Carbon capture article having zeolite and silicone resin, methods of making and using the same

Abstract

This invention discloses a carbon capture article comprising: (i) a ceramic honeycomb assembly including an inlet end, an outlet end, and intersecting walls defining cells through which fluid can flow; (ii) a zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb assembly; and (iii) a silicone resin coating at least partially disposed on the zeolite coating. The zeolite coating may be a 13-X type zeolite. The silicone resin may be a siloxane resin. This invention also discloses a method for manufacturing the carbon capture article, the method comprising a silicone coating step, the silicone coating step comprising coating a silicone resin at least partially onto the zeolite coating to form the carbon capture article, the zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb assembly. Finally, this invention discloses a method for capturing carbon dioxide from the air, the method comprising a flow step, the flow step comprising passing a fluid containing carbon dioxide (CO2) molecules through the carbon capture article.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 599,776, filed November 16, 2023, pursuant to 35 USC § 119, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] This disclosure relates to a carbon capture article, and more specifically, to a carbon capture article having a zeolite coating and a silicone coating to impart hydrophobicity to the zeolite coating. Background Technology

[0004] There are various environmental and economic incentives for capturing carbon dioxide (CO2) from waste streams generated by industrial processes (e.g., post-combustion capture of fossil fuels) before it enters the atmosphere, as well as for extracting CO2 directly from the atmosphere (e.g., direct air capture). Solid materials have been developed for CO2 capture. These solid materials generally fall into one of two categories distinguished by their capture mechanism—physical adsorption (physicosorption) or chemisorption (chemisorption). The former, relying on physical adsorption, are typically highly porous to provide a large surface area for adsorbing CO2 molecules onto their surface via relatively weak van der Waals forces. Activated carbon, metal-organic frameworks, and various zeolites are examples of solid adsorbents. The latter, relying on chemical mechanisms, involve a chemical reaction with CO2 molecules, resulting in molecular bonding (e.g., stronger than van der Waals forces). Amines and alkali metal oxides are examples. In either case, after CO2 molecules are captured, the solid material can be manipulated to induce the release of CO2 molecules, allowing the solid material to be reused to capture more CO2 molecules. For example, heating a solid material can release CO2 molecules from it. The released CO2 molecules can then be directed to storage areas, such as retired natural gas reservoirs, and other options.

[0005] As mentioned above, zeolites are used to capture CO2 molecules via physical adsorption. Generally, zeolites are crystalline aluminosilicate materials. Zeolite coatings have been grown on porous supports (such as monolithic honeycomb ceramics) to produce gas separation products, such as extracting CO2 from fluids passing through them.

[0006] However, a problem exists: zeolites (and therefore membranes made from them) naturally prefer to adsorb water (H2O) molecules rather than CO2 molecules, and therefore, zeolites cannot be used for direct air capture of carbon dioxide due to the presence of water in the air (e.g., humidity). H2O molecules are smaller than CO2 molecules, and thus larger CO2 molecules more easily enter the adsorption sites of zeolites. Additionally, oxygen within the zeolite forms hydrogen bonds with H2O molecules, while CO2 molecules lack hydrogen and therefore do not participate in hydrogen bonding. Furthermore, the surface charge of zeolites may prefer polar molecules (such as H2O) rather than nonpolar molecules (such as CO2). The preferential adsorption of H2O molecules over CO2 molecules by zeolites is problematic because when the goal is to extract CO2, the adsorption of H2O molecules on the zeolite prevents the adsorption of CO2 molecules, thus negating the target. Summary of the Invention

[0007] This disclosure addresses this problem using a carbon capture article comprising a zeolite coating for adsorbing carbon dioxide, and at least partially above the zeolite coating to impart hydrophobicity, which reduces the ability of water molecules to enter the adsorption sites of the zeolite coating, thereby opening those sites to adsorb carbon dioxide molecules.

[0008] According to a first aspect of this disclosure, a carbon capture article comprises: (i) a ceramic honeycomb assembly including an inlet end, an outlet end, and intersecting walls defining a cell through which fluid can flow from the inlet end to the outlet end; (ii) a zeolite coating that at least partially covers the intersecting walls of the ceramic honeycomb assembly; and (iii) a silicone resin coating that at least partially rests on the zeolite coating.

[0009] According to a second aspect of this disclosure, a carbon capture article according to the first aspect is proposed, wherein the zeolite coating comprises zeolite with an average pore size greater than 3.3 Å.

[0010] According to a third aspect of this disclosure, a carbon capture article according to any one of the first to second aspects is provided, wherein the zeolite coating comprises zeolite selected from the group consisting of: type A zeolite, type X zeolite, type Y zeolite, mordenite, magnesium alkali zeolite, chalcogenite, clinoptilolite and ZSM-5 zeolite.

[0011] According to a fourth aspect of this disclosure, a carbon capture article according to the third aspect is proposed, wherein the zeolite coating comprises X-type zeolite.

[0012] According to a fifth aspect of this disclosure, a carbon capture article according to the fourth aspect is proposed, wherein the zeolite coating comprises type 13-X zeolite.

[0013] According to a sixth aspect of this disclosure, a carbon capture article according to any one of the first to fifth aspects is provided, wherein the density of the zeolite coating is in the range of 50 g / L of the ceramic honeycomb material to 400 g / L of the ceramic honeycomb material.

[0014] According to the seventh aspect of this disclosure, a carbon capture article according to any one of the first to sixth aspects is provided, wherein the density of the silicone resin is in the range of 3.0 g / L of the ceramic cell substrate to 7.0 g / L of the ceramic cell substrate.

[0015] According to the eighth aspect of this disclosure, a carbon capture article according to any one of the first to seventh aspects is provided, wherein the silicone resin comprises a siloxane resin.

[0016] According to the ninth aspect of this disclosure, a carbon capture article according to the eighth aspect is proposed, wherein the siloxane resin is alkoxy-functionalized.

[0017] According to the tenth aspect of this disclosure, a carbon capture article according to the ninth aspect is provided, wherein the siloxane resin is methoxy-functionalized.

[0018] According to the eleventh aspect of the present invention, a carbon capture article according to the eighth aspect is provided, wherein the silicone resin comprises one or more silsesquioxane resins.

[0019] According to the twelfth aspect of this disclosure, a carbon capture article according to any one of the first to eleventh aspects is proposed, wherein when a fluid containing carbon dioxide (CO2) molecules and water (H2O) molecules flows through the carbon capture article, the carbon capture per gram of zeolite coating exhibited by the carbon capture article at 0°C is greater than the carbon capture per gram of zeolite coating exhibited by the otherwise identical carbon capture article at 0°C when the same fluid flows through the otherwise identical carbon capture article without the silicone resin coating.

[0020] According to the thirteenth aspect of this disclosure, a carbon capture article is provided as described in any one of the first to twelfth aspects, wherein when air containing carbon dioxide (CO2) molecules and water molecules (CO2) flows through the carbon capture article as the fluid, the carbon capture article exhibits a carbon capture of greater than 2.0 mmol CO2 / g zeolite coating at 0°C.

[0021] According to the fourteenth aspect of this disclosure, a method of manufacturing a carbon capture article includes: using a ceramic honeycomb monolith comprising an inlet end, an outlet end, and intersecting walls defining a cell, through which fluid can flow from the inlet end to the outlet end; and a silicone coating step comprising coating a silicone resin coating at least partially onto a zeolite coating to form a carbon capture article, the zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb monolith.

[0022] According to the fifteenth aspect of this disclosure, a method according to the fourteenth aspect is proposed, wherein the silicone coating step further comprises curing the silicone resin coating to form the carbon capture article.

[0023] According to the sixteenth aspect of this disclosure, a method according to any one of the fourteenth to fifteenth aspects is provided, wherein the silicone resin coating comprises a siloxane resin.

[0024] According to the seventeenth aspect of this disclosure, a method according to the sixteenth aspect is proposed, wherein the siloxane resin is alkoxy-functionalized.

[0025] According to the eighteenth aspect of this disclosure, a method according to the seventeenth aspect is proposed, wherein the siloxane resin is methoxy-functionalized.

[0026] According to the nineteenth aspect of this disclosure, a method according to any one of the fourteenth to fifteenth aspects is provided, wherein the silicone resin comprises a silsesquioxane resin.

[0027] According to the twentieth aspect of this disclosure, a method according to any one of the fourteenth to nineteenth aspects is proposed, wherein coating the silicone resin coating at least partially onto the zeolite coating comprises immersing the zeolite coating disposed on the ceramic honeycomb substrate in a solution of a solvent and the silicone resin.

[0028] According to the twenty-first aspect of this disclosure, the method according to any one of the fourteenth to twentieth aspects further comprises: a zeolite coating forming step, the zeolite coating forming step comprising (i) coating zeolite particles onto at least a portion of the intersecting walls of the ceramic honeycomb substrate, and (ii) calcining the zeolite particles.

[0029] According to the twenty-second aspect of this disclosure, a method according to the twenty-first aspect is proposed, wherein coating the zeolite particles onto at least a portion of the intersecting walls of the ceramic honeycomb assembly comprises immersing at least a portion of the ceramic honeycomb assembly in a solution of water and the zeolite particles.

[0030] According to a twenty-third aspect of this disclosure, a method for capturing carbon dioxide from air includes: a flow step comprising flowing a fluid containing carbon dioxide (CO2) molecules through a carbon capture article, the carbon capture article comprising (i) a ceramic honeycomb assembly including an inlet end, an outlet end, and intersecting walls defining a unit through which the fluid can flow from the inlet end to the outlet end; (ii) a zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb assembly; and (iii) a silicone resin coating at least partially disposed on the zeolite coating, wherein at least a portion of the carbon dioxide (CO2) molecules are captured by the carbon capture article.

[0031] According to the twenty-fourth aspect of this disclosure, a method according to the twenty-third aspect is proposed, wherein the fluid further comprises water (H2O) molecules.

[0032] According to the twenty-fifth aspect of this disclosure, a method according to any one of the twenty-third to twenty-fourth aspects is proposed, wherein the fluid is air.

[0033] According to the twenty-sixth aspect of this disclosure, the method according to any one of the twenty-third to twenty-fifth aspects further comprises: a regeneration step, the regeneration step comprising applying thermal energy to the carbon capture article in which the carbon dioxide (CO2) molecules are captured, until at least a portion of the carbon dioxide (CO2) molecules are released from the carbon capture article. Attached Figure Description

[0034] In the attached diagram:

[0035] Figure 1 This is a perspective view of the carbon capture article disclosed herein, showing a ceramic honeycomb monolith having intersecting walls forming cells extending from the inlet end to the outlet end;

[0036] Figure 2 yes Figure 1 A plan view of the carbon capture product, showing the side connected to a power source via leads. The power source increases the temperature of the carbon capture product during startup for a regeneration step to desorb carbon dioxide from the carbon capture product.

[0037] Figure 3 yes Figure 2 An enlarged view of region III, showing a zeolite coating that at least partially covers the intersecting walls within each unit and a silicone resin coating that at least partially covers the zeolite coating within each unit.

[0038] Figure 4 This is a schematic diagram of various zeolites;

[0039] Figure 5 It is manufacturing Figure 1 A schematic diagram of a method for producing carbon capture articles, which illustrates the zeolite coating forming step and the silicone coating step;

[0040] Figure 6 This is a schematic diagram of a method for capturing carbon dioxide (CO2) from a fluid, showing the fluid flowing through... Figure 1 The flow steps of the carbon capture product and the regeneration steps of desorbing the captured carbon dioxide from the zeolite coating.

[0041] Regarding comparison examples 1A-1C Figure 7A It is a graph showing the change in mmol of carbon dioxide adsorbed onto each gram of zeolite coating as a function of fluid pressure and temperature for different weights of zeolite coating.

[0042] Regarding Examples 1A-1C Figure 7B Is with Figure 7A The same type of chart, but showing the difference from those without silicone coating. Figure 7A In comparison, the silicone coating caused a slight decrease in carbon monoxide adsorption;

[0043] Comparative Examples 1A-1C without Silicone Coating Figure 8A It shows a photograph of a zeolite coating immersed in water droplets that have been applied to it; and

[0044] Examples 1A-C regarding the addition of a silicone coating over a zeolite coating. Figure 8B The image shows a photograph illustrating how a silicone coating causes water droplets to bead up. It demonstrates how the silicone coating imparts hydrophobicity to the zeolite coating, reducing the number of water molecules competing with carbon dioxide molecules for adsorption onto the zeolite coating, thus compensating for factors such as… Figure 7B The silicone coating shown in the figure causes a decrease in adsorption capacity. Detailed Implementation

[0045] refer to Figure 1-3 The carbon capture article 10 includes a ceramic honeycomb block 12. In an embodiment, the ceramic honeycomb block 12 includes an inlet end 14, an outlet end 16, and an intersecting wall 18. The intersecting wall 18 defines a unit 20 (e.g., a passage, channel, etc.) through which fluid can flow from the inlet end 14 to the outlet end 16. In the illustrated embodiment, the unit 20 is not blocked at either the inlet end 14 or the outlet end 16, and fluid flowing into the inlet end 14 is then allowed to flow through the unit 20 and out of the outlet end 16 without being forced through the intersecting wall 18. In an embodiment, the intersecting wall 18 is porous. "Fluid" in this disclosure includes both liquids and gases.

[0046] In other embodiments, although not shown, the portion of unit 20 located at inlet end 14 can be plugged with a plug having the same or similar composition as the intersecting wall 18. A portion of unit 20 at outlet end 16, but not corresponding to a unit at inlet end 14, can also be plugged in a similar pattern. Therefore, in those embodiments, each unit 20 is plugged only at inlet end 14 or outlet end 16. The result may be a checkerboard pattern of the plugs. This configuration of the plugs allows for closer contact between the fluid forced through the carbon capture article 10 and the intersecting wall 18 of the ceramic honeycomb bulk material 12. The fluid is forced into unit 20 (unplugged) at inlet end 14, then through intersecting wall 18, and out through unit 20 (unplugged) at outlet end 16.

[0047] The ceramic honeycomb substrate 12 can be formed from any suitable ceramic. Examples include cordierite, mullite, spinel ceramics, or combinations thereof. Generally, the ceramic honeycomb substrate 12 can be formed from a plasticized ceramic precursor batch composition having inorganic ceramic forming batch components, a pore-forming agent (e.g., potato starch), a liquid medium, and a binder. A green body with the desired shape is then formed from the plasticized ceramic precursor batch composition. The green body is then fired under conditions that effectively transform the green body into the ceramic honeycomb substrate 12.

[0048] In an embodiment, an inorganic batching component may be selected to provide a ceramic honeycomb substrate 12 comprising at least about 93 wt% cordierite. The cordierite is substantially composed of about 49 wt% to about 53 wt% SiO2, about 33 wt% to about 38 wt% Al2O3, and about 12 wt% to about 16 wt% MgO, characterized on a basis of oxide weight percentages. The precursor powder batching composition may include about 33 wt% to about 41 wt% alumina source, about 46 wt% to about 53 wt% silica source, and about 11 wt% to about 17 wt% magnesium oxide source.

[0049] Example alumina forming sources may include alumina or aluminum-containing compounds that, when heated to sufficiently high temperatures, produce substantially 100% alumina. Non-limiting examples of alumina forming sources include corundum or α-alumina, γ-alumina, transition alumina, aluminum hydroxides such as gibbsite and diaspore, boehmite, diaspore, aluminum isopropoxide, etc. On the other hand, suitable silica forming sources may comprise clay or mixtures, such as raw kaolin, calcined kaolin, and / or mixtures thereof. Example magnesium oxide sources may comprise talc.

[0050] Inorganic ingredients and pore-forming agents can be closely blended with liquid mediators and molding aids, which impart plasticity and green strength to the raw materials when they are formed into green bodies. Molding can be accomplished, for example, by molding or extrusion. When molding is accomplished by extrusion, cellulose ether binders such as methylcellulose, hydroxypropyl methylcellulose, methylcellulose derivatives, and / or any combination thereof can be used as binders, and sodium stearate or oleic acid can be used as lubricants. The liquid mediator content can range from 20% to 50% by weight of the plasticizing composition. The liquid mediator component can be water.

[0051] For further reference Figure 3 The carbon capture article 10 also includes a zeolite coating 28. The zeolite coating 28 at least partially covers the intersecting walls 18 of the ceramic honeycomb substrate 12 (e.g., the zeolite coating 28 is disposed within a cell 20). The zeolite coating 28 may extend into the pores of the intersecting walls 18, but at least partially separates the intersecting walls 18 from the passages 30 within the cell 20 formed by the intersecting walls 18. For any given cell 20, the zeolite coating 28 may completely separate the passages 30 from the intersecting walls 18 forming the cell 20, which are disposed within the cell. How the zeolite coating 28 is applied to the ceramic honeycomb substrate 12 will be discussed further below.

[0052] For further reference Figure 4 The zeolite coating 28 comprises zeolite. Zeolite is a hydrated aluminosilicate having symmetrically stacked alumina and silica tetrahedra, which form an open, stable, three-dimensional honeycomb structure with a negative charge. The three-dimensional honeycomb structure provides open cavities in the form of channels and cages. The channels and cages (collectively referred to as “pores”) are large enough to allow desired molecules (here, CO2 molecules) to pass through, thereby allowing the zeolite to adsorb said molecules. In short, the zeolite can be a molecular sieve configured to adsorb CO2 molecules. In an embodiment, the pores of the zeolite are characterized by an average pore size of less than 2.0 nm (20 Å). The average pore size is greater than the critical diameter of the CO2 molecule, which is approximately 3.3 Å.

[0053] More specifically, the chemical composition of zeolites can be expressed by the following types of formulas. This is represented as follows: A is a cation with charge m, (x+y) is the number of tetrahedra per crystal cell, and x / y is the so-called framework silicon / aluminum ratio. Silicon and aluminum in aluminosilicate zeolites are referred to as T atoms. Cation A can be Na... + K + Ca 2+ and / or Mg 2+ .

[0054] Figure 4 The structure of four selected zeolites, along with their corresponding pore systems and pore sizes, is shown in the figure. Figure 4 In the diagram, the T atoms are located at the vertices, and the lines connecting them represent TOT bonds. If 24 tetrahedra are as follows... Figure 4 The top row shows that when connected together, a cubic octahedron, also known as a sodalite unit or β-cage, is formed. If the sodalite units are connected via their hexagonal faces, the structure of the mineral octahedral zeolite is formed.

[0055] In this embodiment, the zeolite of the zeolite coating 28 is one or more of the following: type A zeolite, type X zeolite, type Y zeolite, ZSM-5 zeolite, mordenite, magnesium alkali zeolite, chalcogenide, and clinoptilolite. This list is not exhaustive. Type A zeolite may have the average formula (Na₂O). m Al₂O₃(SiO₂) n (H2O) t Where m is 0.9 to 1.3, n is 1.3 to 4.0, and t is 1 to 6. Its synthesis produces precisely replicated sodalite units. 4A zeolite (example type A zeolite, e.g., Na₂O.Al₂O₃.₂SiO₂·9 / ₂H₂O) can absorb critical diameters less than 4... The molecules of zeolite are present, while those of 3A zeolite (another example of type A zeolite) are not.

[0056] Both X-type and Y-type zeolites are octahedral zeolites. X-type and Y-type zeolites have different molar ratios, with the molar ratio of Al₂O₃ to SiO₂ being higher in X-type than in Y-type. Generally, the pore size of Y-type zeolites is larger than that of X-type zeolites. The average pore size of 13-X-type zeolite (a specific type of X-type zeolite) is approximately 0.9 nm to 1.0 nm (9 Å to 10 Å). ZSM-5 zeolite has more silica and less alumina than octahedral zeolites and contains high-silica zeolite units. Therefore, ZSM-5 zeolite exhibits a smaller average pore size (e.g., approximately 5 Å) compared to X-type and Y-type zeolites. In this embodiment, the zeolite coating 28 comprises X-type zeolite.

[0057] Silene zeolite is naturally occurring and can be synthesized, and can have the formula (Ca, Na2,K2)Al2Si. 10 O 24 ·7H2O. Magnesium alkali zeolite and chabazite are both naturally occurring and can be synthesized. Clinoptilolite is also naturally occurring.

[0058] In the embodiments, the density of the zeolite coating 28 is in the range of 50 g of zeolite coating 28 / L of ceramic honeycomb material to 400 g / L of ceramic honeycomb material 12. In the embodiments, the weight of the zeolite coating 28 is 50 g / L, 100 g / L, 150 g / L, 200 g / L, 250 g / L, 300 g / L, 350 g / L, or 400 g / L, or any range defined by any two of these values ​​(e.g., 50 g / L to 150 g / L, 200 g / L to 300 g / L, etc.). The unit "g / L" here again refers to the number of grams of zeolite coating 28 per liter of ceramic honeycomb material 12. The volume unit (here, liter) is determined using the dimensions of the ceramic honeycomb material 12. For example, if the ceramic honeycomb material 12 is a cube, the volume is the length × width × height of the cube.

[0059] Return to reference Figure 3 The carbon capture article 10 also includes a silicone resin coating 32 that at least partially covers the zeolite coating 28. The silicone resin coating 32 does not need to completely cover the zeolite coating 28 or otherwise completely separate the passageway 30 of the unit 20 from the zeolite coating 28. In an embodiment, the silicone resin coating 32 only partially covers the zeolite coating 28, and some of the zeolite coating 28 is exposed to the passageway 30 within the unit 20. It is believed that a silicone resin coating 32 completely covering the zeolite coating 28 would significantly reduce the ability of the zeolite coating 28 to capture CO2 molecules. The silicone resin coating 32 increases the hydrophobicity of the zeolite coating 28 compared to the absence of the silicone resin coating 32. The silicone resin coating 32 may be in a cured state, but it does not have to be. How the silicone resin coating 32 can be applied to the ceramic honeycomb substrate 12 will be discussed further below.

[0060] In the embodiments, the density of the silicone resin coating 32 is in the range of 3.0 g / L of silicone resin coating 32 to 7.0 g / L of ceramic cell substrate 12. In the embodiments, the density of the silicone resin coating 32 is 3.0 g / L, 3.5 g / L, 4.0 g / L, 4.5 g / L, 5.0 g / L, 5.5 g / L, 6.0 g / L, 6.5 g / L, or 7.0 g / L, or any range defined by any two of these values ​​(e.g., 3.5 g / L to 6.0 g / L, 6.0 g / L to 6.5 g / L, etc.). Similarly, the volume unit (here, liter) is determined using the dimensions of the ceramic cell substrate 12, just as the density of the zeolite coating 28 described above.

[0061] In an embodiment, the silicone resin coating 32 comprises a siloxane resin. The siloxane resin may be alkoxy (e.g., methoxy) functionalized. For example, the silicone resin coating 32 may comprise a single organopolysiloxane or a mixture of various organopolysiloxanes. The organopolysiloxane may have (R3SiO2) 0.5 (R2SiO), (RSiO) 1.5 Any combination of (M) or (SiO2) units (usually referred to as M, D, T, and Q units, respectively), where R can be any monovalent organic group, such as methyl. Organopolysiloxanes can have cyclic, linear, or branched structures.

[0062] In the embodiments, the siloxane resin is a DT resin, for example, essentially composed of (CH3)2SiO with a D:T ratio of 1:20 to 20:1 (e.g., 0.5:2 to 2:0.5). 2 / 2 Unit and (CH3)SiO 3 / 2 Resin composed of unit cells. Example DT resin is DOWSIL. TM 2405 resin, a methoxy-functionalized siloxane resin, is available from Dow Corning Incorporated (Midland, Michigan, USA). In the examples, the siloxane resin is substantially free of (or contains no) hydroxyl groups. The description of siloxane resins is not exhaustive.

[0063] In the embodiment, formula (RSiO) 3 / 2 Some or all of the alkyl groups in the T unit of the siloxane resin are alkyl groups having 1 to 30 carbon atoms, for example, alkyl groups having 6 to 18 carbon atoms, such as octyl. The siloxane resin may be, for example, n-octylsilsesquioxane resin or n-octylmethylsilsesquioxane resin.

[0064] In an embodiment, when a fluid comprising carbon dioxide (CO2) molecules and water (H2O) molecules flows through the carbon capture article 10, the carbon capture article 10 exhibits characteristic carbon capture per gram of zeolite coating 28 disposed on and within the ceramic honeycomb substrate 12. In an embodiment, the carbon capture per gram of zeolite coating 28 obtained from the fluid exhibited by the carbon capture article 10 at 0°C can be greater than the carbon capture exhibited by a otherwise identical carbon capture article 10 without a silicone resin coating 32 disposed on the zeolite coating 28 when the same fluid flows through it. For example, the carbon capture article 10 can exhibit a carbon capture greater than 2.0 mmol CO2 / gram of zeolite coating 28 at 0°C, such as a carbon capture in the range of 2.0 mmol CO2 to 6.8 mmol CO2 / gram of zeolite coating 28 at 0°C.

[0065] Now for reference Figure 5This document describes a method 100 for manufacturing a carbon capture article 10. At the silicone coating step 102, method 100 includes coating a silicone resin coating 32 at least partially onto a zeolite coating 28 to form the carbon capture article 10, the zeolite coating at least partially covering the intersecting walls 18 of the ceramic honeycomb substrate 12. In an embodiment, the silicone coating step 102 further includes curing the silicone resin coating 32 to form the carbon capture article 10. To coat the silicone resin coating 32 onto the zeolite coating 28, the zeolite coating 28, which is at least partially disposed on the ceramic honeycomb substrate 12, can be immersed in a solution of a solvent and a silicone resin. The solvent may be, for example, ethanol. The concentration of the silicone resin coating 32 in the solution can be any concentration that causes the carbon capture article 10 to exhibit a greater CO2 capture per gram of zeolite coating 28 than if the silicone resin coating 32 were not applied to the zeolite coating 28.

[0066] In an embodiment, method 100 further includes a zeolite coating forming step 104. The zeolite coating forming step 104 occurs prior to the silicone coating step 102. The zeolite coating forming step 104 includes coating zeolite particles onto at least a portion of the intersecting walls 18 of the ceramic honeycomb substrate 12, and then calcining the zeolite particles. The ceramic honeycomb substrate 12 can be immersed in a solution of water and zeolite seed particles to coat the zeolite seed particles onto the ceramic honeycomb substrate 12. Alternatively, the solution can be sprayed onto the ceramic honeycomb substrate 12. Calcining the zeolite particles forms a zeolite coating 28. A silicone resin coating 32 is added after the ceramic honeycomb substrate 12 has been fired and the zeolite particles have been calcined to prevent the calcination from damaging the silicone resin coating 32.

[0067] For further reference Figure 6 This document discloses a method 200 for capturing carbon dioxide (CO2) from a fluid. Method 200 includes a flow step 202. Flow step 202 includes flowing a fluid comprising carbon dioxide (CO2) molecules through a carbon capture article 10. For example, the fluid may flow into a passage 30 at an inlet end 14 of the carbon capture article 10. Before the fluid exits the passage 30 from an outlet end 16, a zeolite coating 28 absorbs (and thus captures) at least a portion of the carbon dioxide (CO2) molecules in the fluid. In embodiments, in addition to carbon dioxide (CO2) molecules, the fluid also includes water (H2O) molecules. For example, the fluid may be air with non-zero humidity.

[0068] In an embodiment, method 200 further includes a regeneration step 204. Regeneration step 204 occurs after flow step 202. Regeneration step 204 includes applying heat to carbon capture article 10, in which carbon dioxide (CO2) molecules are adsorbed (e.g., captured). Heat is applied until at least a portion (e.g., substantially all) of the adsorbed carbon dioxide (CO2) molecules are released (e.g., desorbed) from carbon capture article 10. The thus released carbon dioxide (CO2) molecules can be directed to a storage chamber.

[0069] To apply heat to the carbon capture article 10, it may be subjected to heat generated from an external source. For example, a heater may heat the carbon capture article 10, or a fluid of sufficient temperature that does not adhere to the carbon capture article 10 may flow through passage 30. In other embodiments, when the ceramic honeycomb substrate 12 is sufficiently conductive (e.g., comprising graphite), a power source may be used to pass current through leads disposed on opposite sides of the carbon capture article 10. The sides will resist the current and thus generate heat. The resistance may be in the range of 5 ohms to 500 ohms. The current may be controlled over time to achieve a desired temperature for the carbon capture article 10. To desorb carbon dioxide from the zeolite coating 28, the temperature of the carbon capture article 10 (and therefore the zeolite coating 28) may be raised to approximately 350°C, such as in the range of 200°C to 350°C. The temperature should not be so high as to damage the silicone resin coating 32 disposed on the zeolite coating 28.

[0070] The carbon dioxide (CO2) desorbed from the zeolite coating 28 is directed to a storage chamber, such as an underground cavern. Instead of a storage chamber, the carbon dioxide (CO2) desorbed from the zeolite coating 28 can be used in other manufacturing processes, such as the carbonation of beverages. After regeneration step 204, method 200 can be repeated to sequentially execute flow step 202 and regeneration step 204 again.

[0071] The carbon capture article 10 and method 100 of this disclosure solve the problems identified in the prior art, at least in part, because the silicone resin coating 32 is hydrophobic and prevents or reduces the number of water (H2O) molecules that can interact with the zeolite coating 28. Reducing the number of water molecules interacting with the zeolite coating 28 decreases the number of water molecules adsorbed by the zeolite coating 28, which increases the ability of the zeolite coating 28 to adsorb carbon dioxide (CO2) molecules from the fluid in the presence of water (e.g., moisture). This increased ability of the zeolite coating 28 to adsorb carbon dioxide (CO2) molecules from the fluid means that, among other things, type 13-X zeolites can be incorporated into the carbon capture article 10 and used for direct air capture of carbon dioxide. Although type 13-X zeolites have been used to capture carbon dioxide under dry conditions, they have not been used for direct air capture of carbon dioxide until now due to the selective adsorption of water molecules to carbon dioxide. The hydrophobicity induced by the silicone resin coating 32 of this disclosure overcomes the aforementioned problems and makes type 13-X zeolites (and more generally, zeolites) usable for direct air capture of carbon dioxide. Using 13-X type zeolite for direct air capture of carbon dioxide is beneficial because X type zeolite is relatively inexpensive compared to other adsorbents.

[0072] The method disclosed herein is superior to other attempted solutions. Efforts have been made to modify the composition of zeolite coatings to increase hydrophobicity, such as by optimizing the aluminum-to-silicon ratio, or by impregnating the pores of zeolite particles with polyethyleneimine, and other methods. However, these other attempted solutions have not been generalizable due to their relatively high cost and relatively low reaction yields.

[0073] Example

[0074] Examples 1A-1C and Comparative Examples 1A-1C—Obtaining monolithic ceramic honeycomb structures with intersecting porous walls. Each monolithic ceramic honeycomb structure is primarily made of cordierite. Each monolithic ceramic honeycomb structure is coated with 13-X type zeolite particles by impregnation coating to form a zeolite coating over the intersecting porous walls, wherein the zeolite coating faces the pathways formed by the intersecting porous walls. The zeolite coating is then calcined. After calcination, the weight of the zeolite coating in some monolithic ceramic honeycomb structures (here identified as Examples 1A and Comparative Example 1A) is 0.039 g. The weight of the zeolite coating in other monolithic ceramic honeycomb structures (here identified as Examples 1B and Comparative Example 1B) is 0.109 g. Finally, the weight of the zeolite coating in other monolithic ceramic honeycomb structures (here identified as Examples 1C and Comparative Example 1C) is 0.146 g. Comparative Examples 1A-1C are then set aside.

[0075] Each zeolite-coated ceramic cell in Comparative Examples 1A-1C was then coated with a silicone resin (specifically, a siloxane resin). The siloxane resin was then cured at 200°C to form the carbon capture article of this disclosure. After curing, the density of the siloxane resin was 5 g / L of the zeolite-coated ceramic cell.

[0076] Then, carbon dioxide (CO2) adsorption isotherms were obtained for each of Examples 1A-1C and Comparative Example 1A-1 at two different temperatures (0°C and 25°C). The volume of adsorbed CO2 (mmol / g zeolite coating) as a function of pressure (mmHg) was measured using a Micromeritics® High Pressure Volumetric Analyzer (“HPVA”) system with a 1″ sample holder. The isotherm for Comparative Example 1A-1C is shown in [the original text]. Figure 7A Reproduced in [the text]. The isotherm plot of Example 1A-1C is [in the text]. Figure 7B Reproduction was performed. No water molecules were intentionally added to the CO2 gas forced through either Example 1A-1C or Comparative Example 1A-1C. Therefore, the adsorption isotherm plots only pertain to CO2 adsorption. Between each cycle, a regeneration step was performed on the carbon capture article of Example 1A-1C and the zeolite-coated ceramic honeycomb monolith of Comparative Example 1A-1C to desorb the adsorbed carbon dioxide (CO2). The regeneration temperature of the zeolite-coated ceramic honeycomb monolith of Comparative Example 1A-1C was 350°C. The regeneration temperature of the carbon capture article of Example 1A-1C was 200°C. The lower temperature was used to avoid thermally damaging the siloxane coating.

[0077] Compare Examples 1A-1C in Figure 7A The isotherms reproduced in the example are similar to those in Example 1A-1C. Figure 7B Comparison of the regenerated isotherms reveals that the siloxane resin applied over the zeolite coating reduces the zeolite coating's ability to adsorb CO2. However, the reduction is small. For example, Comparative Example 1B absorbs approximately 6.8 mmol of CO2 per gram of zeolite coating at 0°C, while Example 1B absorbs approximately 5.8 mmol per gram. The reduction is approximately 15%. Without being bound by theory, the reduction can be attributed to (i) the siloxane coating blocking access to sites on and within the zeolite coating where carbon dioxide (CO2) molecules can otherwise adsorb, or (ii) the difference in regeneration temperature between Example 1A-1C (200°C) and Comparative Example 1A-1C (350°C), or some combination of (i) and (ii).

[0078] However, the siloxane coating present on Examples 1A-1C imparts hydrophobicity to the zeolite coating, and this hydrophobicity prevents water (H2O) molecules from occupying sites on and within the zeolite coating that CO2 molecules might otherwise occupy. In this regard, droplets or water were placed on a ceramic body coated with zeolite (type 13-X), representing Comparative Examples 1A-1C. An image was taken. [Image in...] Figure 8A Reproduced in [the image]. Similarly, droplets or water were placed on samples of each of the carbon-capturing articles Examples 1A-1C (with a siloxane coating). An image was taken. The image is in [the image]. Figure 8B Reappearance in the middle. Figure 8A and Figure 8B A comparison clearly shows that the zeolite coating (without any siloxane coating) causes the water to bead up when immersed in water, while the siloxane coating of Examples 1A-1C causes the water to bead up. Notably, the contact angle of the water droplets increases with increasing weight of the zeolite coating.

Claims

1. A carbon capture article comprising: A ceramic honeycomb assembly, comprising an inlet end, an outlet end, and intersecting walls defining a unit, through which fluid can flow from the inlet end to the outlet end; A zeolite coating, said zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb monolith; as well as A silicone resin coating that at least partially covers the zeolite coating.

2. The carbon capture article according to claim 1, wherein The zeolite coating comprises zeolite with an average pore size greater than 3.3 Å.

3. The carbon capture article according to any one of claims 1 to 2, wherein The zeolite coating comprises zeolites selected from the group consisting of: type A zeolite, type X zeolite, type Y zeolite, ZSM-5 zeolite, mordenite, magnesium alkali zeolite, chalcogenide, and clinoptilolite.

4. The carbon capture article according to claim 3, wherein The zeolite coating comprises X-type zeolite.

5. The carbon capture article according to claim 4, wherein... The zeolite coating contains 13-X type zeolite.

6. The carbon capture article according to any one of claims 1 to 5, wherein The density of the zeolite coating is in the range of 50 g / L to 300 g / L of the ceramic honeycomb material.

7. The carbon capture article according to any one of claims 1 to 6, wherein The density of the silicone resin coating is in the range of 3.0 g / L to 7.0 g / L of the ceramic honeycomb material.

8. The carbon capture article according to any one of claims 1 to 7, wherein The silicone resin coating comprises a siloxane resin.

9. The carbon capture article according to claim 8, wherein The siloxane resin is alkoxy-functionalized.

10. The carbon capture article according to claim 9, wherein The siloxane resin is methoxy-functionalized.

11. The carbon capture article according to claim 8, wherein The silicone resin coating comprises one or more silsesquioxane resins.

12. The carbon capture article according to any one of claims 1 to 11, wherein When a fluid containing carbon dioxide (CO2) molecules and water (H2O) molecules flows through the carbon capture article, the carbon capture per gram of zeolite coating exhibited by the carbon capture article at 0°C is greater than the carbon capture per gram of zeolite coating exhibited by the otherwise identical carbon capture article at 0°C when the same fluid flows through it without the silicone resin coating.

13. The carbon capture article according to any one of claims 1 to 12, wherein When air containing carbon dioxide (CO2) molecules and water molecules (CO2) flows through the carbon capture article as the fluid, the carbon capture article exhibits a carbon capture of greater than 2.0 mmol CO2 / g zeolite coating at 0°C.

14. A method for manufacturing a carbon capture article, the method comprising: A ceramic honeycomb substrate is used, which includes an inlet end, an outlet end, and intersecting walls defining the cells, through which fluid can flow from the inlet end to the outlet end; A silicone coating step, the silicone coating step comprising coating a silicone resin coating at least partially onto a zeolite coating to form a carbon capture article, the zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb monolith.

15. The method of claim 14, wherein The silicone coating step further includes curing the silicone resin coating to form the carbon capture article.

16. The method according to any one of claims 14 to 15, wherein The silicone resin coating comprises a siloxane resin.

17. The method of claim 16, wherein The siloxane resin is alkoxy-functionalized.

18. The method of claim 17, wherein The siloxane resin is methoxy-functionalized.

19. The method according to any one of claims 14 to 15, wherein The silicone resin coating comprises silsesquioxane resin.

20. The method according to any one of claims 14 to 19, wherein Applying the silicone resin coating at least partially onto the zeolite coating involves immersing the zeolite coating, which at least partially covers the ceramic honeycomb material, in a solution of solvent and silicone resin.

21. The method according to any one of claims 14 to 20, further comprising: The zeolite coating forming step comprises (i) coating zeolite particles onto at least a portion of the intersecting walls of the ceramic honeycomb substrate, and (ii) calcining the zeolite particles.

22. The method of claim 21, wherein Coating the zeolite particles onto at least a portion of the intersecting walls of the ceramic honeycomb assembly comprises immersing at least a portion of the ceramic honeycomb assembly in a solution of water and the zeolite particles.

23. A method for capturing carbon dioxide from the air, the method comprising: A flow step, comprising flowing a fluid containing carbon dioxide (CO2) molecules through a carbon capture article, the carbon capture article comprising: A ceramic honeycomb assembly, comprising an inlet end, an outlet end, and intersecting walls defining a unit, through which fluid can flow from the inlet end to the outlet end; A zeolite coating, said zeolite coating at least partially covering the intersecting walls of the ceramic honeycomb monolith; as well as A silicone resin coating, wherein the silicone resin coating is at least partially disposed on the zeolite coating. At least a portion of the carbon dioxide (CO2) molecules are captured by the carbon capture article.

24. The method of claim 23, wherein The fluid also contains water (H2O) molecules.

25. The method according to any one of claims 23 to 24, wherein The fluid is air.

26. The method according to any one of claims 23 to 25, further comprising: A regeneration step, the regeneration step comprising applying heat energy to the carbon capture article in which the carbon dioxide (CO2) molecules are captured, until at least a portion of the carbon dioxide (CO2) molecules are released from the carbon capture article.

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