolamine, diethylenetriamine, piperazine, pentaethylenehexamine, or tetramethylethylenediamine.

[0141] Polymer amines can have any valid structure. In a non-limiting example, polymer amines include structures having formula (III). -(R A -L) n -(III) In the formula, each R A R is an amine moiety independently containing at least one amine group, each L is independently a linker, and n is an integer greater than 1 (e.g., including 1 to 1000, 1 to 100, 1 to 50, 1 to 20, 1 to 10, 5 to 1000, 5 to 100, 5 to 50, 5 to 20, 5 to 10, and the range in between). A and L may be any of those described herein. In some embodiments, R A -NH-, -NR N1 -, -N(-L-NR) N1 R N2 )-,-N(-L2-NR N3 -L 1 -NR N1 R N2 )-, -N[-L 2 -N(-L 1 -NR N1 R N2 )2]-, -NH2 or -NR N1 R N2is or includes them, where R N1 and R N2 Each of these may be any of those described herein, and each R N3 R N1 and R N2 This may be any of the terms described herein, each L, L 1 or L 2 These are linkers in themselves. Examples of linkers include, for example, covalent bonds, atoms (e.g., carbonyl, oxy, thio, imino, etc.), optionally substituted alkylenes, optionally substituted heteroalkylenes, optionally substituted arylenes, or optionally substituted heteroarylenes.

[0142] Figures 2H and 2I illustrate non-limiting general examples of polymer amine chains that can provide polymer amine 110. The polymer amines in Figures 2H and 2I have amine groups (e.g., -NH-, -NR-). N1 -, -NH2 or -NR N1 R N2 It includes repeating units composed of ) and a linker. In some examples, the linker is a carbon aliphatic-(CH2) n -A spacer group may be present, where n is an integer greater than 1 (e.g., integers such as 1 to 20, 1 to 10, 1 to 12, 1 to 6, etc.). Figure 2H shows an n-propylene (-CH2CH2CH2-)(C3H6) spacer group. Figure 2I shows an ethylene (-CH2CH2- or C2H4) spacer group. Polymer amines have a repeating chain portion (in brackets) of the polymer chain portion having a length of n active groups (e.g., if n=2, there are two repeating groups in the chain portion). Other linkers may be used, e.g., any of those described herein (e.g., optionally substituted alkylenes as described herein), as well as linkers having peptide bonds (e.g., -C(O)NH-) or glycosidic bonds. Linkers may include peptides, polysaccharides, etc. Furthermore, polymer amines may include linear or branched structures, e.g., those present in linear polymers, branched polymers, block polymers, or dendrimers.

[0143] Figure 2H illustrates a polymer amine having n active groups in the repeating chain portion. Figures 2H and 2I illustrate repeating chain portions containing two amine groups (-N(X)-) separated by three (Figure 2H) or two (Figure 2I) carbon spacer groups. In NX, X may be any side group, reactive group, leaving group, or other groups described herein. For example, X may be H, optionally substituted aliphatic, heteroaliphatic, aromatic, etc. Furthermore, X may contain further amine groups. Thus, in some non-limiting embodiments, X may contain any RA groups described herein. Figure 2I illustrates amine groups extending in different directions from the carbon chain, and Figure 2H illustrates amine groups extending in similar directions. Figure 2J is an example of polylysine, which functions as polymer amine 110 in some examples. Figure 2K is an example of natural chitosan, which functions as polymer amine 110 in some examples.

[0144] When exposed to a gaseous mixture containing CO2, the amine compound reacts with CO2, binding CO2 to its functional group. This allows for the functional adsorption of CO2 onto the microparticles 102 via compound 106 bound to the surface of the microparticles 102. While we do not wish to be bound by theory, the total surface area, pore volume, and number of amine groups within the amine and silane compounds determine the adsorption capacity of the functionalized granules 100. The adsorption capacity (e.g., absorption) of the functionalized granules 100 is approximately 0.5 mol to approximately 2.5 mol of CO2 per dry kilogram of functionalized granules 100 (e.g., greater than 1 mol CO2 / kg, greater than 1.5 mol CO2 / kg, greater than 2 mol CO2 / kg, greater than 2.5 mol CO2 / kg, 1 mol to 2 mol CO2 / kg, 1.5 mol to 2 mol CO2 / kg, 1 mol to 1.5 mol CO2 / kg, 1.5 mol to 2.5 mol CO2 / kg, or 2 mol to 2.5 mol CO2 / kg). In some embodiments, the functionalized granules 100 achieve a CO2 adsorption capacity of up to 2 mol CO2 / kg at 420 ppm CO2 under ambient air conditions.

[0145] Under environmental conditions, the atmosphere contains water vapor concentration (e.g., humidity). Functionalized granules 100 recover CO2 under atmospheric conditions within a range of relative humidity levels. For example, functionalized granules 100 recover CO2 under atmospheric conditions with relative humidity (RH) of 0% to 100%, for example, 5% to 95% RH (e.g., 15% to 50% RH, 25% to 40% RH, 10% to 60% RH, 5% to 90% RH, 10% to 90% RH, or 20% to 80% RH). In some embodiments, functionalized granules 100 recover CO2 under atmospheric conditions having RH greater than 60%, greater than 75%, greater than 90%, or greater than 95%.

[0146] In some embodiments, additives can be included in the functionalized mixture to extend the operational life of the functionalized silica. For example, the addition of bis[3-(trimethoxysilyl)propyl]amine) to the mixture can extend the operational life of the functionalized silica. BTMSPA is a two-terminated aminosilane, each terminus having a trimethoxysilyl reactive group. BTMSPA binds to the silica substrate at six bonding sites, in contrast to the three bonding sites of aminosilanes with a single reactive group, such as those found in compounds with a methoxydialkylsilyl reactive group. The increased number of bonding sites increases the binding stability with the silica substrate. BTMSPA further increases the overall binding stability of the network by forming a network on the surface with other aminosilanes and polymer amines.

[0147] In some embodiments, the functionalized particles 100 include an antioxidant additive that prevents the decomposition of the polymer amine 110 by oxygen in the atmosphere and extends the cycle life of the functionalized particles 100. For example, the antioxidant additive can be an organosulfur-containing compound such as 2,2'-thiodiethanol, 2-hydroxyethyldisulfide, and 3,3'-dithiodipropionic acid. Generally, the amount of the antioxidant additive in the functionalized particles 100 is 5% wt / wt (e.g., 3% wt / wt, 4% wt / wt, 6% wt / wt, or 8% wt / wt) with respect to silica. The term wt / wt refers to the weight ratio of the first component to the second component. For example, 1 g of the first substance and 10 g of the second substance define a 10% wt / wt ratio of the first substance to the second substance.

[0148] The antioxidant additive may be added to step 304, 306, or 308 of the following synthesis procedure, or alternatively, dissolved in methanol and then added by soaking silica in the additive / methanol mixture for 1 hour.

[0149] In some embodiments, the functionalized particles 100 may include a hydrophobic silane or other hydrophobic compound including a hydrophobic polymer coating, or may be functionalized thereby. In the case of a hydrophobic silane, it is a silane molecule having one or two or three alkyl chains. The alkyl chains of the silane molecule can increase the hydrophobicity of the silane molecule. When the silane molecule binds to the silica substrate, the hydrophobicity of the functionalized particles 100 increases. Therefore, it can reduce the moisture adsorption capacity of the functionalized particles 100, which can be beneficial in some cases such as when using the sorbent under high humidity conditions. For the same purpose of increasing the hydrophobicity of the functionalized particles 100, an additional hydrophobic polymer coating can be used. Polydimethylsiloxane (PDMS), silicone oil, polyethylene, polytetrafluoroethylene, and polyurethane are possible hydrophobic polymers that can be used to coat the outer surface of the functionalized particles 100 to reduce the adsorption of water in high humidity applications.

[0150] The synthesis of functionalized granules 100 is carried out under industrially applicable reaction conditions, such as liquid applications, for fine particles subjected to rolling or mixing motion. After aggregation and synthesis, the adsorbent is purified, dried, and activated before being used as a CO2 adsorbent, such as functionalized granules 100. Figure 3A is a flowchart detailing a non-limiting process 300 for producing functionalized granules for use in reversible adsorbents, for example, for synthesizing a reversible CO2 adsorbent such as functionalized granules 100. Figure 3B is a flowchart detailing another non-limiting process 310 for producing functionalized granules for use in reversible adsorbents, for example, for synthesizing a reversible CO2 adsorbent such as functionalized granules 100. Figure 4 is a schematic diagram of the aggregation process.

[0151] Referring to both Figures 3A and 3B, in some embodiments, processes 300 and 310 are performed on a large scale, for example, to produce more than 1 kilogram of functionalized granules 100 in a single process. In some embodiments, processes 300 and 310 produce more than 100 kilograms, for example, up to 10,000 kg of functionalized granules 100. For any process conditions or process characteristics described herein, batch or continuous processes may be applied. To maintain the original particle size distribution and reduce further wear, stirring methods that expose the fine particles to relatively low frictional or agitating forces are preferred, such as overhead stirring, gentle rolling, slow and periodic stirring, or vibration.

[0152] In Figure 3A, process 300 includes collecting multiple particulate matter, such as particulate matter 102 in Figure 1 or particulate matter 430 in Figure 4 (step 302). Generally, particulate matter can be collected in the dust collection assembly of a CO2 direct air recovery (DAC) system, such as the exemplary DAC system in Figure 7B. In many examples, the particulate matter is collected from the dust collector of the DAC system, agglomerated into granules, and regenerated into a new sorbent in a container suitable for the total volume of the particulate matter and the reagent applied to the surface.

[0153] Process 300 optionally includes exposing a plurality of microparticles to a liquid binder, such as the liquid binder 420 in Figure 4 (step 304). Generally, but not limited to, the liquid binder may contain water or other solvents and may contain one or more reagents for coating and functionalizing the microparticles, granules, or both. Such reagents may include silanes, aminosilanes, silane moieties, amine moieties, amine moieties bonded to silane moieties, polymeramines, or any combination thereof.

[0154] The liquid binder can be introduced under any effective conditions. These conditions include specifying or adjusting the tip speed, water content, liquid binder addition rate, mixing time, and / or temperature to sufficiently aggregate multiple microparticles, multiple granules (if present), or multiple functionalized microparticles (if present).

[0155] Exposure of multiple fine particles to a liquid binder (step 304) can result in aggregation (e.g., granule formation), coating formation, and / or matrix formation. By optimizing various conditions in the presence of the liquid binder, desired properties can be imparted to the granules, coating, and / or matrix.

[0156] Referring briefly to Figure 4, the two central figures illustrate that a liquid binder 420 is placed between collected fine particles 430. In the first figure from the left, the liquid binder may be provided, for example, by an atomizer of a shear force applied mixer. In the second figure from the left, the liquid binder 420 forms a liquid bridge 442 between the fine particles 430. Although we do not wish to be bound by theory, as shown in the third figure from the left, the surface tension of the liquid binder 420 draws the fine particles 420 into a group of particles that together may contain a solid bridge 444. When a shear force is applied and an optional additional liquid binder is applied, the fine particles 430 may be drawn into larger granules 450, providing granules 100. The application of the liquid binder 420 and / or the application of shearing may be stopped when the granules 450 reach desired constraints, such as average maximum dimension, maximum dimensional distribution, average density, wettability, amount of applied liquid binder (e.g., weight relative to fine particles), or other properties described herein.

[0157] Shearing can be provided in any effective manner. Non-limiting equipment for providing shearing includes pin mixers, paddle mixers, and / or ribbon blenders. In some embodiments, shearing may be provided in the presence of a liquid binder, and non-limiting equipment may include equipment capable of providing both shearing and delivery of the liquid binder. In other embodiments, the equipment may include the use of a first component configured to provide shearing (e.g., a mixer or blender) and a second component configured to provide the liquid binder (e.g., a liquid handler such as a sprayer).

[0158] Generally, the size of the granules 450 depends on the residence time spent on aggregation (e.g., mixing), with longer residence times resulting in larger maximum dimensions of the granules 450 compared to shorter residence times (e.g., mixing time). Other processing variables that may affect one or more desirable parameters of the granules 450 include the mixer tip speed or paddle speed, the final moisture content %wt / wt of the granules 450, the rate of addition of the liquid binder, the mixing temperature, or a combination thereof.

[0159] Referring again to Figure 3A, process 300 includes agglomerating a plurality of microparticles to provide a plurality of granules (step 306). In some embodiments, agglomeration (step 306) may be performed simultaneously with exposing the microparticles to a liquid binder (step 304). In other embodiments, exposing the microparticles to a liquid binder (step 304) may be performed first, and agglomeration (step 306) may include introducing shear to the liquid binder and microparticles to provide granules.

[0160] Process 300 includes forming a coating on the surface of at least one of the granules and / or forming a matrix between the granules (step 308). By coating or forming a matrix on the granules 450, a plurality of functionalized granules are produced that function to adsorb CO2 onto the functionalized surface. The fine particles 430 are portions of a functionalized sorbent having a functionalized surface having a first silane portion and a first amine portion, e.g., aminosilane 108 and polymeramine 110. In some embodiments, the coating and / or matrix may include a silane portion (e.g., a second silane portion) bound to the surface of at least one granule 450 and an amine portion (e.g., a second amine portion) bound to the silane portion, in addition to a coating previously applied to the fine particles 430 (e.g., a previous coating for the fine particles may include a first silane portion and a first amine portion).

[0161] In one example, forming a coating or matrix involves exposing granules to a functionalized mixture, which is formed by introducing a first reagent containing a polymer amine and a second reagent containing a silane moiety and an amine functional group (e.g., those present in aminosilane) into a certain volume of a solvent, such as water.

[0162] In some examples, producing a functionalized mixture may involve introducing, for example, a first reagent containing a polymer amine and a second reagent containing a silane moiety and an amine functional group into a certain volume of water, or introducing, for example, polymer amine 110 and aminosilane 108 into a certain volume of water to form a functionalized mixture. In some cases, the solvent may be an organic solvent. When used herein, reagents and compounds may be used interchangeably. Depending on the use, the reagent may optionally contain one or more solvents, salts or other compounds.

[0163] The first reagent, the second reagent, and a certain volume of water are dispensed and mixed. The first reagent is a polymer amine material, such as a polymer amine compound described herein. To completely suspend the polymer amine material in the container, water must be dispensed, for example, by dispensing 20 mL / g (e.g., 10 mL / g, 15 mL / g, or 25 mL / g) of water onto the polymer amine material. The polymer amine material is added to water in a range of 5% wt / wt to 20% wt / wt (e.g., 6% wt / wt, 8% wt / wt, 10% wt / wt, 12% wt / wt, 14% wt / wt, 16% wt / wt, or 18% wt / wt) of the silica sorbent functionalized in step 308.

[0164] The second reagent is a silane coupling material, including the example of aminosilane 108 described above. The silane coupling material can be dispensed in a range of 20% wt / wt to 70% wt / wt (e.g., 25% wt / wt, 30% wt / wt, 35% wt / wt, 45% wt / wt, 50% wt / wt, or 60% wt / wt) of the silica sorbent coated in step 308.

[0165] The liquid mixture is stirred until the polymer amine material and silane coupling material are completely suspended in water. In some examples, the polymer amine material is dispersed for 5 to 60 minutes (e.g., 10 to 30 minutes, 5 to 30 minutes, 10 to 45 minutes) by mechanical stirring with a propeller, magnetic stirrer, or ultrasonic treatment.

[0166] Optionally, the functionalized mixture is stirred for a certain duration to hydrolyze and thoroughly dissolve the silane coupling material and polymer amine material. Generally, the first period is 1 to 10 minutes (e.g., 5 minutes).

[0167] Optionally, once a coating or matrix is ​​formed on the granules, the functionalized granules are dried. Drying the functionalized granules may include increasing the temperature, decreasing the atmospheric pressure, blowing an inert drying gas onto the sample, blowing a heated drying gas onto the sample, or a combination thereof. Drying the functionalized granules substantially removes all liquid binders and / or functionalized mixtures encompassed in or on the functionalized granules.

[0168] For example, in some embodiments, the functionalized granules are dried in a 70°C oven for 5 to 20 minutes. Drying times exceeding 60 minutes reduce the absorption capacity of the final product. However, drying times can be scale-dependent or condition-dependent. For example, drying under N2 or vacuum may result in longer drying times. In examples where batch drying is performed, even under N2 or vacuum, drying times may be longer than 60 minutes depending on the scale of the functionalized granules being dried. Alternatively, the functionalized silica material is dried in a 70°C oven until a hydration threshold is reached. As a non-limiting example, the hydration threshold refers to a weight loss of 15% of the sample (e.g., weight loss due to water removal) or the point at which no further weight loss is observed at 70°C while flowing with an inert gas (N2) as measured by thermogravimetric analysis (TGA). Alternatively, the functionalized silica is dried in an oven until the water content in the material is less than 5% wt / wt.

[0169] Another non-limiting process is shown in Figure 3B, where process 310 includes collecting multiple particulate matter, such as particulate matter 102 in Figure 1 or particulate matter 430 in Figure 4 (step 312). Some details described herein with respect to Figure 3A are also applicable to the process in Figure 3B. For example, particulate matter may be collected in a dust collection assembly of a CO2 direct air recovery (DAC) system, such as the exemplary DAC system in Figure 7B.

[0170] Process 310 includes forming a coating on at least one surface of the fine particles and / or forming a matrix between the fine particles (step 314). The details described herein with respect to step 308 in process 300 in Figure 3A are similarly applicable to step 314 in process 310 in Figure 3B. In this process 310, the resulting particles are coated fine powders and may be described as functionalized fine particles (e.g., fine particles having a surface functionalized with a first silane moiety such as aminosilane 108 and a first amine moiety and polymer amine 110).

[0171] Next, the functionalized microparticles may be agglomerated. Process 310 includes agglomerating a plurality of functionalized microparticles to provide a plurality of functionalized granules (step 318). The details described herein with respect to step 306 in process 300 in Figure 3A are similarly applicable to step 318 in process 310 in Figure 3B. For example, in some embodiments, agglomeration (step 318) may be performed simultaneously with exposing the microparticles to a liquid binder (step 316). In other embodiments, exposing the microparticles to a liquid binder (step 316) may be performed first, and agglomeration (step 318) may include introducing shear to the liquid binder and microparticles to provide granules.

[0172] Process 310 optionally includes exposing a plurality of microparticles to a liquid binder, such as the liquid binder 420 in Figure 4 or any liquid binder described herein (step 314). Exposure of a plurality of functionalized particles to a liquid binder (step 316) can result in aggregation (e.g., granule formation), formation of an additional coating, and / or formation of an additional matrix. Various conditions in the presence of the liquid binder can be optimized to impart desired properties to the granules, coating, and / or matrix.

[0173] While this specification contains many details, these should not be construed as limitations on the scope of what can be claimed, but rather as descriptions of features specific to particular embodiments. Certain features described herein in relation to separate embodiments can also be combined. Conversely, various features described in relation to one embodiment can be implemented individually or in any suitable combination in multiple embodiments.

[0174] The regenerated adsorbent can be reused through a desorption process. For example, the regenerated adsorbent can be reused more than 100 times (e.g., more than 1,000 times, more than 10,000 times). In the desorption process, the sample is heated at 70°C for 30 minutes under vacuum (the duration may be changed based on the temperature / vacuum level). This facilitates the release of CO2 recovered during the adsorption process, which can be collected for further isolation, as described below with reference to the direct air recovery system. One aspect of the desorption process is to maintain the heated adsorbent in a vacuum environment filled with water vapor (e.g., relative humidity > 10%). This reduces the decomposition of the regenerated adsorbent.

[0175] Aggregation system Figures 5 and 6 show exemplary systems for producing functionalized granules 100 in aggregation and coating methods such as processes 300 and 310 described herein.

[0176] Figures 5 and 6 show two different examples of drum mixers that can be used to mix a functionalized mixture, expose fine particles to a liquid binder, agglomerate the fine particles into granules, and / or dry the functionalized granules. In some embodiments, a drum mixer can be used to mix a functionalized mixture, expose fine particles to the functionalized mixture to provide functionalized fine particles, agglomerate the functionalized fine particles into granules, and / or dry the functionalized granules.

[0177] In the left-hand image of Figure 5, the paddle mixer 500 includes a cylindrical drum 502 in which mixing takes place. A paddle agitator 504 rotates independently of the drum 502 to mix the functionalized mixture or liquid binder and microparticles. Microparticles are dispensed into the drum 502, and the paddle agitator 504 rotates to agitate the microparticles in the liquid binder / functionalized mixture. The agitator 504 applies shear force to the microparticles to cause aggregation into granules.

[0178] In the left-hand image of Figure 6, the ribbon mixer 600 includes a cylindrical drum 602, inside which mixing is performed by a ribbon agitator 604 that rotates independently of the drum 602. Fine particles are dispensed into the drum 602, and the ribbon agitator 604 rotates to agitate the fine particles in the liquid binder and / or functionalized mixture.

[0179] Examples of paddle mixers 500 and ribbon mixers 600 include heating mechanisms such as jacketed drums 502 and 602, or forced gas ventilation mechanisms that pass heated gas over functionalized silica particles after separating particles from a liquid functionalized mixture. In some examples, the heated gas is air or an inert gas (e.g., nitrogen, N2). 2 ) may be. If the heat transfer medium flows through the jacket of a paddle mixer 500 or ribbon mixer 600, the heat transfer medium may be heated oil, steam, or hot water. If the heat transfer medium flows through a container (e.g., a forced gas ventilation mechanism), an inert gas such as N2 may be used. However, in the case of a forced gas ventilation mechanism, air must be avoided to prevent oxidation.

[0180] Recycling methods Generally, the adsorption capacity of the functionalized sorbents described herein may be reduced to below an effective threshold after multiple adsorption and desorption cycles. While we do not wish to be bound by theory, amines bound to the functionalized silica described herein may decompose during the adsorption and desorption cycles. Decomposition mechanisms may include thermal decomposition (e.g., excessive heating), mechanical decomposition (e.g., physical wear), or chemical decomposition (e.g., exposure to reactive oxygen species).

[0181] If an sorbent degrades to the point where it falls below its effective threshold, it may be called a "degraded" sorbent. The effective threshold is the threshold at which the sorbent can no longer efficiently adsorb carbon dioxide, or at which its adsorption capacity becomes commercially unprofitable. In one example, the threshold is determined by the carbon dioxide absorption capacity of the sample sorbent. An sorbent with an absorption capacity of 0.5 molCO2 / kg or less may be considered degraded (e.g., 0.4 or less or 0.3 or less).

[0182] Examples of recycling methods include regeneration methods. Generally, regeneration methods include the aggregation of fine particles (as further described herein) and the regeneration or reduction of amines in degraded sorbents. Amine aggregation and regeneration can produce newly regenerated functionalized silica that can be reintroduced into the carbon recovery processes and systems described herein.

[0183] An example of a recycling method is passivation. Passivation methods can, in some cases, produce passivated sorbents that can be reused as unfunctionalized silica substrates for industrial fillers or raw materials. Passivation methods may include calcination, acid / base stripping, or chemical reactions of degraded sorbents (e.g., ozone treatment).

[0184] In one example, calcination of a degraded sorbent involves heating the degraded sorbent to a temperature or higher at which thermal decomposition of the functionalization network occurs. The functionalization network can be decomposed by the heating process and subsequently removed from the calcined sorbent. The calcined sorbent can then be disposed of or re-functionalized in a functionalization process.

[0185] The temperature at which the degraded sorbent rises may be below the glass transition temperature of the silica substrate to prevent thermal damage to the silica substrate, such as a decrease in the porosity or pore volume of the silica substrate, or, for example, to prevent crystallization of the silica substrate. At high temperatures, amorphous silica may begin to rearrange and become a crystalline phase. The rate of this rearrangement is temperature-dependent. The higher the temperature and the longer the time, the more silica is rearranged and transformed into a crystalline phase. Slow cooling allows time for the silica to crystallize, for example, to continue the annealing process. Rapid heating and cooling burn off the amine coating and reduce the time available for the silica to crystallize.

[0186] The firing temperature may be between 300°C and 900°C (e.g., 350°C to 800°C or 400°C to 700°C). The degraded silica is rapidly heated to the firing temperature in, for example, 90 minutes or less (e.g., 60 minutes or less or 45 minutes or less), or heated to reach the firing temperature. The degraded silica is rapidly cooled to below the firing temperature in, for example, 90 minutes or less (e.g., 60 minutes or less or 45 minutes or less).

[0187] In some cases, calcination is carried out under conditions of limited oxygen supply, such as in a vacuum or under an inert gas such as nitrogen. Performing calcination under inert conditions may result in higher carbon and / or nitrogen content remaining on the calcined substrate from the functionalization network after calcination. Higher carbon and / or nitrogen content can facilitate the use of the calcined sorbent in downstream reuse methods, such as fillers, thickeners, or resin binders.

[0188] In some cases, calcination is carried out under conditions of oxygen presence. Calcination in the presence of oxygen can reduce the carbon content remaining on the surface and in the pores of the calcined substrate, thereby reducing the effect of calcination on the porosity or pore volume of the calcined substrate. Calcined sorbents with relatively high porosity or pore volume can be refunctionalized to produce new sorbents for carbon recovery.

[0189] Optionally, the calcined particles are cooled at a rate sufficient to prevent crystallization of the calcined particles, for example, at a rate of 50°C / minute or more so that they reach a temperature of less than 100°C within 1 hour.

[0190] Examples of regeneration methods include the reduction of degraded sorbents. Reducing a degraded sorbent facilitates the reuse of the reduced sorbent in the regeneration systems described herein, thereby extending the sorbent's lifespan and increasing its cycle count. Reduction may involve exposing the degraded sorbent to a gaseous or liquid reducing agent. Generally, the reducing agent may include, for example, hydrogen gas or a hydride (e.g., sodium borohydride). Examples of reduction products of active alkylamines are amides, imines, and ureas. Reducing these compounds to amines or amides with alpha alcohols can restore the carbon recovery performance of amine coatings.

[0191] Gas-phase reducing agents can produce less waste than liquid-phase reducing agents, and liquid-phase reducing agents can shorten exposure time compared to gas-phase reducing agents.

[0192] An example of gas-phase reduction may involve exposing the degraded sorbent to hydrogen gas. In an example of liquid-phase reduction, a solvent that does not react with the functionalization network, such as a nonpolar solvent, e.g., hexane, benzene, toluene, or tetrahydrofuran (THF), may be used. The reducing agent is then introduced together with the solvent to reduce the functionalization network. The solvent selected for reduction can prevent the formation of salts in the degraded sorbent. By selecting a non-reactive solvent, such as a nonpolar solvent, it is possible to prevent the coated amine from being washed away from the coated sorbent so that the reduced amine remains on the silica surface after reduction.

[0193] Another example of a reduction method involves electrochemical reduction, which involves applying an external voltage to a degraded sorbent suspended in a support. Electrochemical reduction can be performed as an alternative to, or even further than, exposure to a gaseous or liquid-phase reducing agent.

[0194] Further examples of passivation methods include washing the functionalized mixture from the degraded sorbent. The degraded sorbent can be removed from the porous silica substrate by exposing it to a strong acid or strong base cleaning agent, for example, alone or in succession. An example of a cleaning agent may be an aqueous solution with a pH of about 0 or about 14. The silica substrate can then be removed from the cleaning agent. Optionally, the silica substrate can then be exposed to a second cleaning agent having a different pH, or the second cleaning agent may be water. The cleaning agent may be a polar solvent, such as ethyl acetate or acetone. Subsequently, by re-functionalizing the silica substrate, the material cost of providing functionalized silica can be reduced, and the waste flow from producing silica sorbents can be decreased.

[0195] One example of a passivation method involves exposing the degraded sorbent to a strong acid, such as hydrogen chloride (HCl) at pH=0. The acid converts the alkylamine to alkylammonium, which has increased solubility. Subsequently, the degraded sorbent is removed from the acid. Then, the degraded sorbent is exposed to a strong base, such as sodium hydroxide (NaOH) at pH=14. The base treatment neutralizes the acid and dissolves a thin layer on the silica surface, removing any other residues such as aminosilane. Subsequently, the degraded sorbent is removed from the base. Optionally, the degraded sorbent may be washed with a neutralizing agent, such as water, to remove any remaining residues, such as salts, to provide passivated silica. The passivated silica can then be refunctionalized using the methods described herein.

[0196] In cases where the functionalization network includes a polymer, such as PEI, PEI has good solubility in methanol, ethanol, or water, so the degraded sorbent can be exposed to these solvents to remove the PEI relatively easily. Some aminosilanes can also be washed with methanol, ethanol, or water. Subsequently, the silica surface can be completely cleaned by washing with acids and bases to achieve passivation and regeneration.

[0197] Further examples of passivation methods include exposing the degraded sorbent to an oxidizing agent that chemically oxidizes the amine and silane moieties, such as ozone. The amine reaction with ozone produces various examples of oxidation products, such as amides, nitrites, nitroso, or nitrates. Some products of ozone treatment are water, CO2, and N2. An advantage of ozone treatment is that the reaction can be carried out at room temperature. Treating the sorbent with a smaller amount of ozone can passivate it by converting the amine into oxidation products, which can be less environmentally problematic. Treating the sorbent with excess ozone removes organic matter from the silica substrate.

[0198] Examples of recycling methods include reuse methods. Generally, reuse methods include providing degraded sorbents as fillers, providing degraded sorbents as soil additives, or providing degraded sorbents as silica raw materials.

[0199] Degraded sorbents contain porous silica particles with a highly durable silica oxide composition that can be beneficial in industrial processes. Degraded silica sorbents may be useful as mechanical binders or as cost-effective fillers when mixed with other materials in applications that improve resistance to friction. The surface of the degraded sorbent is coated with a functionalized network. In some examples, the functionalized network may be removed before being offered for reuse. Alternatively, the functionalized mixture may be modified to suit the purpose of the reuse application.

[0200] One example of providing degraded adsorbents as fillers is their use as fillers in rubber, such as synthetic rubber, or other polymers. Degraded adsorbents can be used as fillers in synthetic rubber tires. Synthetic rubber containing some silica oxide as a filler can improve the durability of the synthetic rubber (e.g., improve friction resistance and damage resistance). Tires manufactured using some silicon oxide as a filler may have reduced rolling resistance. Degraded adsorbents may be treated to contain sulfur for use in synthetic rubber tires. Another example of providing degraded adsorbents as fillers is their use as epoxy resin fillers or plywood fillers. Amine-containing chemicals may be compatible with common epoxides and formaldehyde-based resins. The amine group may react with the active part of the polymer. Silica flakes are compatible with resins or epoxides and may increase the mechanical strength of the composite.

[0201] High-purity silica oxide compositions of degraded sorbents provide a source for high-purity silica oxide applications, for example, as a silica source for silica production processes. Briefly, though not limiting, silica can be produced from sand and reacted with sodium hydroxide to form sodium silicate. Sodium silicate can be reacted with a strong acid to form silicic acid. The silicic acid can then be solidified to form silica. Degraded sorbents can be used in the same process to reform silica. As another example, amines on degraded sorbents can be passivated or converted to nitrogen sources, such as fertilizers, plant nitrogen sources, or soil additives, facilitating their safe "return" to the environment. In one example, amines coating a degraded sorbent can be decomposed in soil to convert them into urea, which can provide a nitrogen source for plants, for example. Urea conversion can be carried out by exposure of the sorbent amine to a conversion agent such as CO2 or formaldehyde in a gas-phase or liquid-phase batch process. In one example, the degraded sorbent is exposed to a gas containing substantially pure CO2 at a high temperature of 100°C to 120°C. Optionally, the degraded sorbent is dried to a moisture content of 5% wt / wt or less before exposure to the converter.

[0202] Exemplary Regeneration System Examples of systems for direct air capture (DAC) of CO2, collection and aggregation of fine particles, and recycling of the regenerated adsorbent in this disclosure are described with reference to Figure 7A. Figure 7A shows a schematic diagram of an exemplary embodiment of an integrated silica system 700 for functionalization, carbon dioxide extraction, and fine particle regeneration.

[0203] Functionalized silica particles, such as “novel” sorbents, are produced by a coating apparatus 702, such as the example of the mixing and exposure system shown in Figures 5-6. Briefly, a functionalized mixture 722 containing reagents such as polymer amines and aminosilanes as described herein is mixed with silica particles 720 in the coating apparatus 702 to produce functionalized silica particles 740 for carbon recovery and sequestration. The functionalized silica particles are utilized in a direct air recovery (DAC) system 704, an example of which is further described herein with reference to Figures 7B, 8, and 9.

[0204] The DAC system 704 includes an inlet for receiving a new sorbent 740 from the coating equipment 702. The DAC system 704 uses a functionalized silica particle adsorbent in the carbon dioxide extraction process.

[0205] Referring to Figure 7B, a non-limiting example of a DAC system 704 is provided. The carbon dioxide DAC system 704 includes an adsorbent system 742 and a desorbent system 744. The carbon dioxide DAC system 704 may also accept a heated fluid 750, a power input 752, and an ambient airflow input 754. The carbon dioxide DAC system 704 outputs a carbon dioxide supply flow 756 and a carbon dioxide-reduced airflow output flow 758.

[0206] The adsorbent system 742 generally operates to allow an ambient air inlet 754 (containing gaseous carbon dioxide) to pass over or through one or more adsorbent reactors under conditions in which the adsorbent adsorbs CO2 from the air. The adsorbent may include any of the functionalized particles or functionalized granules described herein. Non-limiting reactors may include one or more movable packed beds, fluidized beds, etc. Where used herein, unless otherwise specified, “adsorbent” and “sorbent” may be used interchangeably. In some non-limiting embodiments, the sorbent includes a collection of functionalized granules.

[0207] In some embodiments, the adsorbent includes a solid adsorbent to which atmospheric carbon dioxide in the airflow input 754 binds. For example, the solid adsorbent may be in pellet or powder form. As the airflow input 754 passes over the solid medium, atmospheric carbon dioxide in the airflow input binds to the adsorbent. The adsorbent saturated with carbon dioxide may be called a “rich adsorbent”. If the medium is saturated with carbon dioxide, the medium may be heated (for example, to 80–120°C) to release the carbon dioxide for collection. For example, the rich adsorbent 748 may exit the adsorbent system 742 and enter the desorbent system 744.

[0208] The desorption system 744 uses thermal energy from the heating fluid 750 to heat the solid or liquid rich adsorbent 748. The heat dissolves the bonds between the carbon dioxide and the rich adsorbent 748. The separated carbon dioxide is supplied as a carbon dioxide supply flow 756 from the carbon dioxide DAC system 740. The adsorbent leaving the desorption system 744 may also be called a “lean adsorbent,” for example, a carbon dioxide-free adsorbent. The lean adsorbent 746 leaves the desorption system 744 and is recycled to the adsorbent system 742. The lean adsorbent 746 in the filter of the adsorbent system 742 recovers more carbon dioxide from the ambient airflow input 754. The airflow output 758 typically contains little to no carbon dioxide.

[0209] The rich adsorbent moves between the adsorbent system 742 and the desorbent system 744, causing mechanical stress on individual particles and resulting in particle abrasion into fine powder. Collection of fine particles may occur during the transport of the rich adsorbent 748 and / or lean adsorbent 746 between the adsorbent system 742 and the desorbent system 744, and / or during the transport of the carbon dioxide supply flow 756 or airflow output 758 from the desorbent system.

[0210] The DAC system 704 includes a filtration system that encloses the adsorbent system 742 and the desorbent system 744 to prevent the fine particles from being lost to the environment as dust, and to collect and isolate the fine particles. In some embodiments, the fine particles are collected and transferred for flocculation and regeneration processes such as processes 300, 310, via an outlet to agglomeration equipment 706. Some examples of fine particle collection include vacuum systems, sieving and filtration systems, and cyclone separators. Generally, silica particles with a maximum size of 0.5 mm or less (e.g., 0.4 mm or less, 0.3 mm or less, or 0.2 mm or less) are separated from the adsorbent during handling and transfer processes within the DAC system 704.

[0211] The fine particles 760 are transferred to an agglomeration apparatus 706, such as the examples shown in Figures 4-6. The agglomeration apparatus 706 includes a liquid handler system (e.g., a sprayer) for exposing the fine particles to a liquid binder 764, such as water, a solvent, or any of the substances described herein. The agglomeration apparatus 706 includes a mixer for applying shear force to the wet fine particles to induce the formation of granules, such as granules 450. A functionalized mixture 762 containing aminosilane and polymer amine (e.g., PEI) is introduced into the agglomeration apparatus. The functionalized mixture may be introduced into the fine particles as a liquid binder while shear force is applied to the fine particles or after the fine particles have agglomerated into granules. The timing of the introduction of the functionalized mixture into the fine particles may affect the CO2 absorption capacity, mechanical strength, and / or brittleness of the functionalized granules.

[0212] The DAC system 704 includes a second inlet in the sorbent-containing system of the DAC system 704 for receiving functionalized granules, such as recycled sorbent 766, for reuse in the adsorbent system 710 and the desorbent system 712. In one embodiment, the recycled sorbent 766 can be introduced into the adsorbent system 742 in any effective manner. For example, the recycled sorbent 766 can be combined with lean adsorbent 746 for delivery to the adsorbent system 742. In another example, the recycled sorbent 766 can be introduced into another inlet communicating with the adsorbent system 742 (for example, an inlet communicating with a fluidized bed containing adsorbent, which may contain new and / or recycled granules 100). In yet another example, the recycled sorbent 766 may be combined with a rich adsorbent 748 for delivery to a desorbent system 744, which may then process the recycled sorbent 766 with the rich adsorbent 748 to deliver it again to the adsorbent system 742 as a lean adsorbent 746.

[0213] Optionally, the DAC system 704 includes one or more blowers, each receiving ambient air and arranged to blow the air (for example, as an ambient air inlet 754) into the adsorbent system 742. The new and / or recycled granules 100 contained in the adsorbent system 742 can then adsorb atmospheric CO2 from the ambient air inlet 754.

[0214] Optionally, the DAC system 704 includes one or more exhaust ports, each configured to remove air from the adsorbent system 742 and / or the desorbent system 744. This air may contain particulate matter, which can be supplied to the flocculation device 706. In some embodiments, the outlet of the DAC system is in fluid communication with at least one of the one or more exhaust ports.

[0215] In one example, the exhaust port is configured to remove air (e.g., including accompanying particulate matter) from an inlet to the adsorbent system 742, an outlet from the adsorbent system 742, an inlet to the desorbent system 744, or an outlet to the desorbent system 744. Additionally or alternatively, a flow containing a rich adsorbent 748 or a lean adsorbent 746 may be fluidically connected to the exhaust port, where particulate matter in such a flow may be separated and transported to the exhaust port. Additionally or alternatively, an outlet(s) of the DAC system 704 (e.g., an outlet for providing a carbon dioxide supply flow 756 or an airflow output 758) may be fluidically connected to the exhaust port.

[0216] In some cases, the functionalized granules are sieved, for example, filtered, before the DAC system 704 accepts them. The granules are sieved to remove and separate granules that are outside the desired range of maximum granule size (e.g., granules smaller than 0.5 mm, larger than 2 mm, or both). The separated granules smaller than the minimum and maximum dimensions may be returned to the agglomeration device 706 for further agglomeration and / or coating.

[0217] Exemplary direct air recovery system Examples of CO2DAC systems using the regenerated adsorbent of this disclosure are described with reference to Figures 8 and 9, which are described in U.S. Patent Application No. 17 / 216,902, the entirety of which disclosure is incorporated herein by reference. Figure 8 is a schematic diagram of an exemplary embodiment of a carbon dioxide extraction system 800. As shown, the carbon dioxide extraction system 800 includes an industrial process 805 that generates waste heat 802. In some embodiments, the industrial process utilizes a power input 803. In this example, the waste heat 802 is supplied to a thermal heat reuse system 810 that also utilizes a power input 806. The thermal heat reuse system 810 supplies a heated fluid 804 to the carbon dioxide DAC system 815. The carbon dioxide DAC system 815 also accepts a power input 808 and an ambient airflow input 811. The carbon dioxide DAC system 815 outputs a carbon dioxide supply flow 812, a carbon dioxide-reduced airflow output flow 814, and demineralized water 816.

[0218] Generally, the carbon dioxide extraction system 800 operates to utilize the heated fluid 804 as thermal energy generated from waste heat 802 by the thermal heat reuse system 810. The carbon dioxide DAC system uses the thermal energy in the heated fluid 804 to separate the carbon dioxide recovered from the ambient airflow input 811 and supplies the separated carbon dioxide as a carbon dioxide supply flow 812. Subsequently, the heated fluid 804 returns to the thermal heat reuse system 810 via the heated fluid return section 813, and the waste heat 802 returns to the industrial process 805 via the waste heat return section 817. In some embodiments, the carbon dioxide supply flow 812 may be supplied to the subsurface as an injector during hydrocarbon production operations. In some embodiments, the injected carbon dioxide may be sequestered in the subsurface (with or without assistance for hydrocarbon production operations).

[0219] Industrial process 805 is any process that generates thermal energy as an output in the form of waste heat, including, for example, energy that would be lost by being released into the surrounding environment unless recovered. As an example, industrial process 805 may generally be a computer data center housing computer systems and related components, such as remote communication and storage systems. In some embodiments, the data center includes tens, hundreds, thousands, or more server devices that generate heat, such as hardware processors, voltage regulators, memory modules, switches, and other devices that operate to provide a certain amount of information technology (IT) power.

[0220] Such devices typically operate using electricity and generate heat during operation. For such devices to function correctly, the generated heat must be recovered by a cooling fluid flow (e.g., air, water, refrigerant, etc.) and discharged from the data center. For example, an air handling system (e.g., fans, cooling coils) may operate to recover the generated heat in the airflow circulating over the heat-generating components. The generated heat in the airflow is then transferred, for example, to a cooling liquid in a cooling coil. The heat transferred to the cooling liquid is then typically discharged to the surrounding environment as waste heat via an evaporative cooling system, chiller / cooling tower system, etc. In this example, this waste heat is in the form of waste heat 802.

[0221] An exemplary thermal heat reuse system 810 utilizes waste heat 802 and a power input 808 to provide a heated fluid 804. The thermal heat reuse system 810 consists of a heat pump bank and a heat exchanger bank to provide the heated fluid 804. By balancing the use of passive and active heating, power can be saved and the required temperature of the heated fluid 804 can be provided to the carbon dioxide DAC system. Generally, the thermal heat reuse system 810 includes one or more vapor compression cycles ("heat pumps") that add thermal energy in the form of heat of compression to waste heat 802 and transfer that total energy to a fluid to produce a heated fluid 804 (e.g., a heated liquid). Generally, each heat pump and heat exchanger in the thermal heat reuse system 810 operates to transfer thermal energy from the heat sink to the heat source, i.e., in the opposite direction of natural heat transfer. One or more heat pumps in the thermal heat reuse system 810 use a power input 806 to accomplish the task of transferring energy from the heat source to the heat sink. Each heat pump in the thermal heat reuse system 810 includes an expansion device (e.g., a valve or fixed orifice) and a compressor (e.g., a centrifugal compressor, screw compressor, reciprocating compressor, scroll compressor, or other compressor), which are the main components of two heat exchangers (one acting as an evaporator and the other as a condenser). Each of these components is fluidically coupled within a closed-loop refrigerant circuit in the heat pump.

[0222] As is generally known, in a vapor compression heat pump cycle, the refrigerant exits a first heat exchanger where heat from the refrigerant is released into a first medium. The refrigerant then enters a compressor where it is compressed, and heat of compression is added to it. Next, the refrigerant enters a second heat exchanger where heat from a second medium is added to it. Finally, the refrigerant enters an expansion device where it undergoes a pressure drop of oneenthalpy. The refrigerant then enters an evaporator, completing the cycle by releasing the heat of compression and heat from the second medium back into the first medium.

[0223] This disclosure describes a vapor compression heat pump cycle as a heat transfer system between a waste heat source and a carbon dioxide DAC system, but other thermodynamic cycles may be used instead of (or in conjunction with) the described vapor compression heat pump cycle. For example, one or more vapor adsorption cycles may be used instead of (or in conjunction with) the described vapor compression heat pump cycle. For example, a vapor adsorption cycle may consist of, for example, a cycle of desorption, condensation, expansion, evaporation, followed by adsorption.

[0224] The carbon dioxide DAC system 815 generally operates to pass an ambient airflow input 811 (containing gaseous carbon dioxide) over or through one or more media (e.g., “filters”). In some embodiments, one or more fans (not shown) utilize a power input 808 to circulate the ambient airflow input 811. In some embodiments, the media or filters include a solid adsorbent to which atmospheric carbon dioxide in the airflow input 811 binds. The adsorbent saturated with carbon dioxide may be called a “rich adsorbent”.

[0225] In the case of solid sorbents, such as those described in this disclosure, when the airflow input 811 passes over the solid medium or filter, atmospheric carbon dioxide in the airflow input 811 binds to the medium or filter. Once the medium or filter is saturated with carbon dioxide, it may be heated (e.g., up to 600-620°C, 60-100°C) to release and collect the carbon dioxide (as described below).

[0226] Using thermal energy from the heated fluid 804, the heat is added to the solid or liquid adsorbent, breaking the bond between carbon dioxide and the adsorbent. The separated carbon dioxide is supplied as a carbon dioxide supply flow 812 from the carbon dioxide DAC system 815. The current "lean adsorbent" (i.e., solid or liquid) that does not contain carbon dioxide is recycled and returned to recover more carbon dioxide from the ambient airflow input 811. The airflow output 814 typically contains little to no carbon dioxide.

[0227] Figure 9 is a schematic diagram of an exemplary embodiment of an integrated powdered carbon dioxide DAC system (integrated system) 900. As shown, the integrated system 900 includes a natural gas plant 920 attached to a CCS exhaust gas carbon dioxide scrubbing tower 925 that generates waste heat 902. In this example, the waste heat 902 is supplied to a thermal heat reuse system 910 that also utilizes a power input 906. The thermal heat reuse system 910 provides a heated fluid 904 to a carbon dioxide direct air recovery (DAC) system 915.

[0228] The natural gas plant 920 generates carbon dioxide-containing exhaust gas 932 and power 928, which are sent to the CCS exhaust gas carbon dioxide scrubbing tower system 925. The scrubbing tower system 925 separates carbon dioxide 912 from the exhaust gas 932. The scrubbing tower system 925 provides waste heat 902 to the carbon dioxide direct air recovery (DAC) system 915. The carbon dioxide DAC system 915 also accepts power input 908 and ambient airflow input 911. The carbon dioxide DAC system 915 outputs a carbon dioxide supply flow 912 and a carbon dioxide-reduced airflow output flow 914.

[0229] Generally, the integrated system 900 recovers waste heat 902, generates a heated fluid 904 containing the thermal energy of the waste heat 902 and the heat of compression from the thermal heat reuse system 910, and utilizes such thermal energy in the heated fluid 904 to separate carbon dioxide recovered from the ambient airflow input 911 and supply the separated carbon dioxide as a carbon dioxide supply flow 912. In some embodiments, the carbon dioxide supply flow 912 may be provided to the subsurface as an injector during the hydrocarbon generation operation. In some embodiments, the injected carbon dioxide may be sequestered in the subsurface (with or without assistance to the hydrocarbon generation operation).

[0230] In this embodiment, the industrial process 905 is powered by the natural gas plant 920 rather than the power grid, since the electricity 926 is considered carbon-negative electricity.

[0231] An exemplary thermal heat reuse system 910 utilizes waste heat 902 from a CCS exhaust gas CO2 scrubbing tower 925 and a power input 906 to provide a heated fluid 904. Generally, a thermal heat reuse system 910 includes one or more vapor compression cycles ("heat pumps") that add thermal energy in the form of compressed heat to the waste heat 902 and transfer that total energy to a fluid to produce a heated fluid 904 (e.g., a heated liquid). Generally, each heat pump in a thermal heat reuse system 910 operates to transfer thermal energy from a heat sink to a heat source, i.e., in the opposite direction of natural heat transfer. One or more heat pumps in a thermal heat reuse system 910 use a power input 906 to accomplish the task of transferring energy from a heat source to a heat sink. Each heat pump in the thermal heat reuse system 910 includes an expansion device (e.g., a valve or fixed orifice) and a compressor (e.g., a centrifugal compressor, screw compressor, reciprocating compressor, scroll compressor, or other compressor), which are the main components of two heat exchangers (one acting as an evaporator and the other as a condenser). Each of these components is fluidically coupled within a closed-loop refrigerant circuit in the heat pump.

[0232] The carbon dioxide DAC system 915 generally operates to pass an ambient airflow input 911 (containing gaseous carbon dioxide) over or through one or more media (e.g., “filters”). In some embodiments, one or more fans (not shown) utilize a power input 908 to circulate the ambient airflow input 911. In some embodiments, the media or filters include a solid adsorbent to which atmospheric carbon dioxide in the airflow input 911 binds. The adsorbent saturated with carbon dioxide may be called a “rich adsorbent”.

[0233] In the case of solid sorbents, such as those described in this disclosure, when the airflow input 911 passes over the solid medium or filter, atmospheric carbon dioxide in the input 911 binds to the medium or filter. Once the medium or filter is saturated with carbon dioxide, it may be heated (e.g., up to 100-120°C, 60-100°C) to release and collect the carbon dioxide (as described below).

[0234] Using thermal energy from the heated fluid 904, heat is added to the solid adsorbent, breaking the bond between carbon dioxide and the adsorbent. The separated carbon dioxide is provided as a carbon dioxide output flow 912 from the carbon dioxide DAC system 915. The current "lean adsorbent" (i.e., solid or liquid) that does not contain carbon dioxide is recycled and returned to recover more carbon dioxide from the ambient airflow input 911. The airflow output 914 typically contains little to no carbon dioxide. The carbon dioxide DAC system 915 outputs carbon dioxide 912 and desalinated water 916.

[0235] As further shown in the exemplary embodiment of Figure 9, the integrated system 900 includes a power plant 920 (e.g., a natural gas power plant) and a cleaning system 925 (e.g., a CCS exhaust gas CO2 cleaning system). As shown in this example, the power plant 920 may provide waste heat 902 (e.g., generated by the power generation by the power plant 920) to the DAC system 915. In this example, the power plant 920 also generates power 922 and 928. In some embodiments, as shown, power 922 passes through one or more switches 930 (shown as one herein, but more switches are possible) to provide power 924 to the DAC system 915 and backup power 926 to the industrial process 905.

[0236] As shown in this example, the power output of the power plant 920 may be sized to provide the sum of power 924 to the DAC system 915 and power 928 to the cleaning system 925 during normal operation, and to provide backup power 926 to the industrial process 905 as needed (i.e., if the industrial process 905 loses or cannot use grid power 917). Thus, in some embodiments, when the industrial process 905 requires backup power 926, power 928 and power 924 are still provided to their respective users. Alternatively, in some embodiments, the power output of the power plant 920 may be sized to provide the sum of power 924 to the DAC system 915 and power 928 to the cleaning system 925 during normal operation, and to provide backup power 926 to the industrial process 905 as needed (i.e., if the industrial process 905 loses or cannot use grid power 917), and to provide one or both of the power inputs 906 or 908.

[0237] Alternatively, in some embodiments, the power output of the power plant 920 may be sized only to provide backup power 926 to the industrial process 905 as needed (i.e., if the industrial process 905 loses or cannot use grid power 917). Thus, during periods of operation when the industrial process 905 does not require backup power 926, power 928 and / or power 924 (and other power inputs) may be provided by the power plant 920. During periods of operation when the industrial process 905 requires backup power 926, power 928 and / or power 924 (and other power inputs) may not be provided by the power plant 920. For example, power 922 may be routed through switch 930 as backup power 926 during such periods of operation.

[0238] In some embodiments, the power 926 supplied from the power plant 920 to the industrial process 905 may not be "backup" power, but instead may be a primary power source for the industrial process 905. For example, in some embodiments, the power plant 920 may not only supply primary power 926 to the industrial process 905, but may also be sized to provide one or more other components shown in the integrated system 900.

[0239] Furthermore, as shown in Figure 9, in some embodiments, the waste heat 902 generated from the scrubbing tower system 925 may be used by the thermal heat reuse plant 910 to provide a heated fluid to the DAC system 915. In some embodiments, the heated fluid 904 is then returned to the thermal heat reuse system 910 via the heated fluid return section 913, and the waste heat 902 is returned to the industrial process 905 via the waste heat return section 917.

[0240] As shown in this exemplary embodiment, the cleaning system 925 also receives exhaust fluid 932 (e.g., exhaust gas containing 100% CO2) from the power plant 920. For example, in some embodiments, the power plant 920 may be a natural gas power plant that burns natural gas to drive power generation equipment that operates to produce electricity as shown in Figure 9. In another embodiment, the power plant 920 may use carbon-based fuels other than natural gas. In yet another embodiment, the power plant 920 may generate electricity using non-carbon fuels (e.g., geothermal, solar energy). In the case of a natural gas power plant 920, although not specifically shown here, such equipment may include, for example, a compressor rotatably coupled to a gas turbine, which drives the compressor. The gas turbine receives a combustion product fluid from a combustion chamber that receives compressed natural gas from the compressor. This combustion product fluid drives the gas turbine, which is then coupled to a generator, which drives the generator to produce electricity.

[0241] The output from such a gas turbine (at a lower pressure than the combustion product fluid) is the exhaust fluid 932 (e.g., exhaust gas). The pressure difference between the combustion product fluid and the exhaust fluid 932 drives the gas turbine and generates electricity from the generator. As shown in this example, the exhaust fluid 932 is separated into multiple output flows by a scrubbing system 925. For example, exhaust gas 932 containing 100% CO2 is separated into a carbon dioxide output and an exhaust gas flow 936 containing 5% CO2. The exhaust gas flow 936 containing 5% CO2 is sent to a DAC system 915 to remove the remaining carbon dioxide from the output airflow of the natural gas plant 920. This makes the resulting electricity generated from the natural gas plant carbon-negative electricity. For example, the outputs of the carbon dioxide supply flow 912 and the carbon dioxide-reduced airflow output flow 914 may also be output from the scrubbing system 925, similar to the DAC system 915.

[0242] In some embodiments, the carbon dioxide supply stream 912 may be sold (for example, for CO2-EOR, sequestration, and / or other processes). For example, the carbon dioxide supply stream 912 may generate profits through emission allowances and federal tax credits. In some embodiments, such profits may offset the capital costs and / or operating costs of the DAC system 915, the power plant 920, both, or other components of the system 900.

[0243] The integrated system 900 may also advantageously utilize the power plant 920, which may normally be idle, to generate marketable products in the carbon dioxide fluid flow 912, which also provides environmental benefits. Furthermore, even if a power outage occurs in the industrial process 905, the power plant 920 is already operational, thus reducing the delay time from the power outage to the supply of power to the process 905. In addition, by using thermal energy 902 from waste heat 902 from the scrubbing towers 925 and 934, the operating cost of the DAC system 915 can be significantly reduced, so that the recovered carbon dioxide can not only cover the construction costs of the DAC system 915 but also subsidize the cost of backup power for the industrial process. Furthermore, the integrated system 900 can also generate water from the ambient humidity when the DAC system 915 extracts carbon dioxide from the air. This water can be sold or used, for example, in the industrial process 905. [Examples]

[0244] Example 1 Functionalized silica produced using the process 300 described herein may be characterized by CO2 absorption measurements. Figure 10A schematically shows an exploded view (left) and an assembled view (right) of the sorbent sample holder 1000. Functionalized silica particles or granules may be placed in a sample space 1006 (e.g., glass wool) positioned between two layers of filter 1004 within the sample holder 1000. The sealing end 1002 of the sample holder 1000 may include an inlet 1008 and an outlet 1010 that allow gas flow. The sealing end 1002 may include a reversible screw connection for assembling the sample holder 1000. The sample holder 1000 may be sealed against gas inflow by other means when assembled (right side).

[0245] Figure 10B shows a schematic diagram of the experimental apparatus 1020. Referring here to Figures 10A and 10B, a gas source, for example, an air compressor 1022, may supply compressed ambient air to the inlet 1008 of the test sample holder 1000, and the compressed ambient air may then pass through a filter 1004, exposing the functionalized silica to the ambient air. The air may be discharged from an outlet 1010. The concentration of CO2 in the compressed ambient air may be measured by gas analyzers, for example, CO2 gas analyzers 1024 and 1026, before it enters the inlet 1008 and / or after it exits the outlet 1010.

[0246] Samples of functionalized silica may be treated in an activation process before data acquisition. For example, the adsorbent may be activated by heating the sample to 70°C for 30 minutes under vacuum (e.g., 0.3 psi) in a vacuum dryer (e.g., vacuum heater 1028) as an activation process. Alternatively, as shown in Figure 10B, a heating element and vacuum system 1030 may be separate elements of the apparatus 1020 and function in coordination to heat the sample holder 1000 and apply vacuum. In some embodiments, a cooling element 1032 may be included in the apparatus 1020 to further control the temperature of the environment within the sample holder 1000. The activation process can facilitate the removal of residual solvent media in the pores of the functionalized silica, e.g., by evaporation, and facilitate the desorption of CO2 molecules bound during the synthesis processes 300, 310 for release into the atmosphere.

[0247] For the adsorption procedure, a sample of functionalized silica in the range of 0.5 g to 10 g can be placed between two layers of glass fiber filter 1004 in a test sample holder 1000. The activated functionalized silica can be exposed by continuously supplying compressed ambient air (e.g., input air) from a gas source 1022 through the test sample holder 1000 at a flow rate of 1 to 10 standard liters per minute (slpm). The activated functionalized silica can be exposed for a period of 30 to 60 minutes. The humidity of the input air can be controlled to 15% to 50% RH at 21°C. The same sample holder can then be evacuated by a vacuum system 1030 and heated by a vacuum heater 1028 to extract carbon dioxide from the sample. The amount of extracted carbon dioxide can be analyzed by a gas analyzer 1026.

[0248] Humidity can be controlled by mixing "dry air" and "humid air" using a flow meter (not shown). For example, to produce input air with 50% RH at a flow rate of 5 slpm, 2.5 slpm of dry air (e.g., <10% RH) and humid air (e.g., >95% RH, 100% RH) can be mixed at 2.5 slpm each. Flow control of the dry and humid air can be achieved using a closed-loop controller.

[0249] Compressed ambient air containing CO2 concentration can be monitored throughout the experiment by gas analyzers 1024 and 1026 at the input and output of the test sample holder 1000 in units of moles of CO2 per kg of adsorbent.

[0250] Example 2 - Agglomeration Test Tables 1 and 2 below show two tests for forming recycled silica particles by agglomerating fine particles onto a silica base. CO2 absorption (mol / kg), abrasion loss (wt%), crushing strength (MPa), and / or bulk density (g / L) were determined.

[0251] A base raw silica product was used as the base for the aggregated particles. The CO2 absorption of the base raw silica was determined using the method described herein, and a normalized absorption was determined for comparison with the aggregated samples.

[0252] Aggregated samples were formed using base silica as described herein. The agglomerated samples in Table 1 were agglomerated using dry roller compression under pressures according to the specific columns, for example, under either 20 kilopounds / square inch (kSi) or 30 kSi. In the "Conditions" column, the term "ground" means that the size of the base material was less than 100 microns. The term "unground" means that the size of the base material was up to 500 microns.

[0253] Abrasion tests were conducted on the aggregated samples. Briefly, 100g of each sample was placed in a sieve shaker using a 20-mesh sieve. The samples were stirred in the shaker using a container for 5 minutes. 50g of the product with a mesh size of 20 or larger was placed in a 20-mesh sieve. 50 ceramic beads of 9.5mm size were added to the 20-mesh sieve. The samples were stirred for 5 minutes without the container. The weight percentage of fine powder observed in the base pan after stirring with the ceramic beads was determined by comparing it to the original sample.

[0254] After aggregation, the samples were coated with a functionalized mixture and tested for CO2 absorption, all of which were as described herein. Briefly, the functionalization / coating process involved immersion coating of 100 g of silica substrate with a PEI / DAMO / aqueous solution, in which 7.7 wt% PEI and 36 wt% DAMO were added to 160 wt% water. After immersion coating, the samples were dried under vacuum at 70°C for 24 hours. Next, the absorption performance of the samples was measured by the method described in Example 1.

[0255] [Table 1]

[0256] Agglomerated samples, shown in Table 2 (below), were prepared using a liquid-binding mixture of PVA and water at various weight percentages (PVA to water weight percentages) as a binder. The samples in Table 2 were agglomerated using a mixer with the liquid-binding mixture. The CO2 absorption capacity and abrasion were determined as shown for the samples in Table 1.

[0257] The aggregated particles in Table 2 were characterized for their compressive strength. The bulk compressive strength test utilized a test fixture consisting of a lower crushing platform and an upper crushing head. The lower crushing platform included a flat surface on which the sample was placed. The upper crushing head included a crushing head with a flat underside substantially parallel to the surface plane, thereby ensuring that the force was evenly distributed between the crushing head and the surface while the force was applied. The crushing head had an outer diameter (OD) of 72.6 mm and a surface diameter of 124.5 mm. The crushing platform had a diameter of 125.4 mm. In another example, the crushing platform had a diameter of 146 mm.

[0258] During the test, a layer of particles, such as a sample layer, was tightly packed onto the crushing platform and roughly aligned with the center of the crushing head. The diameter of the particle layer was approximately 90 mm to 2 mm in thickness. The dry weight of the sample ranged from 3 to 6 g depending on the particle coating component. The force applied to the crushing head was recorded as the displacement changed. The packed particle layer was crushed until its compressive strain reached 50% (for example, until the value obtained by dividing the displacement by the initial sample layer thickness was 50%), and the stress (MPa) at that time (for example, the value obtained by dividing the force by the contact area) was reported as the 50% strain crushing strength. Samples of both uncoated and coated particles were tested. For both types of particles, at least three samples were tested to obtain the average bulk compressive strength performance.

[0259] The bulk density was measured according to ASTM D1895 Method A. Briefly, the fine granules were poured through a V-shaped funnel. The material to be tested was poured into a cylinder cup of known volume (100 mL). The test results were averaged using four or more measurements.

[0260] [Table 2]

[0261] Several embodiments have been described. Needless to say, it is understood that various modifications can be made without departing from the spirit and scope of the invention. Therefore, other embodiments are within the scope of the following claims.

Claims

1. A plurality of fine particles, each comprising at least one first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion, Functionalized granules comprising a coating disposed on at least a portion of the surface of at least one of the plurality of microparticles, which optionally comprises a second silane moiety and a second amine moiety and is optionally configured to bond to the plurality of microparticles.

2. The functionalized granules according to claim 1, wherein the plurality of fine particles have an average dimension or average size (e.g., diameter) of about 25 microns to about 500 microns.

3. The functionalized granule according to claim 1 or 2, wherein at least one of the plurality of fine particles includes a plurality of pores.

4. The functionalized granules according to claim 3, wherein the plurality of pores have an average or average dimension (e.g., diameter) of about 60 angstroms to about 600 angstroms.

5. The functionalized granule according to any one of claims 1 to 4, wherein the coating comprises the second silane portion, and the second amine portion is bonded to the second silane portion.

6. The coating further comprises a polymer, as described in any one of claims 1 to 5.

7. The functionalized granules according to claim 6, wherein the polymer comprises a polymer amine.

8. The coating is a functionalized granule according to any one of claims 1 to 7, which is disposed on the surface of the plurality of fine particles.

9. The functionalized granule according to any one of claims 1 to 8, further comprising a matrix disposed between at least some of the plurality of fine particles, wherein the matrix comprises the second silane portion and the second amine portion.

10. A functionalized granule according to any one of claims 1 to 9, wherein the average dimension or average dimension (e.g., diameter) is about 500 microns to about 2 millimeters.

11. A functionalized granule according to any one of claims 1 to 10, comprising a plurality of pores.

12. Bulk density is approximately 10 lb / ft ３ ~About 4lb / ft ３ (For example, about 15 lb / ft) ３ , about 30lb / ft ３ A functionalized granule according to any one of claims 1 to 11, characterized in that the average pore size is about 60 angstroms to about 600 angstroms, the crushing strength (e.g., stress at 50% compressive strain) is in the range of about 1 MPa to about 4 MPa, the abrasion loss rate according to the ASTM D4058 test (e.g., loss measured over a duration of about 30 minutes at a rolling speed of about 60 rpm) is 0 wt% to about 4 wt% (e.g., about 1.5 wt% or about 3 wt%), and / or the pore volume is about 0.1 mL / g to about 2.0 mL / g (e.g., about 0.5 mL / g or about 1.5 mL / g).

13. Collecting a plurality of fine particles, each containing at least one first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion, The process includes generating a plurality of functionalized granules using the plurality of fine particles, each having an average dimension or average dimension (e.g., diameter) that is larger than the average dimension or average dimension (e.g., diameter) of the plurality of fine particles. A method wherein, optionally, at least one of the plurality of functionalized granules comprises a second porous silica, a second silane moiety bonded to the surface of the second porous silica, and a second amine moiety bonded to the second silane moiety.

14. The above generation is, To provide multiple granules by aggregating the aforementioned multiple fine particles, The method according to claim 13, comprising generating the plurality of functionalized granules by forming a coating on at least a portion of the surface of at least one of the plurality of granules and / or forming a matrix between at least a portion of the plurality of fine particles or between at least a portion of the plurality of granules, wherein the coating and / or the matrix comprises the second silane portion bonded to the surface of at least one granule and the second amine portion bonded to the second silane portion.

15. The above generation is, To provide the plurality of functionalized microparticles by forming a coating on at least a portion of the surface of at least one of the plurality of microparticles, the coating comprising the second silane portion bonded to the surface of at least one microparticle and the second amine portion bonded to the second silane portion, and / or by forming a matrix between at least a portion of the plurality of microparticles. The method according to claim 13, comprising generating the plurality of functionalized granules by agglomerating the plurality of functionalized fine particles.

16. The above generation is, The method according to any one of claims 13 to 15, comprising exposing the plurality of fine particles, the plurality of granules (if present), or the plurality of functionalized fine particles (if present) to a liquid binder.

17. The method according to claim 16, wherein the exposure includes specifying or adjusting the tip speed, water content, rate of addition of liquid binder, mixing time and / or temperature to sufficiently aggregate the plurality of microparticles, the plurality of granules (if present), or the plurality of functionalized microparticles (if present).

18. The above generation is, The method according to any one of claims 13 to 17, comprising spraying a liquid binder onto the plurality of fine particles, the plurality of granules (if present), or the plurality of functionalized fine particles (if present).

19. The method according to any one of claims 16 to 18, wherein the liquid binder comprises water, a solvent, silane, aminosilane, the second silane portion, the second amine portion, the second amine portion bonded to the second silane portion, and / or a polymer amine.

20. The above generation is, The method according to any one of claims 13 to 19, comprising applying shear to the plurality of fine particles, the plurality of granules (if present), or the plurality of functionalized fine particles (if present).

21. The method according to claim 20, wherein the shearing is provided by a pin mixer, a paddle mixer and / or a ribbon blender.

22. The method according to any one of claims 13 to 21, wherein the collection includes obtaining the plurality of fine particles from an inlet to a reactor containing a powder adsorbent, or from an outlet to a reactor containing a powder adsorbent (e.g., an adsorption reactor, a desorption reactor, or another reactor).

23. The method according to claim 22, wherein the powder adsorbent comprises the first porous silica, the first silane portion bonded to the surface of the first porous silica, and / or the first amine portion bonded to the first silane portion.

24. The method according to any one of claims 13 to 23, wherein at least one of the plurality of functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica.

25. The method according to any one of claims 13 to 24, wherein at least one of the plurality of functionalized granules includes a functionalized granule according to any one of claims 1 to 12.

26. The plurality of functionalized granules are dried (for example, in a vacuum oven at 80°C until the hydration threshold of water for the coated silica substrate reaches less than 5% wt / wt). The method according to any one of claims 13 to 25, further comprising:

27. A first inlet configured to receive a first powder adsorbent, A second inlet is configured to receive recycled powder adsorbent material obtained by recycling at least a portion of the first powder adsorbent material, Using the first powder adsorbent and the recycled powder adsorbent, CO2 is removed from the surrounding air. ２ An adsorbent system configured to adsorb, CO2 is obtained from the first powder adsorbent and the recycled powder adsorbent. ２ A detachable body system configured to allow attachment and detachment, A direct air recovery (DAC) system comprising: an outlet configured to deliver a plurality of particulate matter from the amount of air that has entered, passed through, or exited the adsorbent system.

28. The system according to claim 27, wherein the first powder adsorbent comprises a plurality of first functionalized granules, at least one of the plurality of first functionalized granules comprising a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion.

29. The system according to claim 27 or 28, wherein at least one of the plurality of fine particles comprises the first porous silica from at least one of the plurality of first functionalized granules, the first silane portion bonded to the surface of the first porous silica, and / or the first amine portion bonded to the first silane portion.

30. The system according to any one of claims 27 to 29, wherein the recycled powder adsorbent comprises a plurality of second functionalized granules, at least one of the plurality of second functionalized granules comprising a second porous silica, a second silane portion bonded to the surface of the second porous silica, and a second amine portion bonded to the second silane portion.

31. The system according to claim 30, wherein at least one of the plurality of second functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica, or at least one of the plurality of first functionalized granules of the first porous silica.

32. The system according to any one of claims 27 to 32, wherein at least one of the plurality of second functionalized granules comprises a functionalized granule according to any one of claims 1 to 12.

33. One or more blowers, each receiving ambient air and arranged to blow air into the adsorbent system, The system according to any one of claims 27 to 32, further comprising one or more exhaust ports, each configured to remove air from the adsorbent system and / or the desorbent system.

34. The system according to claim 33, wherein the outlet is in fluid communication with at least one of the one or more exhaust ports.

35. A first inlet is configured to receive a plurality of fine particles, at least one of which comprises a first porous silica, a first silane portion bonded to the surface of the first porous silica, and a first amine portion bonded to the first silane portion. A second inlet configured to accept a liquid binder, A reactor configured to produce a plurality of functionalized granules having an average dimension or average dimension (e.g., diameter) larger than the average dimension or average dimension (e.g., diameter) of the plurality of fine particles, A flocculation system comprising an outlet configured to deliver the plurality of functionalized granules outside the reactor.

36. The system according to claim 35, wherein at least one of the plurality of functionalized granules comprises a second porous silica, a second silane portion bonded to the surface of the second porous silica, and a second amine portion bonded to the second silane portion.

37. The system according to claim 36, wherein at least one of the plurality of functionalized granules of the second porous silica comprises at least one of the plurality of fine particles of the first porous silica.

38. The system according to any one of claims 35 to 37, wherein at least one of the plurality of functionalized granules includes a functionalized granule according to any one of claims 1 to 12.

39. The system according to any one of claims 35 to 38, wherein the reactor includes a liquid handler (e.g., a sprayer) configured to expose the plurality of fine particles to a liquid binder.

40. The system according to claim 39, wherein the liquid binder comprises water, a solvent, silane, aminosilane, the second silane portion, the second amine portion, the second amine portion bonded to the second silane portion, and / or a polymer amine.

41. The system according to any one of claims 35 to 40, wherein the reactor includes a mixer configured to apply shear to the plurality of fine particles.

42. The system according to claim 41, wherein the mixer includes a pin mixer, a paddle mixer and / or a ribbon blender.

43. A method for producing calcined particles, Collecting a plurality of degraded functionalized particles, each containing porous silica, a silane portion bonded to the surface of the porous silica, and an amine portion bonded to the silane portion, The method comprising heating the plurality of degraded functionalized particles to a temperature sufficient to thermally decompose the silane portion and the amine portion, thereby producing a plurality of calcined particles.

44. The aforementioned multiple degraded functionalized particles are 0.5 mol CO2 ２ CO2 less than / kg ２ The method according to claim 43, having absorption capacity.

45. The method according to claim 43 or 44, wherein the temperature is sufficient to prevent the crystallization of the plurality of degraded functionalized particles.

46. The method according to any one of claims 43 to 45, comprising maintaining the temperature for a duration sufficient to thermally decompose the silane portion and the amine portion.

47. The method according to claim 46, comprising cooling the calcined particles at a rate sufficient to prevent crystallization of the calcined particles after the duration of time.

48. The method according to claim 47, wherein the heating, the cooling, or both are performed independently for a duration not exceeding one hour.

49. The method according to any one of claims 43 to 46, further comprising providing at least a portion of the calcined particles as the plurality of fine particles in the method according to claim 1 or 13.

50. Collecting a plurality of degraded functionalized particles, each containing porous silica, a silane portion bonded to the surface of the porous silica, and an amine portion bonded to the silane portion, A method comprising exposing a plurality of degraded functionalized particles to a sedative so that the plurality of degraded functionalized particles are no longer reactive.

51. The method according to claim 50, wherein the exposure includes exposing the plurality of degraded functionalized particles to a reducing agent that chemically reduces the amine portion.

52. The method according to claim 50, wherein the exposure comprises exposing the plurality of degraded functionalized particles to an oxidizing agent that chemically oxidizes the amine portion and the silane portion.

53. The method according to claim 50, wherein the exposure includes exposing the plurality of degraded functionalized particles to a converter so as to convert the amine portion into a nitrogen source.

54. The method according to claim 53, wherein the nitrogen source is a urea-containing nitrogen source.

55. The method according to claim 53, wherein the conversion agent is carbon dioxide or formaldehyde.

56. The method according to claim 53, comprising drying the plurality of degraded functionalized particles to a moisture content of 5% wt / wt or less before the aforementioned exposure.

57. The method according to claim 50, wherein the exposure comprises exposing the plurality of degraded functionalized particles to one or more polar solvents sufficient to remove the amine portion and the silane portion from the porous silica.

58. The method according to claim 50, wherein the exposure comprises exposing the plurality of degraded functionalized particles to a first aqueous solution with a pH of approximately 2 or less and a second aqueous solution with a pH of 12 or more, the pH being sufficient to remove the amine portion and the silane portion from the porous silica.

59. The method according to any one of claims 50 to 56, further comprising providing at least a portion of the porous silica as the plurality of fine particles in the method according to claim 1 or 13.

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