Structured sorbent articles and methods of making

Abstract

A structured sorbent article and methods of making are disclosed herein. The structured sorbent article is at least 65 wt% of a sorbent material and an organic binder. The sorbent material is an organic material, an organic-inorganic hybrid material, or a combination thereof. A total of organic components in the structured sorbent article is at least 80 wt% of the structured sorbent article.

Description

Attorney Docket No.: SP25-043PCT STRUCTURED SORBENT ARTICLES AND METHODS OF MAKINGCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S.Provisional Application No. 63 / 788,387 filed April 14, 2025, the content of which is incorporated herein by reference in its entirety.FIELD

[0002] The present disclosure relates generally to structured sorbent articles and methods of making the same and more particularly to structured sorbent articles having a honeycomb form factor, and even more particularly to structured sorbent articles useful in the capture of carbon dioxide or other target gaseous compounds.BACKGROUND

[0003] Efforts to address the effects of climate change include carbon dioxide capture technology, which includes flowing a carbon dioxide containing gas, such as ambient air or carbon dioxide containing exhaust, over or through a sorbent material capable of adsorbing at least a portion of the carbon dioxide. Sorbents are known that can be utilized for capturing or separating a variety of other compounds from gaseous streams. The sorbent material can be regenerated (the captured compound desorbed) by subjecting the sorbent material to a corresponding condition, such as heating for many sorbent materials. For example, heat can be supplied by an external heater, by a flow of heated steam, by Joule heating due to electrification of an article that supports or holds the sorbent material, or by other source of heat. The performance of a sorbent material can be enhanced by structuring the sorbent material into a desired form factor, such as a honeycomb form factor, such as by coating a base substrate with the sorbent material or including the sorbent material in a mixture that is extruded in the desired form.SUMMARY

[0004] According to embodiments, a structured sorbent article comprises at least 65 wt% of a sorbent material, wherein the sorbent material is an organic material, an organic-inorganic hybrid material, or a combination thereof; and an organic binder, wherein a total ofAttorney Docket No.: SP25-043PCT organic components in the structured sorbent article is at least 80 wt% of the structured sorbent article.

[0005] In embodiments, the total content of organic components is at least 90 wt% of the structured sorbent article.

[0006] In embodiments, the total content of organic components is at least 96 wt% of the structured sorbent article.

[0007] In embodiments, the total content of organic components is at least 99 wt% of the structured sorbent article.

[0008] In embodiments, the structured sorbent article further comprises porous inorganic filler particles.

[0009] In embodiments, the structured sorbent article comprises at least 3 wt% of the porous inorganic filler particles.

[0010] In embodiments, the structured sorbent article comprises from 3 wt% to 20 wt% of the porous inorganic filler particles.

[0011] In embodiments, the porous inorganic filler particles are sepiolite.

[0012] In embodiments, the structured sorbent article comprises at least 70 wt% of the sorbent material.

[0013] In embodiments, the structured sorbent article comprises at least 75 wt% of the sorbent material.

[0014] In embodiments, the structured sorbent article comprises at least 80 wt% of the sorbent material.

[0015] In embodiments, the structured sorbent article comprises at least 90 wt% of the sorbent material.

[0016] In embodiments, the structured sorbent article comprises from 65 wt% to 90 wt% of the sorbent material.

[0017] In embodiments, the sorbent material comprises an amine ion exchange resin, a polyamine, an amine-containing material, an amine-functionalized material, a zeolite, a metal-organic framework (MOF), a covalent organic framework (COF), a carbonate, activated carbon, or a combination thereof.

[0018] In embodiments, the sorbent material comprises a solid sorbent material and the structured sorbent article comprises at least 64 wt% of the solid sorbent material.Attorney Docket No.: SP25-043PCT

[0019] In embodiments, the sorbent material comprises both the solid sorbent material and a liquid sorbent material.

[0020] In embodiments, the liquid sorbent material is polyethyleneimine (PEI).

[0021] In embodiments, the structured sorbent article has a honeycomb form factor comprising a plurality of intersecting walls defining a plurality of channels extending axially through the structured sorbent article.

[0022] In embodiments, the sorbent material is homogeneously incorporated within and integrally distributed throughout the intersecting walls to form the intersecting walls.

[0023] In embodiments, the structured sorbent article further comprises a base substrate, wherein the sorbent material is a coating at least partially on surfaces of base substrate within the plurality of channels.

[0024] According to embodiments, a structured sorbent article comprises: at least 3 wt% sepiolite; at least 50 wt% of a sorbent material; and an organic binder.

[0025] In embodiments, the sorbent article comprises from 3 wt% to 20 wt% sepiolite.

[0026] In embodiments, the sorbent article comprises at least 7 wt% sepiolite.

[0027] In embodiments, the structured sorbent article comprises from 3 wt% to 20 wt% sepiolite.

[0028] In embodiments, a ratio of the sepiolite to the sorbent material is at least 1 :25, by weight.

[0029] In embodiments, a ratio of the sepiolite to the sorbent material is in the range of 1:25 to 1:4.5, by weight.

[0030] In embodiments, the sorbent material comprises an amine ion exchange resin, a polyamine, an amine-containing material, an amine-functionalized material, a zeolite, a metal-organic framework (MOF), a covalent organic framework (COF), a carbonate, activated carbon, or a combination thereof.

[0031] In embodiments, the structured sorbent article has a honeycomb form factor comprising a plurality of intersecting walls defining a plurality of channels extending axially through the structured sorbent article.

[0032] In embodiments, the structured sorbent article further comprises a base substrate and the sorbent material is formed as a coating on surfaces of the base substrate within the plurality of channels.Attorney Docket No.: SP25-043PCT

[0033] In embodiments, the sorbent material is homogeneously incorporated within and integrally distributed throughout the intersecting walls to form the intersecting walls.

[0034] Additional features and advantages of the embodiments disclosed herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the disclosed embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.

[0035] It is to be understood that both the foregoing general description and the following detailed description present embodiments intended to provide an overview or framework for understanding the nature and character of the claimed embodiments. The accompanying drawings are included to provide further understanding and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments of the disclosure, and together with the description serve to explain the principles and operations thereof.BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1 shows an article having a honeycomb form factor of intersecting walls and channels, which can represent either a structured sorbent article or a base substrate until which a sorbent material can be coated, according to embodiments herein.

[0037] FIG. 2 shows a system for shaping a structured sorbent article or base substrate via extrusion, according to embodiments herein.

[0038] FIG. 3 shows a flow chart describing two methods of making a structured sorbent article and a method of capturing a selected or target gaseous component of a gas stream, according to embodiments herein.DETAILED DESCRIPTION

[0039] Reference will now be made in detail to the present preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. Whenever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. However, this disclosure may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.Attorney Docket No.: SP25-043PCT

[0040] Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, for example by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0041] Directional terms as used herein - for example up, down, right, left, front, back, top, bottom - are made only with reference to the figures as drawn and are not intended to imply absolute orientation.

[0042] Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order, nor that with any apparatus specific orientations be required. Accordingly, where a method claim does not actually recite an order to be followed by its steps, or that any apparatus claim does not actually recite an order or orientation to individual components, or it is not otherwise specifically stated in the claims or description that the steps are to be limited to a specific order, or that a specific order or orientation to components of an apparatus is not recited, it is in no way intended that an order or orientation be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps, operational flow, order of components, or orientation of components; plain meaning derived from grammatical organization or punctuation, and; the number or type of embodiments described in the specification.

[0043] As used herein, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” component includes aspects having two or more such components, unless the context clearly indicates otherwise.

[0044] As used herein, the term “gas capture” refers to the capture (separation) of one or more target gases from a flow of multiple gaseous components, such as the separation of carbon dioxide from an exhaust stream or ambient air, via adsorption and / or absorption from a sorbent material selective to the target gas(es). As used herein, gas capture includes not only carbon dioxide capture but also capture (separation) of other gases such as acidic gases and / or aldehyde effluents.Attorney Docket No.: SP25-043PCT

[0045] As used herein, the terms “incorporated with” or “incorporating” or “incorporates” refer to a relationship between a first referenced composition and a second referenced composition, structure, or material wherein the first referenced composition deposited on (e.g., coated on) or present within the second referenced composition, structure, or material. For example, the recitation “adsorbing composition incorporated with the substrate” includes situations where the adsorbing composition is not only deposited on (e.g., coated on) a substrate but also situations where the adsorbing composition is present within the substrate material (e.g., within the pores of the material, etc.), further including situations where the substrate is directly formed (e.g., via extrusion) from a mixture that comprises the sorbent.

[0046] Consistent with the above, as used herein the term “sorbent material” refers to a material that is selective with respect to one or more targeted or selected compounds, such as carbon dioxide, such that the sorbent material is arranged to trap or capture molecules of the selected compounds via adsorption or absorption to separate the target gas from a gaseous flow containing the target gas. Similarly, a “structured sorbent article” refers to an article that comprises or incorporates a sorbent material that has been shaped or formed into a desired form factor, such as via extrusion of a mixture comprising the sorbent material into the desired form factor, or coated onto a substrate already having the desired form factor from a mixture comprising the sorbent material. When the sorbent material is directly used as an ingredient for forming the walls of the structured sorbent article (e.g., is part of a batch mixture), the sorbent material is homogeneously incorporated within and integrally distributed throughout the intersecting walls. For the purposes of this disclosure, the terms “coat”, “coating”, “coated”, and the like also refers to not only providing the coating on top of a substrate, but also at least partially impregnating the mixture into the pores of a porous substrate, as applicable. To facilitate discussion, in situations in which a substrate is first formed (e.g. extruded) without the sorbent material, and then is subsequently coated by the sorbent material, the substrate may be referred to as an existing substrate or a base substrate.

[0047] As used herein, the term “median particle size” refers to the particle size of a referenced material wherein half of the particles of that material have a larger particle size than the median particle size and half of the particles have a smaller particle size than the median particle size. Similarly, the term “median pore size” refers to the pore size of a referenced material wherein half of the pores of that material have a larger pore size than the median pore size and half of the particles have a smaller pore size than the median pore size. Unless statedAttorney Docket No.: SP25-043PCT otherwise, all provided median pore sizes herein are obtainable via mercury intrusion porosimetry, with all measured values provided herein having been obtained utilizing an AutoPore poromiseter commercially available from Micromeritics.

[0048] Embodiments disclosed herein include structured sorbent articles, gas capturing apparatuses comprising structured sorbent articles, as well as mixtures and methods for the manufacture thereof.

[0049] In certain exemplary embodiments where the sorbent material is applied as coating, the base substrate comprises a ceramic substrate, a glass substrate, a metal substrate, a carbonbased substrate, a polymeric substrate, a glass-ceramic substrate, or a substrate comprising a combination of these materials. In certain exemplary embodiments, the base substrate comprises at least one of cordierite, silica, alumina, titania, clay, talc, aluminum titanate, silicon carbide, diatomaceous earth, hollow glass microspheres, or other ceramic or ceramic-precursor materials. In certain exemplary embodiments, the base substrate comprises a porous substrate. In certain exemplary embodiments, the base substrate is a columnar article having a honeycomb or cellular form factor that comprises an array of intersecting walls that define a plurality of channels extending axially therethrough and the adsorbing composition is deposited on the walls and / or within the pores of the walls. In certain exemplary embodiments, the structured sorbent article comprises at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, or even at least 90 wt% of the sorbent material including ranges having these values as end points, such as from 65 wt% to 90 wt%.

[0050] FIG. 1 shows an example of an article 100 having a honeycomb or cellular structure in accordance with embodiments disclosed herein. As described herein, the article 100 is a structured sorbent article manufactured by either coating a porous material of a base honeycomb substrate with a sorbent material, or by directly forming (e.g., via extrusion) the structured sorbent article from a mixture that comprises a sorbent material. Since the general shape of the article 100 does not change due to the incorporation of a sorbent material, FIG. 1 is also representative of the shape of the base honeycomb substrate before coating by a sorbent material. For ease of discussion herein, the base honeycomb substrate may be identified and referred to herein as base substrate 10.

[0051] The article 100 comprises a plurality of intersecting walls 102 that define a plurality of channels 104 extending axially through the article 100 from a first end face 106 to a second end face 108. Similarly, in embodiments in which the base substrate 10 is subsequently coatedAttorney Docket No.: SP25-043PCT by a sorbent material, the base substrate 10 similarly comprises a plurality of intersecting walls that define axially extending channels that resemble that shown in FIG. 1. During use, one of the first end face 106 or the second end face 108 can be arranged as an inlet face, while the other is arranged as an outlet face, such that the flow of gas traveling through the channels 104 can interact with sorbent material incorporated within the article 100 for capture of one or more target gases as discussed herein. Each repeating segment of the honeycomb structure of the article 100 that contains one of the channels 104 enclosed by the walls 102 may be referred to as a cell. Since each cell encloses one channel, the number of cells and channels is the same. The article 100 may be interchangeably referred to as having a cellular or honeycomb structure, and accordingly, the article 100 may be interchangeably referred to as a cellular or honeycomb substrate.

[0052] As described herein, manufacture of the article 100 or of the base substrate 10 from which the article 100 is formed can be accomplished by extrusion. FIG. 2 illustrates an example of a system 200 that comprises an extruder 202. The extruder 202 is arranged to receive a mixture 110 (each of which may be interchangeably referred to as a batch mixture or batch composition), such as via a hopper 204 or other inlet into the extruder 202. The extruder 202 is illustrated in FIG. 2 as a twin screw extruder comprising screw elements 206, but it is to be recognized that the extruder can be any type of extruder, such as ram extruder, capable of applying an extrusion pressure on the mixture 110 suitable to forcibly move the mixture 110 through the extruder 202 in an extrusion direction 208. The mixture 110 is forced by the extruder 202 through an extrusion die 210, such as a honeycomb extrusion die, in order to form the mixture into an extrudate 112 having the desired form factor, e.g., a honeycomb or cellular structure.

[0053] Upstream of the extrusion die 210, the extruder 202 may be equipped with additional extrusion hardware 212, including one or more components such as a homogenizer, bow breaker, screen, or the like, for controlling the properties of the mixture 11, 110 as it reaches and is extruded by the extrusion die 210. A cutting implement 214 can be included for cutting pieces of a desired length from the extrudate 112, thereby resulting in the base substrate 10 or article 100. The cutting implement 216 can be any device suitable for cutting through the extrudate 112, such as a wire, saw, knife, blade, laser, or combination thereof. The base substrate 10 can be formed in essentially the same manner, but with the mixture 110 substituted by a corresponding mixture 11 to form the base substrate 10 (e.g., a ceramic-forming mixture).Attorney Docket No.: SP25-043PCT

[0054] After extrusion and cutting to length, the base substrate 10 and / or article 100 may be dried, fired, calcined, or otherwise subjected to elevated temperature or other condition (e.g., UV light exposure, microwave energy, etc.) to activate or cure the binder materials, remove the liquid vehicle from the batch, sinter particles together, or, particularly in the case of firing ceramic bodies, reacting precursors to form one or more desired ceramic phases. Any suitable drying or firing equipment and processes can be utilized, including air flow, heat, and microwave or radio frequency energy. In some embodiments, the base substrate 10 and / or article 100 is treated at a suitably low temperature or other condition so that substantially only drying of the liquid vehicle occurs, and thereby desired organic components are not burned out, pyrolyzed, or otherwise decomposed. In particular, in embodiments in which the batch 110 is utilized that already comprises the sorbent material, conditions such as high temperature that could degrade the performance of the sorbent material should be avoided.

[0055] While FIG. 1 shows an example of a honeycomb article, e.g., the substrate 10 or article 100, having a rectangular cross section with rectangular channels, embodiments disclosed herein include other geometries for the substrate 10 and / or article 100, such other polygonal-shaped cross-sections (e.g., triangular, pentagonal, hexagonal, etc.) or circular or elliptical cross-sections (e.g., cylindrical-shaped substrates), as well as any such articles having channels with other polygonal-shaped cross-sections (e.g., triangular, pentagonal, hexagonal, etc.) or channels with circular or elliptical cross-sections (e.g., cylindrical-shaped channels).

[0056] Articles having honeycomb structures having a regular pattern of channels and walls can be described or defined with respect to the number of channels (or cells) per unit area and the thickness of the walls. In certain exemplary embodiments, the honeycomb structure comprises from 50 to 800 cells per square inch, such as from 100 to 600 cells per square inch, wherein “cells per square inch” refers to the number of channels (or cells) per square inch as viewed from an end face of the article. In certain exemplary embodiments, walls of parallel channels 104 may have a thickness in the range from 2 mils to 12 mils, such as from 4 mils to 10 mils. The geometry of a substrate may be nominally designated with the nomenclature CPSI / tw, where CPSI is the nominal cells per square inch and tw is the nominal thickness of the wall in mils. For example, a “100 / 7” geometry refers to an article having nominally 100 cells per square inch and nominally a wall thickness of 7 mils. Due to manufacturing variability and growth / shrinkage during drying or firing steps, it is understood that any values provided with respect to the geometry of a honeycomb article are nominal values, and that the actualAttorney Docket No.: SP25-043PCT values may differ from the nominal values. An actual CP SI may differ by up to 20% from the targeted nominal value, while an actual wall thickness tw may vary by up to 1.0 mil.

[0057] FIG. 3 represents a flow chart to describe steps that can be utilized in the manufacture and / or use of the article 100. In general, manufacture can be achieved by a method 300 or a method 301, or a combination thereof as described further below. The method 300 of manufacturing the article 100 may start from a step 302 in which the base substrate 10 is formed. The base substrate 10 can be formed from the batch mixture 11 and manufactured into a desired form, e.g., via the system 200 described above with respect to FIG. 2. In certain exemplary embodiments, the porous material of the base substrate 10 (which ultimately forms the basis of the walls 102 of the article 100), comprises a ceramic, a glass, a metal, a carbon, a polymer, or a glass-ceramic material, or combinations thereof. Accordingly, the step 302 can be achieved by extruding a batch mixture (e.g., in accordance with the system 200 in FIG. 2) to form a green body, then drying and / or firing the green body to create the base substrate 10. The base substrate 10 may comprise, or be formed from any material useful as a honeycomb body used in catalyst substrates or particulate filters, such as at least one of cordierite, silica (e.g., silica gel, amorphous silica, fused silica, etc.) or other silica-based materials such as diatomaceous earth or hollow glass microspheres, alumina (e.g., gamma-alumina, alphaalumna, etc.), titania, aluminum titanate, silicon carbide, as well as ceramic precursors such as clay or talc.

[0058] In certain exemplary embodiments, the porous material of the base substrate 10 (from which the intersecting walls 102 of the article 100 will be formed) has a porosity ranging from about 30% to about 90%. Higher porosities may be generally desired to reduce the thermal mass of the part in temperature-based desorb processes in order to reduce the parasitic or waste heat that goes into non-sorbent materials during desorb of the sorbent material. However, higher porosities may not be practical in some embodiments because higher porosity generally comes at a tradeoff to lower strength. Accordingly, porosities from about 60% to about 80% are preferred in some embodiments to provide a generally good tradeoff between low thermal mass and sufficient mechanical strength for a variety of different materials, although higher porosities can be utilized if sufficient strength is maintained. In certain exemplary embodiments, material of the base substrate 10 may have a median pore size (D50) ranging from about 5 pm to about 30 pm.Attorney Docket No.: SP25-043PCT

[0059] Once the base substrate 10 is obtained, e.g., after the base substrate 10 is formed in step 302, the base substrate 10 is coated by a sorbent material in accordance with step 304 in order to yield the article 100. For example, the sorbent material may be first added to a coating mixture, such as a coating slurry, for application onto and / or impregnation into base substrate 10, thereby forming the walls 102 as a combination of the sorbent material and the porous material of the base substrate 10. As described further herein, a coating mixture may comprise the sorbent material, a coating binder, a liquid carrier (e.g., water or alcohol based), and optionally a porous filler material (e.g., sepiolite particles as described further herein). For example, coating in step 304 can be accomplished by at least one of wash coating, dip coating, piston coating, vacuum coating, spray coating, spin coating, or any other suitable process known to or discovered by persons having ordinary skill in the art.

[0060] Alternatively, manufacture the article 100 may be carried out in accordance with the method 301. The method 301 begins at step 303 in which a mixture comprising the sorbent material is made, e.g., the mixture 110. As described further herein, the mixture 110 may comprise the sorbent material, one or more binders, a porous filler material (e.g., sepiolite particles as described further herein), and a liquid carrier (e.g., water or alcohol based), as well as any additives or extrusion aids, such as plasticizers (if separate from the binder) or lubricants. The mixture is then shaped into the structured sorbent article, such as via extrusion, e.g., as described with respect to the system 200 forming the mixture 110 into the structured sorbent article 100. As described herein, since exposure to high temperature will destroy or degrade many sorbents, the structured article 100 may be manufactured without a firing step, instead being only dried at low temperature (e.g., less than 200°C, less than 150°C, or even less than 100°C).

[0061] After the structured sorbent article 100 is formed, the structured sorbent article 100 may be used in a method 310 of capturing (separating) a select or target component from a gaseous flow. The method 310 starts at step 312 in which a gas stream comprising the selected or target gaseous component is flowed through the structured sorbent article. At step 314 the selected or target gaseous component is captured via adsorption on and / or absorption in the sorbent material in the structured sorbent article. At step 316 the structured sorbent article is subjected to a condition, such as elevated temperature, to desorb the selected or target gaseous component from the sorbent material to enable the gaseous component to be collected. For example step 316 may be accomplished via a flow of steam, Joule heating, or some other sourceAttorney Docket No.: SP25-043PCT of heat suitable to elevate the temperature of the sorbent above a desorption temperature. After desorbing the gaseous component from the sorbent material, the adsorb-desorb cycle can be repeated to capture and collect more of the target gaseous component (e.g., carbon dioxide).

[0062] Embodiments disclosed herein include those in which the structure sorbent article 100 comprises a binder. In embodiments, the binder is an organic binder. In embodiments, the binder comprises a polyvinyl compound such as polyvinyl alcohol (PVA), polyvinyl butyral (PVB), or polyvinylpyrrolidone (PVP), a cellulosic material such as methylcellulose, an acrylic latex, or combinations thereof. In certain exemplary embodiments the binder is polyvinylpyrrolidone (PVP), methylcellulose, or a combination thereof.

[0063] In some embodiments, the structured sorbent article comprises a combination of at least two binders. In some embodiments a first binder is selected from the aforementioned materials, and a second binder is selected to act as a plasticizer and / or stabilizer. Non-limiting examples of such materials include those comprising polypropylene glycol polymers, such as polyethylene glycol (PEG). In certain embodiments, the second binder is polyethylene glycol (PEG). For the purposes of this disclosure, reference to PEG shall include different molecular weights, including those that may be associated with the term polyethylene oxide (PEO), and therefore, PEG and PEO are used herein interchangeably as referring to the same material.

[0064] In certain exemplary embodiments when the binder extruded as part of the batch 110 to form the structured sorbent article 100, the binder comprises from 10 wt% to 25 wt%. When included in a coating slurry used to coat a base substrate, the coating slurry, on a dry basis separate from the liquid vehicle, may comprise from 5 wt% to 20 wt% of the coating slurry, such as from 5 wt% to 10 wt%. In certain exemplary embodiments when the binder is coated onto a base substrate as part of a coating slurry, a ratio of coating mass (excluding the liquid vehicle) to substrate volume ranges from 50 grams of coating to 600 grams of coating per liter of substrate, such as from 100 grams to 550 grams of coating per liter of substrate, and further such as from 300 grams to 550 grams of coating per liter of substrate.

[0065] In certain exemplary embodiments, the sorbent material comprises at least one of an amine ion exchange resin, polyamine, or other amine-containing or amine-functionalized material, zeolite, metal-organic framework (MOF), covalent organic framework (COF), carbonate, or activated carbon. In certain exemplary embodiments, the amine-containing material comprises a polyamine such as polyethylenimine (PEI). In certain embodiments, the sorbent material is a solid sorbent material. In certain embodiments, the sorbent materialAttorney Docket No.: SP25-043PCT comprises a solid sorbent material and a liquid sorbent material. Unless stated otherwise herein, the phase (solid, liquid, gas) of a material can be determined at 20°C at 1 atm of pressure. In certain exemplary embodiments, the amine-containing material comprises at least one of a resin, for example an ion exchange resin, or an amine-functionalized metal-organic framework. Other materials useful for stabilizing or being functionalized by amines can also be used, such as intercalated, layered metal oxides or micro-mesoporous oxides, such as clays or layered double hydroxides. In certain exemplary embodiments, the resin comprises a crosslinked polystyrene resin, such as a crosslinked polystyrene resin with amine functional groups. Examples of amine resins include Lewatit VPOC 65 available from Lanxess, Purolite Al 10 available from Purolite, or Diaion WA21 J available from Diaion. Examples of MOF materials include HKUST-1 (also known as MOF-199), ZIF-8, CALF-20, NH2-MIL-53, NH2-MIL-101, or UiO-66, each with or without amine functionalization, as applicable. Examples of other useful MOFs include those with aromatic cages capable of sequestering amines with ether groups.

[0066] In certain embodiments, the sorbent material is an organic material or a hybrid organic-inorganic material. In further embodiments, the structured sorbent article is at least 80 wt% organic components, where reference to “organic components” as used herein is defined to mean both organic materials (e.g., organic sorbent materials such as resins, amines, and COFs, as well as any organic binders) and organic-inorganic hybrid materials (such as MOFs).

[0067] In general, higher sorbent material loadings are usually desirable in order to increase the amount of gas able to be captured by a structured sorbent article of a given size in comparison to a similarly sized structure sorbent article having a lesser amount of sorbent material. Additionally, particularly high sorbent material loadings (e.g., at least 65 wt%) may be especially advantageous when utilized in a gas capture system that utilizes heat to initiate the desorption of captured gas from the sorbent material. That is, since both the sorbent and non-sorbent material will be heated during the desorb process, a structured sorbent article having a high sorbent material loading will correspondingly have a lower percentage of non-sorbent material into which “parasitic” heat is wasted. In other words, the thermal mass of the non-sorbent materials that do not participate in gas capture is reduced, which leads to less wasted heat, and therefore more efficient energy usage per unit of gas captured.

[0068] Furthermore, it is noted that structured sorbent articles have two main requirements for use in a gas capture system: (i) high gas capture performance and (ii) sufficient strength.Attorney Docket No.: SP25-043PCT Due to their generally high selectivity, organic sorbent materials (including organic-inorganic hybrids like MOFs) are attractive options to provide high gas capture, while due to their low density and high ability to impart strength, organic binders are an attractive option to impart the necessary strength into a body. Accordingly, structured sorbent articles having particularly high organic loading (e.g., at least 80 wt%) may be particularly advantageous as these embodiments enable the components directly corresponding to the requirements of gas capture performance and strength (sorbent material and binder, respectively) to be maximized, thereby further reducing cost, complexity, and the aforementioned issue of parasitic heat.

[0069] As noted above, generally higher amounts of sorbent are typically desired to increase the gas capture capacity per unit volume of structured sorbent article. However, it is noted that gas capture performance, and in particular the kinetics or speed of gas capture, may be negatively affected if the structured sorbent article has insufficient porosity and / or the sorbent material particles of the structure sorbent article are too closely packed together, as this may prevent the gas flow from being able to readily contact or interact with sorbent material that is deep within the bulk of the material of the structured sorbent article (i.e., the sorbent material located in the middle of the walls 102, spaced away from the surfaces of the channels 104). Organic sorbents such as amine ion exchange resins are particularly susceptible to degradation in capture performance if the particles are too closely packed together. In such embodiments, the inclusion of high porosity filler particles can be useful to assist in distributing the sorbent material throughout the material of the structured sorbent article by physically spacing particles of the sorbent material away from each other. Surprisingly, the inventors have found that certain high porosity materials, such as bentonite, do not work well to distribute the sorbent material.

[0070] In contrast, sepiolite particles have exhibited a superior ability to space apart and distribute sorbent material particles, even at relatively small amounts, such as at least 3 wt%. In some embodiments, the structured sorbent article comprises at least 7 wt% sepiolite. In some embodiments, the structured sorbent article comprises from 3 wt% to 20 wt% of sepiolite. In embodiments, a ratio of the sepiolite to the sorbent material is at least 1 :25, by weight, such as is in the range of 1 :25 to 1 :4.5, by weight.

[0071] Examples

[0072] Embodiments disclosed herein are further illustrated by the following non-limiting examples.Attorney Docket No.: SP25-043PCT

[0073] Mixtures were prepared utilizing a MOF material as the sorbent material, which are reported in Tables 1 and 2. The MOF material was synthesized by the inventors from the precursors and to achieve the structure generally as described in a research article by Lin et al., A scalable metal-organic framework as a durable physisorbent for carbon dioxide capture, Science, vol. 374, pp. 1464-1469, 17 December 2021, which article is hereby incorporated by reference to the extent necessary to describe a possible synthesis process and structure of the MOF material utilized in the Examples. PVP refers to polyvinylpyrrolidone and PEI refers to a branched polyethylenimine. The PVP used in the examples had a molecular weight of about 1,300,000 g / mol, while the PEI had a molecular weight of about 600 g / mol. De-ionized water was included as a liquid vehicle for the Examples of both Tables 1-2 to aid in combining the mixture into a formable paste, and was included in the indicated amount as a weight percent super addition (wt% SA) with respect to the total weight of the other ingredients. More particularly, the water addition is reflected as a super addition because after the extruded body is dried, it is expected that the resulting sorbent article will comprise the other components, totaling up to 100 wt%, without the water addition.

[0074] Table 1 - Example mixtures evaluated for extrudability that comprised a MOF

[0075] The mixtures of Table 1 were assessed for formability, e.g., the ability to be formed such as via extrusion, by combining the materials in the amounts indicated to form a paste-like mixture and then spreading the resulting paste-like mixture onto a flat surface. Example 1 exhibited the best formability by spreading into a continuous smooth sheet, thereby indicating good formability (e.g., good extrudability). Since the PEI was in a liquid form, the water addition from Example 1 was reduced and replaced with a similar amount of PEI in Example 2. The mixture of Example 2 also created a continuous sheet, although the materials could be visually observed as not being as homogenously and smoothly combined as in Example 1. InAttorney Docket No.: SP25-043PCT Example 3 even more PEI was added and the water addition was reduced further with respect to the mixture of Example 2. As a result, the mixture of Example 3 tended to fracture into clumps of material instead of spreading into a continuous sheet, indicating generally poor formability. The amount of water was significantly increased in both Examples 4 and 5, and the amount of sepiolite was correspondingly increased to accommodate the increased amount of liquid. Example 5 also included an amount of PEI between the amounts included in Examples 2 and 3. Both Examples 4 and 5 could be smoothly spread, although with the tendency of the sheets to tear into smaller pieces, which indicates a lower green strength, and correspondingly less formability than that seen in Example 1 or 2.

[0076] Table 2 describes further Example mixtures that comprised either the MOF material of Examples 1-5 or a Lewatit VP OC 1065, ion exchange resin (in Table 2 as Resin). Any ingredients in Examples 6 and 7 that are shared with Examples 1-5 were as described above with respect to Table 1 unless stated otherwise. In Table 2, sodium stearate was added as a processing aid and lubricant to facilitate in smooth material flow by reducing friction and preventing sticking of the material during extrusion. The sodium stearate used is available from Peter Greven under the name Liga. PEG refers to polyethylene glycol, and can be included as a secondary binder as described herein to act as plasticizer to further improve flexibility and mechanical compliance of both the batch during extrusion and of the extruded body, as well as to aid in adhesion provided by the binder (e.g., methylcellulose, PVP, etc.).

[0077] Table 2 - Example mixtures comprising different sorbent types extruded into honeycomb bodies

[0078] The mixtures of Examples 6, 7, and 8 were successful in forming a honeycomb article by extrusion of the corresponding mixture through a honeycomb extrusion die. Example 6 and 7 both used the above-identified MOF as the sorbent material, but with PVP used as a binder in Example 7 in contrast to methylcellulose in Example 6. Examples 6 and 8 were similarAttorney Docket No.: SP25-043PCT except that Lewatit VP OC 1065 ion exchange resin was utilized as the sorbent material in Example 8 in comparison to the CALF-20 MOF used in Example 6. As described throughout this disclosure, the particular sorbent materials used in the Examples can be interchanged, in whole or in part, with other sorbent materials, including different MOFs or different amine resins, than those utilized in these Examples.

[0079] A batch mixture according to a comparative example was made resembling Example 6 but with the sepiolite replaced by bentonite. Surprisingly, the bentonite-based comparative example was not able to be successfully extruded into a honeycomb body. Without wishing to be bound by theory, it is believed that the particularly high porosity, high surface area (e.g., greater than 300 m2 / g), and non-swelling behavior of the sepiolite enables it to provide the desired function, while other high porosity materials such as bentonite do not function suitably.

[0080] Further examples were prepared by coating a base substrate with a coating slurry, i.e., generally in accordance with the method 300, by first forming a cordierite honeycomb body (as the base substrate 10) and then coating the cordierite honeycomb with a coating slurry that comprised the sorbent material. An Example 9 for the coating slurry is provided in Table 3 below. The MOF material prepared as described with respect to Examples 1-7 was utilized as the sorbent material for Example 9. PEG and PVP in Table 3 were as described above. Isopropyl alcohol (IP A) was used as the solvent, with the components of Table 3 loaded to a solid loading of about 30-35 wt% in the IPA for each example.

[0081] Table 3 - Example slurry for coating a sorbent material onto a base substrate

[0082] In the test of Example 9, the coating was successful, however, the MOF material tended to Without wishing to be bound by theory, it is believed that the MOF material had a wide particle size distribution and contained some particles larger desired, which resulted in the channels of the base substrate being clogged by the MOF material agglomerating in the channels despite a high amount of water used to thin the slurry. In Example 10, the PEG was added, which, in addition to continuous stirring of the prepared slurry overnight for thoroughAttorney Docket No.: SP25-043PCT mixing, was successful in addressing this channel clogging issue without altering the particle size distribution of the MOF material.

[0083] It will be apparent to those skilled in the art that various modifications and variations can be made to embodiment of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure cover such modifications and variations provided they come within the scope of the appended claims and their equivalents.

Claims

Attorney Docket No.: SP25-043PCT What is claimed is:

1. A structured sorbent article comprising:at least 65 wt% of a sorbent material, wherein the sorbent material is an organic material, an organic-inorganic hybrid material, or a combination thereof; andan organic binder,wherein a total of organic components in the structured sorbent article is at least 80 wt% of the structured sorbent article.

2. The structured sorbent article of claim 1, wherein the total content of organic components is at least 90 wt% of the structured sorbent article.

3. The structured sorbent article of claim 1, wherein the total content of organic components is at least 96 wt% of the structured sorbent article.

4. The structured sorbent article of claim 1, wherein the total content of organic components is at least 99 wt% of the structured sorbent article.

5. The structured sorbent article of any one of claims 1-4, further comprising porous inorganic filler particles.

6. The structured sorbent article of claim 5, wherein structured sorbent article comprises at least 3 wt% of the porous inorganic filler particles.

7. The structured sorbent article of claim 5, wherein the structured sorbent article comprises from 3 wt% to 20 wt% of the porous inorganic filler particles.

8. The structured sorbent article of any one of claims 5-7, wherein the porous inorganic filler particles are sepiolite.

9. The structured sorbent article of any one of claims 1-8, wherein the structured sorbent article comprises at least 70 wt% of the sorbent material.Attorney Docket No.: SP25-043PCT 10. The structured sorbent article of any one of claims 1-9, wherein the structured sorbent article comprises at least 75 wt% of the sorbent material.

11. The structured sorbent article of any one of claims 1-10, wherein the structured sorbent article comprises at least 80 wt% of the sorbent material.

12. The structured sorbent article of any one of claims 1-11, wherein the structured sorbent article comprises at least 90 wt% of the sorbent material.

13. The structured sorbent article of any one of claims 1-12, wherein the structured sorbent article comprises from 65 wt% to 90 wt% of the sorbent material.

14. The structured sorbent article of any one of claims 1-13, wherein the sorbent material comprises an amine ion exchange resin, a polyamine, an amine-containing material, an amine-functionalized material, a zeolite, a metal-organic framework (MOF), a covalent organic framework (COF), a carbonate, activated carbon, or a combination thereof.

15. The sorbent article of any one of claims 1-14, wherein the sorbent material comprises a solid sorbent material and the structured sorbent article comprises at least 64 wt% of the solid sorbent material.

16. The sorbent article of claim 15, wherein the sorbent material comprises both the solid sorbent material and a liquid sorbent material.

17. The sorbent article of claim 16, wherein the liquid sorbent material is polyethyleneimine (PEI).

18. The structured sorbent article of any one of claims 1-17, wherein the structured sorbent article has a honeycomb form factor comprising a plurality of intersecting walls defining a plurality of channels extending axially through the structured sorbent article.

19. The structured sorbent article of claim 18, wherein the sorbent material is homogeneously incorporated within and integrally distributed throughout the intersecting walls to form the intersecting walls.Attorney Docket No.: SP25-043PCT20. The structured sorbent article of claim 18, further comprising a base substrate, wherein the sorbent material is a coating at least partially on surfaces of base substrate within the plurality of channels.

21. A structured sorbent article comprising:at least 3 wt% sepiolite;at least 50 wt% of a sorbent material; andan organic binder.

22. The structured sorbent article of claim 21, wherein the sorbent article comprises from 3 wt% to 20 wt% sepiolite.

23. The structured sorbent article of any one of claims 21-22, wherein the sorbent article comprises at least 7 wt% sepiolite.

24. The structured sorbent article of any one of claims 21-23, comprising from 3 wt% to 20 wt% sepiolite.

25. The structured sorbent article of any one of claims 21-24, wherein a ratio of the sepiolite to the sorbent material is at least 1 :25, by weight.

26. The structured sorbent article of any one of claims 21-25, wherein a ratio of the sepiolite to the sorbent material is in the range of 1 :25 to 1 :4.5, by weight.

27. The structured sorbent article of any one of claims 21-26, wherein the sorbent material comprises an amine ion exchange resin, a polyamine, an amine-containing material, an amine-functionalized material, a zeolite, a metal-organic framework (MOF), a covalent organic framework (COF), a carbonate, activated carbon, or a combination thereof.Attorney Docket No.: SP25-043PCT 28. The structured sorbent article of any one of claims 21-27, wherein the structured sorbent article has a honeycomb form factor comprising a plurality of intersecting walls defining a plurality of channels extending axially through the structured sorbent article.

29. The structured sorbent article of claim 28, further comprising a base substrate and the sorbent material is formed as a coating on surfaces of the base substrate within the plurality of channels.

30. The structured sorbent article of claim 28, wherein the sorbent material is homogeneously incorporated within and integrally distributed throughout the intersecting walls to form the intersecting walls.

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