Systems and methods for fluid capture using silicon-containing cross-linked binders

Abstract

Described herein are adsorbents functionalized with ligands having amino silicone functional groups. Also described herein are methods of making adsorbents functionalized with ligands having amino silicone functional groups. Also described herein are methods of using adsorbents functionalized with ligands having amino silicone functional groups.

Description

BACKGROUND

[0001] The subject matter disclosed herein relates to techniques for capturing one or more target fluids. More specifically, the subject matter disclosed herein relates to forming a fluid capture material or coating using a binder and sorbent combination or mixture.

[0002] Certain industrial systems can produce a variety of fluids, such as water and carbon dioxide (CO2), during operation of the industrial systems. In certain instances, the fluids can be emitted as exhaust gases or otherwise not utilized. Certain components (e.g., substrates) of the industrial systems can include a coating capable of capturing or extracting the fluids. SUMMARY

[0003] The following outlines certain embodiments that are commensurate in scope with the originally filed claims. These embodiments are not intended to limit the scope of the present technology, but rather these embodiments are only intended to provide a brief overview of possible forms of the present technology. Indeed, the systems and methods of the present invention can include a variety of forms that can be similar or different from the embodiments set forth below.

[0004] In one embodiment, the present disclosure relates to a gas capture system. The gas capture system includes a substrate and a gas capture material formed on one or more surfaces of the substrate. The gas capture material includes a sorbent material that binds one or more gases. The gas capture material also includes one or more silicon-containing binder materials, and the one or more silicon-containing binders are at least partially cross-linked.

[0005] In one embodiment, the present disclosure relates to a method. The method includes providing a sorbent material that binds one or more gases. The method also includes providing a plurality of binder materials, where the plurality of binder materials includes a silicon-containing binder material. Further, the method includes producing a sorbent-binder material using the sorbent material, the plurality of binder materials, and a solvent. Still further, the method includes forming a fluid capture material using the sorbent-binder material applied to a substrate, where the fluid capture material includes a cross-linked composite material.

[0006] In one embodiment, the present disclosure relates to a gas capture system. The gas capture system includes a fluid capture material that binds one or more fluids. The fluid capture material includes a sorbent material that binds one or more fluids, the one or more fluids including water, carbon dioxide, sulfur oxides, or combinations thereof. Further, the fluid capture material includes a plurality of binder materials, the plurality of binder materials including a silicon-containing binder material and a vinyl binder material, where the plurality of binder materials are at least partially cross-linked. Still further, the fluid capture material includes a fluid contactor having one or more surfaces coated with the fluid capture material. Attached Figure Description

[0007] These and other features, aspects, and advantages of the invention will be better understood when the following detailed description is read with reference to the accompanying drawings, in which the same reference numerals denote the same parts throughout the drawings, wherein:

[0008] Figure 1 This is a flowchart of an embodiment of a method for capturing a target fluid using a fluid capture system having one or more substrates, according to the present disclosure;

[0009] Figure 2 It is in accordance with this disclosure for use in Figure 1 A flowchart of an implementation scheme for using a combination of binders and adsorbents in a fluid capture system to produce a fluid capture material;

[0010] Figure 3 It is coated with according to this disclosure Figure 2 A cross-sectional view of an embodiment of a fluid trapping material substrate;

[0011] Figure 4 It is a graph depicting the carbon dioxide (CO2) concentration versus time of a fluid flow guided to a substrate having a fluid trapping material according to the present disclosure;

[0012] Figure 5 This is a visual flowchart illustrating the operational aspects of a fluid trapping system according to this disclosure, having one or more substrates coated with a fluid trapping material; and

[0013] Figure 6 It is a graph depicting the weight increase of a substrate with a fluid trapping material exposed to a fluid flow as per the present disclosure over time. Detailed Implementation

[0014] One or more specific embodiments of this disclosure will now be described. To provide a concise description of these embodiments, not all features of the actual implementation may be described in the specification. It should be understood that, as in any engineering or design project, numerous implementation-specific decisions must be made in the development of any such implementation to achieve the developer's specific objectives, such as complying with system-related and business-related constraints, which may vary from implementation to implementation. Furthermore, it should be understood that such development work may be complex and time-consuming, but remains a routine task of design, fabrication, and manufacturing for those skilled in the art who benefit from this disclosure.

[0015] When describing the elements of various examples of this disclosure, the articles “a,” “the,” and “the” are intended to mean one or more elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that additional elements may exist in addition to the listed elements. Furthermore, it should be understood that references to “an example” or “example” in this disclosure are not intended to be construed as excluding the existence of other examples that also include the listed features.

[0016] In the context of this invention, the terms “about” or “approximately” are intended to indicate that the indicated value is not precise and that the actual value may differ from the indicated value without substantially altering the manner in which the relevant operation is performed. For example, the terms “about” or “approximately” as used herein are intended to convey a suitable value within a particular manufacturing or operating tolerance (e.g., ±10%, ±5%, ±1%, ±0.5%), as will be understood by those skilled in the art.

[0017] As generally discussed herein, certain systems (e.g., gas turbines) that generate one or more fluids (e.g., water, CO2, H2S, and / or other fluids) may include one or more substrates having a surface coating that incorporates the one or more fluids, thereby extracting or capturing the one or more fluids from a source fluid (e.g., exhaust gas streams and ambient air streams). For example, these systems may include combustion systems that utilize a fuel source (e.g., fossil fuels). Thus, one or more substrates of these combustion systems may include a surface coating capable of extracting carbon dioxide. As another non-limiting example, these systems may include water capture systems that typically include a surface coating capable of extracting water from ambient air. In some embodiments, it may be desirable to capture at least a portion of these fluids, such as to address the guidance (e.g., government regulation) and / or utilize the one or more fluids, rather than not capturing them, such as by discharging or otherwise releasing them into the surrounding airspace or other adjacent environment.

[0018] This disclosure relates to techniques for improving the efficiency of capturing or extracting certain fluids from a fluid flow by using an adsorbent material (e.g., an adsorbent component) and a crosslinkable binder material and crosslinking the binder material (e.g., using a crosslinking agent) to form a fluid-capturing material or fluid-capturing coating. As described in more detail herein, adsorbent materials typically include materials capable of binding certain fluids, such as undesirable gases (e.g., greenhouse gases, acid gases, etc.), water (H2O), oxygen (O2), or other gas molecules that can be formed due to decomposition reactions (e.g., combustion). For example, undesirable gases may include carbon oxides (CO). X Such as carbon dioxide (CO2) and carbon monoxide (CO), nitrogen oxides (NO) X Such as nitrogen dioxide (NO2) and sulfur oxides (SO4).X Examples of fluid trapping agents include sulfur dioxide (SO2) and / or hydrogen sulfide (H2S). For instance, adsorbent materials may include metal-organic frameworks (MOFs) and / or covalent organic frameworks (COFs). In some embodiments, adsorbent materials may include polymeric resins, silica, zeolites, and other materials capable of trapping fluids as discussed herein. Binder materials may include one or more materials that prevent, reduce, or mitigate the decomposition or dissolution of the adsorbent material (i.e., improve stability). As described in more detail herein, it is now recognized that using adsorbent materials and cross-linked binder materials to form fluid trapping materials can provide improved fluid binding capacity (e.g., in a reversible or irreversible manner) compared to conventional fluid-binding materials or coatings.

[0019] More specifically, the disclosed fluid trapping material or coating can be formed by crosslinking a binder material capable of forming a crosslinked polymer. In at least some cases, the disclosed fluid trapping material may include a portion (e.g., by mass percentage) of a crosslinked polymer (e.g., a crosslinked binder material). For example, such a portion may be less than 20% by mass, between 1% and 15% by mass, between 5% and 10% by mass, or less than 10% by mass of the total mass of the fluid trapping material. Generally, the crosslinked polymer can be formed using thermal techniques, radiation techniques (e.g., irradiation with ultraviolet (UV) light), and / or chemical techniques (e.g., via free radical polymerization or condensation reaction using a crosslinking agent). In embodiments using a crosslinking agent, the fluid trapping material may also include the crosslinking agent. That is, the crosslinking agent may be present in the fluid trapping material. It is currently recognized that fluid trapping materials comprising cross-linked polymers (e.g., fluid trapping materials formed using cross-linked polymers) can produce fluid trapping materials with a relatively large amount of adsorbent (e.g., a relatively small amount of binder material (e.g., less than 15% by mass, less than 12% by mass, less than 10% by mass, less than 8% by mass, less than 5% by mass) compared to fluid trapping materials formed using uncross-linked and / or non-cross-linked binders or polymers). Therefore, increasing the amount of adsorbent material improves the fluid binding capacity of the fluid trapping material by having a larger amount of adsorbent material in the fluid trapping material. Furthermore, by forming the fluid trapping material with a cross-linked polymer, the disclosed fluid trapping material can have improved adhesion or bonding to substrates (e.g., metal substrates, polymer substrates (e.g., glass-filled nylon), polymer composite substrates, etc.) and improved stability or resistance to dissolution.

[0020] With this in mind, Figure 1This is a flowchart of an embodiment of a method 10 for capturing or extracting fluid from a fluid stream. As shown, a fluid capture system 12 receives fluid from a fluid source 14. In some embodiments, the fluid capture system 12 includes a gas capture system, such as a carbon capture system. Generally, the fluid source 14 may include an exhaust fluid stream (e.g., an exhaust gas stream) and / or ambient air. As described herein, the fluid source 14 may include one or more target fluids (e.g., one or more target gases) that may be desired to capture or otherwise extract or separate from the exhaust fluid stream. For example, it may be desirable to capture certain combustion products (e.g., undesired gases). For example, undesired gases may include carbon oxides (CO). X Such as carbon dioxide (CO2) and carbon monoxide (CO), nitrogen oxides (NO) X Such as nitrogen dioxide (NO2) and sulfur oxides (SO4). X Such as sulfur dioxide (SO2) and / or hydrogen sulfide (H2S). Therefore, in some cases, the fluid capture system 12 (e.g., a carbon capture system) can be configured to capture carbon-containing gases (e.g., CO). X Such as CO and CO2) to reduce carbon emissions entering the environment (e.g., according to certain regulations). Additionally or alternatively, the fluid capture system 12 (e.g., a water capture system) may be configured to capture H2O to reduce the moisture content of the airflow. As another non-limiting example, the fluid capture system 12 (e.g., nitrogen oxides (NOx)) may be configured to capture H2O to reduce the moisture content of the airflow. x The capture system can be configured to capture NO present in the exhaust gas. x As another non-limiting example, fluid capture system 12 (e.g., sulfur oxides (SO₄)) x The capture system can be configured to capture SO2 present in the exhaust gas. x As another non-limiting example, the fluid capture system 12 (e.g., a hydrogen sulfide (H2S) capture system) may be configured to capture H2S present in fuel gas. In any case, the fluid capture system 12 typically receives fluid from a fluid source 14, and one or more substrates 16 of the fluid capture system 12 extract one or more target fluids 18 from the fluid from the fluid source 14, thereby producing a purified gas stream 20.

[0021] In some embodiments, the fluid capture system 12 may be provided as part of a gas turbine system, a chemical production system, or other system that generates a fluid flow (e.g., a gas flow, an exhaust gas flow) containing gas molecules that may be desired to be captured. As shown, the fluid capture system 12 may include one or more substrates 16. As described herein, the substrate 16 may include a coating formed of one or more semi-permeable materials (e.g., materials capable of allowing certain gases to permeate through the substrate) capable of binding certain fluids (i.e., target fluid 18 or gas). For example, the coating may be a fluid capture material formed using an adsorbent material and a binder material capable of forming a cross-linked polymer.

[0022] As described herein, fluid trapping materials can improve the amount of target fluid 18 extracted from fluid source 14 and / or may have improved stability compared to certain coatings used for extracting fluid from fluid source 14. To illustrate this, Figure 2 This is a flowchart of an embodiment of a method 30 for generating air contact with a fluid trapping material.

[0023] To begin method 30, at block 32, an adsorbent-binder material 38 is generated using adsorbent material 34, binder material 36, and crosslinking agent 37. Generally, the use of adsorbent material 34, binder material 36, and crosslinking agent may include forming a mixture, such as a solution or slurry comprising adsorbent material 34 and binder material 36 in a suitable solvent capable of dissolving at least a portion of the adsorbent material and / or binder material. Examples of such solvents include, but are not limited to, toluene, ethyl acetate, ethanol, 2-(2-butoxyethoxy)ethyl acetate, water, isopropanol, methyl ethyl ketone, or any combination thereof (i.e., for miscible solvents). As discussed herein, crosslinking agent 37 may include certain chemical crosslinking agents. Therefore, crosslinking agent 37 may also be added to the mixture of adsorbent material 34 and binder material 36. In some embodiments, crosslinking agent 37 may be added after the mixture of adsorbent material 34 and binder material 36 has been formed. For example, in embodiments where the binder material 36 is a polymer material, the crosslinking agent 37 may be added after a time period corresponding to a suitable degree of polymerization of the binder material 36 (e.g., after initiating the polymerization of the binder material 36). However, in some embodiments, the crosslinking agent 37 may be added before initiating the polymerization of the binder material 36.

[0024] The adsorbent material 34 is typically a material capable of adsorbing fluids such as water and / or undesirable gases (e.g., CO2). In some embodiments, the adsorbent material 34 may comprise a metal-organic framework (MOF) and / or a covalent organic framework (COF). For example, the adsorbent material may comprise MOFs capable of adsorbing fluids as described herein, such as iron-based MOFs, zirconium-based MOFs (e.g., MOF-808, such as MOF-808-Gly), aluminum-based MOFs (e.g., MOF-303, MIL-160), zeolite imidazole ester frameworks (ZIFs), amine-containing MOFs, other MOFs, amine-containing COFs, ZIFs, and silica, etc. In some embodiments, the adsorbent material 34 may comprise a polymer resin, silica, zeolite, or a combination thereof. In some embodiments, the adsorbent material 34 includes coordination framework compounds, porous coordination polymers (PCPs), crystalline porous materials, crystalline open frameworks, network chemical components, silica particles, zeolites, silica-alumina-phosphate (SAPO), aluminum-phosphate (AlPO), polyaromatic frameworks (PAFs), activated carbon, molecular organic solids, and combinations thereof or selected from the group consisting of them.

[0025] As mentioned in this article, MOF compounds are a class of compounds comprising metal ions or clusters that coordinate with organic ligands to form one-dimensional, two-dimensional, or three-dimensional structures. The metal ions or clusters act as junctions and are bound via multidirectional organic ligands, which act as connectors within the network structure. MOF compounds possess modular properties that allow for tunable synthesis, providing fine chemicals and structural control. Properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications.

[0026] In some embodiments, the adsorbent is a MOF metal or a MOF compound containing a metal cluster and a MOF linker. In some embodiments, the MOF metal of the adsorbent material 34 can be any suitable MOF metal known in the art that promotes the functionalization of the adsorbent described herein. In other embodiments, the MOF metal is a metal selected from the group consisting of: alkali metals, alkaline earth metals, transition metals, Ca, Mn, Cr, Fe, Co, Ni, Cu, Zn, their ions, their hydrates, their salts, their halides, their fluorides, their chlorides, their bromides, their iodides, their nitrates, their acetates, their sulfates, their phosphates, their carbonates, their oxides, their formates, their carboxylates, and combinations thereof. In some embodiments, the MOF metal includes Mg.

[0027] The binder material 36 may comprise one or more oligomer or polymer materials, polymerizable monomers or oligomers, or combinations thereof. In at least some embodiments, the binder material 36 may improve the affinity of the adsorbent material 34 for a gas or gases and / or improve the stability (e.g., thermal stability) of the adsorbent material 34. In some embodiments, the binder material 36 may comprise materials that form polymers having a thermal stability of about 200°C. In some embodiments, the binder material 36 may comprise silicone-containing polymers or binders (e.g., siloxanes or silanes, such as aminopropyl silsesquioxane, aminoethylaminopropyl silsesquioxane, alkoxysilane), vinyl polymers (e.g., polyvinyl esters, such as polyvinyl acetate; polyvinyl alcohol) and their copolymers such as polyvinyl butyral. In some embodiments, the binder material 36 may comprise polysaccharides (e.g., ethyl cellulose, starch, and alkyl cellulose), and nitrogen-containing polymers (e.g., polyethyleneimine (PEI)). In some embodiments, the binder material 36 may comprise combinations of the aforementioned polymers (i.e., two, three, four, or more than four of these polymers). For example, the binder material 36 may be a “hybrid binder mixture.” As mentioned herein, a “hybrid binder mixture” may include a mixture or blend of different types of binder materials, such as a mixture of organic polymers and silsesquioxane binders, or other combinations of binder materials described herein. In at least some cases, the binder material 36 may be selected to enhance the adsorption of the target fluid onto a coating (e.g., a fluid trapping material) created using the adsorbent material 34. For example, in embodiments using PEI as the binder material, the PEI may include PEI-low (e.g., M... W Between approximately 20,000 g / mol and 25,000 g / mol, and M n Between approximately 8,000 g / mol and 12,000 g / mol) or PEI-high (e.g., M W Between approximately 70,000 g / mol and 80,000 g / mol, and M n Between approximately 55,000 g / mol and 65,000 g / mol.

[0028] As described herein, the binder material 36 can be a crosslinkable polymer material. That is, it is now recognized that the formation of a fluid trapping material in which at least a portion of the polymer portion of the adsorbent-binder material 38 is a crosslinked polymer can reduce the likelihood of decomposition and / or dissolution of the fluid trapping material 34. Furthermore, the use of a crosslinked polymer allows the fluid trapping material to have a relatively large amount of adsorbent material bound to the target fluid 18, and thus a higher fluid binding capacity compared to a coating formed without a crosslinked polymer. In other words, conventional techniques for combining adsorbent material 34 and binder material 36 can produce fluid-binding materials with a relatively low fluid binding capacity compared to the adsorbent material (e.g., due to a dilution effect or knockdown effect). It is now recognized that crosslinking the binder material 36 can produce a fluid trapping coating or fluid trapping material with a relatively high binding capacity compared to not crosslinking the binder material 36. Furthermore, the binding capacity of the disclosed fluid trapping coating or material (i.e., including cross-linked binder materials) may be approximately equal to the binding capacity of the adsorbent material 34 itself (e.g., adsorbent material 34 in powder form).

[0029] In one embodiment, the binder material 36 comprises a self-crosslinking material. For example, the binder material 36 may comprise silanol (SiOH) functional groups and / or alkoxysilane (SiOR) functional groups. It should be noted that binder materials 36 containing such functional groups can undergo intermolecular condensation reactions, which result in crosslinking of the binder material 36 upon heating. For example, it is currently recognized that amine-containing components (e.g., amine-containing MOFs) can cause certain binder materials 36 (e.g., epoxy resins) to crosslink. As another non-limiting example, amine-containing components can crosslink certain Si-O or R2-Si-O (where R = alkyl group) polymeric structures (such as silsesquioxanes) to form crosslinked Si-O or R2-Si-O polymeric structures (e.g., amine-impregnated organosilicon).

[0030] In one embodiment, the binder material comprises a polyvinyl alcohol polymer. Suitable polyvinyl alcohol polymers include, but are not limited to, polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers. In one embodiment, the binder polymer composition comprises a polyvinyl alcohol-polyvinylamine copolymer (PVA-PVAm) containing a first crosslinkable functional group and a second crosslinkable functional group. Although polyvinyl alcohol derivatives are suitable for the practice of this invention, other polymeric materials may also be used in the binder polymer composition, including, but not limited to, polyacrylates, polymethacrylates, polyhydroxyethyl methacrylates, and functionalized polyarylenes containing amines, carboxylic acids, amides, hydroxyl moieties, etc. In one embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one polymer with a number average molecular weight greater than about 2,500 Daltons. In another embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one polymer with a number average molecular weight in the range of greater than 2,500 Daltons to about 500,000 Daltons. In yet another embodiment, the binder polymer composition for preparing the fluid trapping material comprises at least one hydrophilic polymer with a number average molecular weight in the range of about 75,000 Daltons to about 250,000 Daltons. Number-average molecular weight can be determined using a variety of techniques known to those skilled in the art, including 1 H-NMR spectroscopy and gel permeation chromatography (GPC).

[0031] As described above, adhesive material 36 may include a PVA copolymer. In some embodiments, adhesive material 36 may include a copolymer formed by the reaction of PVA with alkyl aldehydes and / or acetates. For example, adhesive material 36 may include polyvinyl butyral or other “Butvar” polymers. In at least some cases, it may be advantageous to use a PVA copolymer having 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, or 10% or less of unreacted hydroxyl groups of PVA. It is recognized that the use of such PVA copolymers can be used for crosslinking as described herein. As several non-limiting examples, adhesive material 36 may include: Butvar-79, which includes between approximately 11.0% and 13.5% unreacted hydroxyl groups of PVA; Butvar-98, which includes between approximately 18% and 20% unreacted hydroxyl groups of PVA; or combinations thereof.

[0032] As described above, the adhesive material 36 may comprise a mixture of crosslinkable polymeric materials. For example, the adhesive material 36 may comprise a mixture of polyvinyl alcohol (PVA) and polyacrylic acid (PAA). For example, the mixture may comprise 10% by weight of PVA and 90% by weight of PAA, 30% by weight of PVA and 70% by weight of PAA, 50% by weight of PVA and 50% by weight of PAA, 70% by weight of PVA and 30% by weight of PAA, or 90% by weight of PVA and 10% by weight of PAA.

[0033] In some embodiments, the binder material 36 may be dissolved in a solvent to a specific viscosity. For example, in embodiments where the binder material 36 comprises ethyl cellulose, the binder material 36 may comprise a 7-15 cP solution in a 6% toluene-ethanol solution. When dissolved in a 1:1 toluene-2-(2-butoxyethoxy)ethyl acetate solvent, the resulting slurry may comprise 30% solids and 11% binder. As another non-limiting example, in embodiments where the binder material 36 comprises ethyl cellulose, the binder material 36 may comprise a solution of approximately 300 cP in a 5% toluene-ethanol solution.

[0034] Generally, the amount of crosslinking agent 37 can be less than the amount of binder material 36. In some embodiments, the ratio of crosslinking agent 37 added to binder material 36 to form adsorbent-binder composite material 38 can be less than about 1 / 3, less than about 1 / 4, less than about 1 / 5, or less than about 1 / 6. For example, adsorbent-binder composite material 38 can be formed by mixing 10% by mass of a binder material 36 solution and 2% by mass of a crosslinking agent 37 solution (i.e., the ratio of crosslinking agent 37 to binder material 36 is 1 / 5).

[0035] It should be noted that, at least in some cases, crosslinking agent 37 can also be adhesive material 36. That is, crosslinking agent 37 can be a polymer capable of crosslinking. For example, PAA can be used as a crosslinking agent for PVA.

[0036] As described herein, crosslinking agent 37 crosslinks the binder material 36. In some embodiments, the degree of crosslinking (i.e., crosslinking density, which refers to the density of chains or segments connecting two parts of the polymer network, rather than the density of crosslinking junctions) may be greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%.

[0037] Regarding the adsorbent-binder material 38 (e.g., an adsorbent-binder composite material), the amounts of the binder material 36 and the adsorbent material 34 may be such that the adsorbent-binder material 38 comprises more than 50% adsorbent material, more than 60% adsorbent material, more than 70% adsorbent material, more than 80% adsorbent material 34, more than 85% adsorbent material 34, or more than 90% adsorbent material 34.

[0038] A wide variety of crosslinking agents can be used to react with binders, and these crosslinking agents can be monomers, oligomers, or polymers, or combinations thereof. In some embodiments, crosslinking agent 37 may include chemical crosslinking agents such as epoxy resins and acid anhydrides. In some embodiments, crosslinking agent 37 may include one or more materials such as nanoparticles, micron-sized particles, or larger particles, or molecular precursors that can form particles. For example, the crosslinking agent may include silica particles, such as colloidal silica. In some embodiments, the crosslinking agent may include silanes (e.g., tetraalkoxysilanes). In some embodiments, crosslinking agent 37 may include particles with different size distributions. That is, crosslinking agent 37 may include particles with a first size distribution and a second size distribution. For example, crosslinking agent 37 may have a micron-sized distribution. In some embodiments, crosslinking agent 37 may have a nanon-sized distribution and a micron-sized distribution (i.e., a bimodal size distribution). In at least some cases, a bimodal size distribution can improve abrasion resistance. In embodiments where crosslinking agent 37 includes particles with different size distributions, the mixture of particles may vary. For example, the mixture may include 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc., of nano-sized particles and 90 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, 30 wt%, etc., of micron-sized particles. In embodiments where the crosslinking agent 37 comprises particles (e.g., micron-sized particles, nanoparticles, or larger particles), the particles may have a shape distribution. For example, the crosslinking agent 37 may comprise 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 95% spherical micron-sized particles. In at least some cases, the combination of particle shape (e.g., spherical) and different size distributions can improve the properties of the resulting fluid trapping material discussed herein.

[0039] In some embodiments, the crosslinking agent 37 comprises functional groups sensitive to the formation of free radicals induced by exposure to high-energy irradiation (e.g., ultraviolet light or electron beams) and / or heat. Those skilled in the art will appreciate that the structure of a free radical is understood to determine its reactivity, and the structure of the crosslinking agent can be selected to provide higher or lower levels of chemical reactivity for free radicals generated by such crosslinkable functional groups under irradiation or heat exposure. In one embodiment, the crosslinking agent comprises functional groups capable of forming secondary or tertiary aliphatic or cycloaliphatic free radicals. In another alternative embodiment, the crosslinking agent comprises functional groups capable of forming aromatic free radicals (e.g., benzyl free radicals). Other crosslinkable functional groups include methacrylates, acrylates, acrylamides, vinyl ketones, styrene derivatives, vinyl ethers, vinyl groups, allyl groups, benzyl groups, and groups containing tertiary carbon-hydrogen bonds, such as isobutyl groups.

[0040] Suitable crosslinking agents 37 include, but are not limited to, methacrylates, acrylates, and vinyl ketones. These agents can covalently bond with the binder material or self-form crosslinked polymers upon exposure to high-energy radiation or heat. For example, suitable crosslinking agents include, but are not limited to, the following reagents: acryloyl chloride, (2E)-2-butenoyl chloride, maleic anhydride, 2(5H)-furanone, methyl acrylate, 5,6-dihydro-2H-pyran-2-one, ethyl acrylate, methyl crotonate, allyl acrylate, vinyl crotonate, ethyl 2-isocyanate methacrylate, methacrylic acid, methacrylic anhydride, methacryloyl chloride, glycidyl methacrylate, 2-ethylacryloyl chloride, 3-methylenedihydro-2(3H)-furanone, 3-methyl-2(5H)-furanone, methyl 2-methacrylate, trans-2-methoxyacrylate, citraconic anhydride, itaconic anhydride, (2E)-2-methyl-2-butenoic acid methyl ester, ethyl 2-methacrylate, ethyl 2-cyanoacrylate, dimethyl... Lemon anhydride, allyl 2-methacrylate, ethyl (2E)-2-methyl-2-butenoate, ethyl 2-ethyl acrylate, methyl (2E)-2-methyl-2-pentenoate, 2-hydroxyethyl 2-methacrylate, methyl 2-(1-hydroxyethyl)acrylate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(diethoxymethylsilyl)propyl methacrylate, 3-(trichlorosilyl)propyl 2-methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-tris(trimethylsiloxy)silylpropyl methacrylate, 6-dihydro-1H-cyclopenta(c)furan-1,3(4H)-dione, methyl 2-cyano-3-methylcrotonate, trans-2,3-dimethacrylic acid, and N-(hydroxymethyl)acrylamide.

[0041] Suitable vinyl and allyl reagents that can be used as crosslinking agents include, but are not limited to, allyl bromide, allyl chloride, diene ketone, 5-methylene dihydro-2(3H)-furanone, 3-methylene dihydro-2(3H)-furanone, 2-chloroethyl vinyl ether and 4-methoxy-2(5H)-furanone.

[0042] Suitable isocyanate reagents that can be used as crosslinking agents include, but are not limited to, vinyl isocyanate, allyl isocyanate, furfuryl isocyanate, 1-ethyl-4-isocyanate phenylene, 1-ethyl-3-isocyanate phenylene, 1-(isocyanate methyl)-3-methylbenzene, 1-isocyanate methyl-3,5-dimethylbenzene, 1-bromo-2-isocyanate ethane, (2-isocyanate ethyl)benzene, 1-(isocyanate methyl)-4-methylbenzene, 1-(isocyanate methyl)-3-methylbenzene, 1-(isocyanate methyl)-2-methylbenzene, etc.

[0043] Suitable styrene reagents that can be used as crosslinking agents include, but are not limited to, 3-vinylbenzaldehyde, 4-vinylbenzaldehyde, 4-vinylbenzyl chloride, trans-cinnamoyl chloride, phenyl maleic anhydride, 4-hydroxy-3-phenyl-2(5H)-furanone, etc.

[0044] Suitable epoxide reagents that can be used as crosslinking agent 37 include, but are not limited to, glycidyl methacrylate, glycidyl vinyl ether, 2-(3-butenyl)ethylene oxide, 3-vinyl-7-oxabicyclo[4.1.0]heptane, limonene oxide, etc.

[0045] In some embodiments, the crosslinking agent 37 may include multiple (e.g., two, three, or more than three) different types of functional groups that can promote the formation of the fluid trapping material 44. Generally, the crosslinking agent 37 may include a first functional group that reacts with the binder material 36 and a crosslinkable second functional group. For example, the crosslinking agent 37 may include anhydride and acrylate functional groups, epoxide and acrylate functional groups, isocyanate and methacrylate functional groups, etc. As a non-limiting example, the binder material 36 may include poly(vinyl alcohol) and the crosslinking agent 37 may include ethyl 2-isocyanate methacrylate (2-IEM), which includes both isocyanate and methacrylate functional groups. As another non-limiting example, the binder material 36 may include poly(vinyl butyral) and the crosslinking agent 37 may include 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane.

[0046] In some embodiments, one or more additives may be added to form the adsorbent-binder material 38. For example, the additive may include a dispersant to promote the formation of a suspension, such as anionic dispersants, cationic dispersants, nonionic dispersants, defoamers, wetting agents, thickeners, or any combination thereof. Suitable anionic dispersants may include polymeric alkoxylates or phosphate esters. Suitable nonionic dispersants may include polyurethanes. Suitable cationic dispersants may include polyoxyethylene fatty ammonium sulfate. Generally, the amount of dispersant added may be less than the amount of binder material 36. For example, the adsorbent-binder material 38 may include 10% by weight of binder material 36 and 0.5% by weight of dispersant, 1% by weight of dispersant, or more than 1% by weight of dispersant. As another non-limiting example, the adsorbent-binder material 38 may include 15% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or more than 5% by weight of dispersant. As another non-limiting example, the adsorbent-binder material 38 may include 13% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or more than 5% by weight of dispersant. For example, in an example adsorbent-binder material 38 where binder material 36 is aminopropylsilsesquioxane, binder material 36 may be formed using a binder solution having 13% binder and 2% dispersant. The dispersant may include polyethyleneimine (PEI), such as PEI-low (e.g., M... W Between approximately 20,000 g / mol and 25,000 g / mol, and M n Between approximately 8,000 and 12,000) or PEI-high (e.g., M W Between approximately 70,000 g / mol and 80,000 g / mol, and M n Between approximately 55,000 and 65,000.

[0047] In block 40, adsorbent-binder material 38 is deposited, applied to, integrally formed therewith (e.g., during manufacturing), or otherwise attached thereto, such as to one or more surfaces of substrate 16, thereby forming a fluid-capturing coated substrate 42. In some embodiments, the substrate may include certain metallic substrates (e.g., aluminum, titanium) or 3-D printed metallic substrates. For example, substrate 16 may include a fluid contactor having a metallic surface. In some embodiments, substrate 16 includes a metallic alloy (e.g., chromium-nickel-iron alloy or stainless steel). As mentioned herein, a “fluid contactor” or “direct fluid contactor” refers to a structure configured to receive a flow of fluid, and this structure may include porous and / or semi-porous materials such that a portion of the fluid flow can permeate through the fluid contactor. In some embodiments, the fluid flow may include an ambient air flow. In some embodiments, the fluid flow may include a flue gas flow or exhaust gas flow from a power generation device (e.g., a gas turbine). Therefore, the binder material 36 may be selected to have relatively high adhesion to metallic surfaces.

[0048] In some embodiments, the substrate 16 may be a polymer or a polymer composite. Polyolefins (e.g., polyethylene, polypropylene, polymethylpentene, polystyrene, substituted polystyrene, poly(vinyl chloride) (PVC), polyacrylonitrile), polyamides, polyesters, polysulfones, polyethers, acrylic and methacrylic polymers, polystyrene, polyurethanes, polycarbonates, polyesters (e.g., polyethylene terephthalate, polybutylene terephthalate), polyethersulfones, polypropylene, polyethylene, polyphenylene sulfones, cellulose polymers, polyphenylene ethers, polyamides (e.g., nylon, polyphenylene terephthalamide), and combinations of two or more of the aforementioned polymers may be used as the substrate. Fluoropolymers that can be used as substrates include, but are not limited to, ePTFE, polyvinylidene fluoride (PVDF), poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP), poly(ethylene-alternating-tetrafluoroethylene) (ETFE), polychlorotrifluoroethylene (PCTFE), poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP), and polyvinyl fluoride (PVF).

[0049] Generally, depositing adsorbent-binder material 38 onto substrate 16 may include curing the adsorbent-binder material 38, including crosslinking agent 37, to form a fluid trapping material 44 or coating of polymer and adsorbent composite material. In other words, fluid trapping material 44 refers to adsorbent-binder material 38, wherein binder material 36 is crosslinked by one or more crosslinking agents 37. As described herein, crosslinking of adsorbent-binder material 38 can provide a material and / or coating (i.e., fluid trapping material 44) with relatively high structural integrity compared to non-crosslinked adsorbent-binder material 38. Furthermore, crosslinking of adsorbent-binder material 38 can provide a material and / or coating with relatively high binding capacity to fluids.

[0050] It should be noted that, at least in some cases, the adsorbent-binder material 38 may be deposited multiple times on the substrate 16. It is recognized that, at least in some cases, depositing relatively thick layers (e.g., greater than 1 mm, greater than 2 mm, or greater than 5 mm) can result in one or more cracks in the fluid trapping material 44 (e.g., the fluid trapping material or fluid trapping coating). Therefore, to reduce, prevent, or mitigate cracking (e.g., mud cracking), depositing multiple layers to ultimately form a fluid trapping material 44 with a desired thickness (e.g., between 0.1 mm and 0.9 mm, between 1.1 mm and 1.3 mm, between 0.1 mm and 2.0 mm, between 2.5 mm and 3.5 mm) may be advantageous. For example, the fluid trapping material 44 may comprise three layers with a total thickness of 1.2 mm. As another non-limiting example, the fluid trapping material may comprise six layers with a total thickness of 3 mm. For example, to deposit multiple layers, method 30 may include depositing a first amount of adsorbent-binder material 38, curing the first amount of adsorbent-binder material to form a first layer, and repeating the method once or more to form one or more additional layers, thereby forming a fluid trapping material having multiple layers (e.g., 2, 3, 4, 5, 6, 7). In some embodiments, the first layer of fluid trapping material 44 may be pre-wetted before the addition of a second layer. Generally, pre-wetting includes providing the first layer with a suitable solvent, such as toluene, ethanol, water, or combinations thereof. After pre-wetting the first layer, a second layer may be formed on top of the pre-wetted first layer. Generally, the second layer may be formed in a manner substantially similar to that described with respect to the first layer.

[0051] In some embodiments, the total thickness of the fluid trapping material or coating may be less than 1 mm. For example, the total thickness may be between 0.1 mm and 0.9 mm, between 0.2 mm and 0.8 mm, between 0.2 mm and 0.7 mm, between 0.3 mm and 0.6 mm, or between 0.4 mm and 0.5 mm. In some embodiments, each layer of the fluid trapping material 44 may have the same thickness, such that the thickness formed for each layer (e.g., as per...) Figure 2 The thickness (as described) is the total thickness / n, where "n" is the number of layers formed. In some embodiments, one or more layers of the fluid trapping material 44 may have different thicknesses. For example, each subsequently formed layer may have a thinner thickness than the preceding layer. Alternatively, each subsequently formed layer may have a thicker thickness than the preceding layer.

[0052] As described herein, fluid trapping material 44 can be deposited onto one or more surfaces of substrate 16, such as an air contactor. To illustrate this, Figure 3 A cross-sectional view is shown of a substrate 16 (i.e., a fluid-capturing coating substrate 42) including fluid-capturing material 44. In the illustrated embodiment, substrate 16 is a material formed using additive printing. Furthermore, as shown, the fluid-capturing material 44 includes one or more channels 46 that generally permeate a portion of the fluid-capturing material 44. Generally, the adsorbent material 34 is capable of forming a porous material. Therefore, one or more channels 46 may also be formed in the fluid-capturing material 44.

[0053] As shown, each channel 46 typically includes a wall 48 to which a fluid trapping material 44 is bonded. Thus, a gas flow passing through the channel of the fluid trapping coated substrate 42 can contact the fluid trapping material 44, and therefore promotes the binding of the target fluid (e.g., CO2) with the fluid trapping material 44.

[0054] As described herein, the disclosed fluid trapping material 44 can have a relatively high fluid binding capacity (e.g., water capacity and / or CO2 capacity). Table 1 shows the results of CO2 capacity measurements for certain substrates coated with fluid trapping material 44. Generally, the fluid trapping material 44 corresponding to Table 1 is applied to 2-inch × 2-inch Chromium Nickel Iron 718 specimens using a scraper and the CO2 trapping performance (e.g., CO2 capacity) at 0.04 kPa is evaluated. Sampling of the MOF-binder composite material in an aluminum weighing pan is evaluated to determine the film curing conditions, the initial structural integrity of the film, and environmental adsorption measurements. An example method for coating specimens with a slurry (i.e., adsorbent-binder material 38) requires mixing MOF powder (i.e., adsorbent material 34) with a suitable binder material 36, wetting agent, additives, and solvent in a container. The mixture can be vortexed for 1 to 2 minutes and then sonicated in an ultrasonic bath at 72 kHz for 20 minutes. The slurry is then applied to the substrate 16 using a doctor blade with an appropriate gap (10 to 50 mils, 254 µm to 1270 µm) and allowed to dry under ambient conditions. For coatings in aluminum discs, the slurry can be added to the disc using a plastic pipette, tilting the disc to cover the bottom, and allowed to dry under ambient conditions. Once dry, the disc or sample is cured and activated using appropriate conditions.

[0055] Table 1 - CO2 capacity of certain fluid capture materials

[0056]

[0057] Table 1 shows examples of fluid trapping materials 44 that can be used to capture CO2. Generally, Table 1 shows the CO2 capacity of a control (e.g., Example 1) compared to samples comprising fluid trapping materials 44 formed using an adsorbent material (i.e., MOF-808-Gly) and a crosslinkable binder material (e.g., Examples 2 and 3). More specifically, Example 1 comprises the adsorbent material MOF-808-Gly in powder form, not deposited on the sample. Example 1 has a CO2 capacity of 0.3 mmol / g at 20°C and 20% RH in N2 with 400 ppm CO2.

[0058] Examples 2 and 3 illustrate fluid trapping materials 44 formed using an adsorbent material and a ultimately crosslinked binder material. More specifically, Example 2 is a fluid trapping material 44 having an adsorbent material 34 (e.g., MOF-808-Gly) and a crosslinkable binder material 36 (e.g., aminopropyl silsesquioxane). To prepare Example 2, 2.44 g of a 25% aqueous solution of aminopropyl silsesquioxane, 17.6 g of deionized water, and 0.12 g of Triton were used. ™X-100 and 5.1 g of MOF-808-Gly were mixed to prepare a slurry. After mixing, the slurry was coated onto a 2"×2" chromium-nickel-iron alloy sample, dried, and cured overnight under vacuum at 120°C. A high-quality coating with an equilibrium CO2 absorption rate (e.g., CO2 capacity) of 0.37 mmol / g was obtained when exposed to 400 ppm CO2 in a N2 gas stream at 20°C and 20% RH.

[0059] Example 3 is a fluid trapping material 44 comprising adsorbent material 34 (e.g., MOF-808-Gly), binder material 36 (e.g., PVA), and crosslinking agent 37 (e.g., PAA). To prepare Example 3, 1.55 g of an aqueous solution of 15% PVA (e.g., 88% hydrolyzed) and 3% PAA, 5.2 g of deionized water, and approximately 3 mg of Triton were used. ™ X-100 and 2.5 g of MOF-808-Gly were mixed to prepare a slurry. After mixing, the slurry was coated onto a 2"×2" chromium-nickel-iron alloy sample, dried, and cured overnight under vacuum at 125°C. A fluid trapping material was obtained that scored 3B in the ASTM D3359-17 adhesion test and had an equilibrium CO2 absorption rate of 0.38 mmol / g when exposed to 400 ppm CO2 in a stream of N2 gas at 20°C and 75% RH. Generally, Examples 2 and 3 illustrate two crosslinked aqueous binder formulations used with MOF-808-Gly to form fluid trapping material 44, which has a CO2 binding capacity approximately equal to that of Example 1. Furthermore, the fluid trapping materials of Examples 2 and 3 exhibit good adhesion to the substrate.

[0060] In some embodiments, the fluid trapping material 44 can be formed using a non-aqueous solvent. For example, another example of the fluid trapping material 44 (i.e., Example 4) typically comprises an adsorbent material 34 (e.g., MOF-808-Gly) and a crosslinkable silicone-containing binder material 36. First, a 0.2 g / mL solution of 1.2 mL of SPR100 in methyl ethyl ketone (MEK) is mixed with 94 mg of disilanol PDS-1615, 53 µL of alkoxysilane SIB1140.0, and 69 mg of Hypermer. ™-KD1 was mixed in a vial. Separately, 3.0 g of MOF-808-Gly was mixed with 5 mL of isopropanol (IPA). The solution containing SPR100 was added to the MOF-808-Gly / IPA suspension. The SPR100 vial was rinsed with 2 × 0.5 mL MEK and added to the combined mixture. The slurry was further diluted with 2 mL of IPA to obtain a viscosity suitable for coating. Then, 38 µL of trihexylamine was added to the slurry and the mixture was coated onto a 2" × 2" chromium-nickel-iron alloy sample, dried, and cured under vacuum at 90°C for 1 hour. A high-quality coating was obtained, scoring 4A in the ASTM D3359-17 adhesion test.

[0061] As described above, in some embodiments, the fluid trapping material 44 is capable of binding water. Several embodiments of the fluid trapping material 44 according to this disclosure and the performance of such fluid trapping material 44 are described below.

[0062] A first embodiment of the water-binding fluid trapping material 44 may include an adsorbent material 34 (i.e., MOF-303), a binder material 36 (i.e., PVA), and a crosslinking agent (i.e., PAA) deposited on a metal substrate. More specifically, the first embodiment of the water-binding fluid trapping material 44 can be prepared by mixing 0.56 g of an aqueous solution of 15% poly(vinyl alcohol) [PVA, 88% hydrolyzed] and 3% poly(acrylic acid) [PAA], 2.0 g of deionized water, approximately 3 mg of AGITAN 351, 1.0 g of MOF-303, and 0.02 g of Tergitol 15-S-7 to form a slurry. After mixing, the slurry is coated onto a 2"×2" chromium-nickel-iron alloy sample and cured overnight at 125°C. A high-quality coating with good adhesion and a balance water absorption rate of 26-28% is obtained when tested in a humidity test chamber set to 20% RH and 25°C.

[0063] A second embodiment of the water-binding fluid trapping material 44 comprises an adsorbent material 34 (e.g., MOF-303), a binder material 36 (e.g., PVA), and a crosslinking agent (e.g., PAA) deposited on a glass-filled nylon sample (e.g., a glass-filled nylon substrate). More specifically, the second embodiment of the water-binding fluid trapping material 44 can be prepared by forming a slurry similar to that described above with respect to the first embodiment of the water-binding fluid trapping material 44 and coating the slurry onto a 2"×2" glass-filled polyamide (PA12) nylon sample. The coated sample is allowed to dry at room temperature and then cured overnight at 120°C. Once cooled to room temperature, the sample is immersed in water to release air bubbles and then patted dry. A second layer of slurry is then applied in the same manner as before. This process is repeated once more. After final curing at 120°C, the coating weighs 0.9216 g and adheres well to the substrate. The equilibrium water absorption rate at 20% RH / 25°C is 28%.

[0064] A third embodiment of the water-bound fluid trapping material 44 includes various binder materials 36. For example, the third embodiment of the water-bound fluid trapping material 44 may include binder materials 36 such as PVA, PAA, and poly(methyl / phenyl silsesquioxane). More specifically, the third embodiment of the water-bound fluid trapping material 44 can be prepared by mixing 1.78 g of an aqueous solution of 7.5% PVA [80% hydrolyzed] and 1.5% PAA with 3.5 g of deionized water, 0.02 g of DISPERBYK 190, approximately 3 mg of AGITAN 351, and 2.0 g of MOF-303. A solution of 0.08 g of Wacker MP-50E silicone emulsion diluted with 0.5 g of deionized water is added to the mixture. After mixing, the slurry is coated onto a 2"×2" glass-filled PA12 nylon sample. After drying at room temperature, the sample is cured at 120°C for 4 hours. After cooling, the sample was immersed in water to release air bubbles, gently patted dry, and then another layer of slurry was applied. This drying / curing process was then repeated in the same manner. Two or more layers of slurry were then applied over the first two layers using the same procedure. The dried / cured coating weighed 1.4946 g at the end of the process. The coating adhered well and was free of cracks. The equilibrium water absorption rate at 20% RH / 25°C was 31% to 32%.

[0065] A fourth embodiment of the water-binding fluid trapping material 44 includes an adsorbent material 34, such as MIL-160. To prepare the fourth embodiment of the water-binding fluid trapping material, 2.44 g of an aqueous solution of 13.5% PVA [88% hydrolyzed] and 4.5% PAA was mixed with 5.9 g of deionized water, 0.040 g of DISPERBYK 190, 0.030 g of AGITAN 351, 4.34 g of MIL-160, and 0.050 g of Tergitol 15-S-7. After mixing, the slurry was applied to a 2"×2" chromium-nickel-iron alloy sample. The sample was allowed to dry at room temperature and then overnight at 120°C. After cooling, the sample was immersed in water to release air bubbles and then gently patted dry. A second layer of slurry was applied in the same manner as before and allowed to cure. The second layer did not adhere to the first layer but subsequently peeled off.

[0066] A fifth embodiment of the water-bound fluid trapping material 44 includes a variety of binder materials 36, such as silicone-containing binder materials, PVA, and PAA. It is recognized that using hybrid binder materials 36 (i.e., two, three, four, or more than four different or unique binder materials) can improve the adhesion properties of the fluid trapping material 44 or layer to the substrate and / or the adhesion properties of each layer of a multilayer coating. To prepare the fifth embodiment of the water-bound fluid trapping material, 8.0 g of an aqueous solution of 7.5% PVA (80% hydrolyzed) and 1.5% PAA was mixed with 9.0 g of deionized water, 0.10 g of DISPERBYK 2055, 0.015 g of AGITAN351, and 8.0 g of MIL-160. A solution of 0.08 g of Wacker MP-50E silicone emulsion diluted with 2.0 g of deionized water was added. After mixing, the slurry was used to coat a small chromium-nickel-iron alloy heat exchanger. After drying at room temperature, the sample was cured at 120°C for 2 hours. After cooling, the sample was immersed in water to release air bubbles, patted dry, and then another layer of slurry was applied. The drying / curing process was then repeated in the same manner. Finally, a third layer was applied in the same way. After final curing overnight at 120°C, 3.1 g of well-adhesive coating was obtained. The equilibrium water absorption rate at 20% RH / 25°C was 30% to 32%.

[0067] It was further recognized that crosslinking of the composite coating can improve the structural integrity of the fluid trapping material 44 or the coating. To illustrate the improved structural integrity based on the addition of crosslinking agent 37, two compositions of adsorbent material 34 and binder material 36 were prepared. The first composition was based on the disclosed fluid trapping material 44 and was therefore formed by crosslinking of binder material 36 (i.e., by adding PAA). In the second composition, binder material 36 was not crosslinked (i.e., no PAA was added). To prepare the first composition, a slurry was prepared by mixing 0.56 g of an aqueous solution of 13.5% poly(vinyl alcohol) [PVA, 88% hydrolyzed] and 4.5% poly(acrylic acid) [PAA], 1.4 g of deionized water, 0.02 g of DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated onto a 1"×1" chromium-nickel-iron alloy sample, dried at room temperature, and cured overnight in a vacuum oven at 125°C. The sample was cooled to room temperature in a vacuum desiccator and then rapidly weighed. The sample was then immersed in 10 mL of deionized water and placed in an oven at 90°C for 2 hours. At the end of this time, the sample was removed and dried at 90°C for 1 hour, followed by drying in a vacuum oven at 125°C for 2 hours. Finally, the sample was cooled in a vacuum desiccator and weighed again in the same manner as before. The weights were: (1) uncoated sample: 5.0038 g; (2) coated sample after curing: 5.3206 g (i.e., the coating weight was 0.3168 g); (3) coated sample after immersion / drying: 5.3087 g (i.e., the coating weight was 0.3049 g); and (4) the weight of the coating retained after immersion: 96.2%.

[0068] To prepare the second composition (i.e., without the use of crosslinking agent 37), a slurry was prepared by mixing 0.67 g of an aqueous solution of 15% poly(vinyl alcohol) [PVA, 88% hydrolyzed], 1.3 g of deionized water, 0.02 g of DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated onto a 1"×1" chromium-nickel-iron alloy sample, dried at room temperature, and cured overnight in a vacuum oven at 125°C. The sample was cooled to room temperature in a vacuum desiccator and then rapidly weighed. It was then immersed in 10 mL of deionized water and placed in an oven at 90°C for 2 hours. Shortly after immersion in water, the coating began to crack and peel off from the sample. At the end of this time, the sample was removed and dried at 90°C for one hour, followed by drying in a vacuum oven at 125°C for 2 hours. Finally, the sample was cooled in a vacuum desiccator and re-weighed in the same manner as before. The weights were: (1) uncoated sample: 5.0320 g; (2) coated sample after curing: 5.1974 g (i.e., coating weight is 0.1654 g); (3) coated sample after immersion / drying: 5.0573 g (i.e., coating weight is 0.0253 g); and (4) coating weight retained after immersion: 15.3%. Specifically, the first composition (i.e., the embodiment of fluid trapping material 44 including a crosslinking binder) contained PAA, and the cured film obtained in this case retained 96% of its mass after 2 hours in water at 90°C. Conversely, using the second composition (i.e., using PVA without any crosslinking agent), only 15% of that mass was retained after testing in the same manner.

[0069] As described herein, the fluid trapping material 44 can be formed using a crosslinking agent 37 having different types of functional groups that promote the formation of the fluid trapping material 44. In an example of preparing this composition, 0.30 g of poly(vinyl butyral) was dissolved in 6.0 g of isopropanol. Furthermore, 0.065 g of 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, 3.0 g of amine-treated silica adsorbent, and 0.07 g of BYK9076 were then mixed in. The resulting slurry was applied to an aluminum sample using a doctor blade. After drying at room temperature, the sample (e.g., the aluminum sample coated with the slurry) was placed in a 90°C oven for one hour to cure. The CO2 absorption rate was measured using 400 ppm CO2 in nitrogen under drying conditions at 25°C. The average value was determined to be 0.734 mol CO2 / kg coating (0.032 g / g).

[0070] Figure 4This is a graph with a y-axis corresponding to the amount of CO2 (ppm) and an x-axis corresponding to time (minutes (min)). In this embodiment, a fluid trapping material 44 is formed using a binder material 36 comprising PVA / PAA, as described in Table 1 for Example 3. Furthermore, the fluid trapping material 44 is subjected to a fluid flow of 50 standard cubic centimeters per minute (sccm) having 400 ppm CO2 and 75% RH. As roughly shown in the figure, CO2 is detected approximately 170 minutes after the fluid flow enters the fluid trapping material or coating.

[0071] As described herein, the fluid trapping material 44 is capable of trapping a target fluid, such as H2O. In such embodiments, it is now recognized that forming the fluid trapping material 44 capable of releasing the trapped fluid can be advantageous. To illustrate this, Figure 5 This is an example of a method used to capture target fluids (e.g., as described in...). Figure 1 A diagram of method 60 describing the target fluid 18 and subsequently releasing the target fluid in a controlled manner (i.e., when it may be desirable to remove the target fluid 18). For example, in an embodiment where the target fluid 18 includes water, it may be desirable to extract water from a fluid source (such as air with a relatively high moisture content, e.g., greater than 500 ppm of water) using the disclosed fluid trapping material 44 and subsequently release the water to produce pure water.

[0072] Referring to method 60, at block 62, a gas flow 64 is provided to a substrate 16 coated with fluid trapping material 44. Water in the gas flow 64 combines with the trapping coating, thereby producing a dry gas flow 66. At block 68, a heat exchanger 70 is heated (e.g., using hot air at a temperature greater than 80°C, 85°C, 90°C, or 95°C). In any case, the water combined with the fluid trapping material 44 can be released as steam 72. At block 74, a condenser 76 can receive and cool the steam 72, thereby producing water 78. At block 80, heat can be recovered. In this way, the fluid trapping material 44 can be used to extract fluid and, in some embodiments, to release fluid.

[0073] As described herein, the fluid trapping material 44 may include a crosslinking agent 37 (i.e., a polymer used to crosslink the fluid trapping material 44). In some embodiments, the crosslinking agent 37 may include colloidal silica. Figure 6A graph is shown with an x-axis corresponding to time and a y-axis corresponding to the weight increase (%). In this graph, the relationship between the weight increase and time is shown for the gas-trapping coating formed by: PVA as a binder and MOF as an adsorbent (i.e., "PVA+MOF"); PVA as a binder and silica as a crosslinking agent and MOF as an adsorbent (i.e., "PVA+Silica+MOF"); and silica and starch as crosslinking agents and MOF as an adsorbent (i.e., "PVA+Silica+Starch+MOF"). As shown, the fluid-trapping material with crosslinking agents (i.e., thus having a crosslinked polymer composite matrix) exhibits a relatively high weight increase, which corresponds to more target fluid 18 being adsorbed onto the fluid-trapping material 44.

[0074] In some embodiments, the fluid trapping material 44 includes a silicon-containing binder material 36 (e.g., a silicon-containing binder material, such as a silane). For example, the silicon-containing binder material 36 may include one or more hydroxyl-containing silanes or alkoxysilanes that form hydroxyl groups via condensation. The silane may include one, two, three, or four alkoxy groups. In embodiments where the silane includes fewer than four alkoxy groups, the silane may include an epoxide, other cyclic ether, or another functional group capable of crosslinking. Thus, the silicon-containing binder material may include three or fewer Si-O bonds. For example, the silicon-containing binder material 36 may include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Several additional examples of fluid trapping materials 44 including silicon-containing binder material 36 according to this disclosure and the properties of such fluid trapping materials 44 are described below.

[0075] A first example of a silicon-containing fluid trapping material was prepared by dissolving two binder materials 36 (0.049 g Eastman Butvar B-79 and 0.020 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g ethanol. Then, 0.5 g of an amine-containing MOF was mixed with the two binder materials 36 to form a slurry. The resulting slurry was drip-cast onto an aluminum sample. After drying at room temperature, the sample (e.g., an aluminum sample coated with the slurry) was placed in an oven at 120 °C overnight to cure. The CO2 absorption rate was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 1.90 mol CO2 / kg coating (0.083 g / g).

[0076] A second example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.035 g Eastman Butvar B-79 and 0.007 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g ethanol. Additionally, 0.5 g of an amine-containing metal-organic framework was mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 2.06 mol CO2 / kg coating (0.090 g / g). Although the second sample was described using adsorbent material 34 as an amine-containing MOF, it should be noted that other adsorbent materials 34 can be used to prepare silicon-containing fluid trapping materials.

[0077] A third example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.042 g Eastman Butvar B-79 and 0.008 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g ethanol. Then, 0.5 g of an amine-containing metal-organic framework was mixed with the two binder materials 36, and the resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 1.99 mol CO2 / kg coating (0.087 g / g). Although the third sample was described using adsorbent material 34 as an amine-containing MOF, it should be noted that other adsorbent materials 34 can be used to prepare silicon-containing fluid trapping materials.

[0078] A fourth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.051 g Eastman Butvar B-79 and 0.011 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g ethanol. Then, 0.5 g of an amine-containing metal-organic framework was mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. CO2 absorption was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 1.97 mol CO2 / kg coating (0.086 g / g).

[0079] A fifth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.064 g Eastman Butvar B-98 and 0.064 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 6.0 g ethanol. Furthermore, 2.0 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing.

[0080] In some embodiments, the fluid trapping material 44 can be prepared using relatively less silane compared to the PVA copolymer. To illustrate this, a sixth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.050 g Eastman Butvar B-98 and 0.010 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g ethanol. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate of the membrane was not quantified.

[0081] The silicon-containing fluid trapping material 44 described above was prepared using ethanol. It should be noted that other solvents, such as toluene, isopropanol, butyl acetate, methanol, denatured 200 proof ethanol, or combinations thereof, can be used. Examples of silicon-containing fluid trapping materials prepared using alternative solvents are provided below.

[0082] A seventh example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.043 g Eastman Butvar B-79 and 0.014 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g butyl acetate. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate of the membrane was not quantified.

[0083] An eighth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.043 g Eastman Butvar B-98 and 0.018 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 1.5 g methanol. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate of the membrane was not quantified.

[0084] A ninth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.086 g Eastman Butvar B-98 and 0.036 g 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane) in 3.0 g ethanol. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate of the membrane was not quantified.

[0085] A tenth example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.086 g Eastman Butvar B-79 and 0.036 g 3-glycidoxypropyltrimethoxysilane) in 3.0 g ethanol. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. The CO2 absorption rate was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 2.29 mol CO2 / kg coating (0.100 g / g).

[0086] An eleventh example of a silicon-containing fluid trapping material 44 was prepared by dissolving two binder materials 36 (0.086 g Eastman B-98 and 0.036 g 3-glycidoxypropyltrimethoxysilane) in 3.0 g ethanol. Furthermore, 0.5 g of an amine-containing metal-organic framework was then mixed with the two binder materials 36. The resulting slurry was drop-cast onto an aluminum sample. After drying at room temperature, the coated sample was placed in an oven at 120 °C overnight for curing. CO2 absorption was measured at 60 °C using 5% CO2 in nitrogen at 30% relative humidity. The average value was determined to be 2.33 mol CO2 / kg coating (0.102 g / g).

[0087] While the example silica-containing fluid trapping material 44 described above includes adsorbent material 34 as an amine-containing MOF, it should be noted that other adsorbent materials 34 can be used to prepare the silica-containing fluid trapping material 44. Furthermore, the silica-containing fluid trapping material 44 is prepared with an adsorbent material 36 to solvent mass ratio between 1 / 6 (e.g., 3.0 g ethanol and 0.5 g amine-containing MOF) and 1 / 3 (e.g., 1.5 g ethanol and 0.5 g amine-containing MOF). In some embodiments, the solvent ratio can be greater than 1 / 3, such as 1 / 2, 2 / 3, 3 / 4, 3 / 5, or 1. As another non-limiting example, the fluid trapping material 44 can be prepared using 0.086 mg of Eastman B-98 and 0.034 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or other silanes including epoxides as binder material 36. In addition, the fluid capture material can be prepared using 3.0 g of denatured 200 proof ethanol and 1.0 g of adsorbent material (e.g., amine-containing adsorbent material or other adsorbent material as described herein).

[0088] Furthermore, the example silicone-containing fluid trapping material 44 described above comprises a combination of two binder materials 36 (e.g., a vinyl binder material 36 (e.g., a vinyl reagent) and a silicone binder material 36). As generally described above, the ratio of the silicone binder material 36 to the vinyl binder material can be approximately between 1 and 1 / 10. For example, the ratio of the silicone binder material 36 to the vinyl binder material 36 can be between 1 and 1 / 10, 1 to 1 / 8, 1 / 2 to 1 / 8, 1 / 3 to 1 / 6, approximately 1 / 7, approximately 1 / 6, approximately 1 / 5, approximately 1 / 4, approximately 1 / 3, approximately 1 / 2, or approximately 1. In some embodiments, the silicone-containing fluid trapping material 44 may comprise only the silicone binder material 36. As an additional non-limiting example, the fluid trapping material 44 may have... 1 / 5 to 3 The mass ratio of the silicone-containing binder material to the vinyl binder material is between 1 / 5 (e.g., approximately 1 / 4, approximately 1 / 3, approximately 1 / 2, approximately 2 / 5), and the mass ratio of the solvent to the adsorbent material is between 1 / 4 and 1 / 2 (e.g., approximately 2 / 5, approximately 1 / 3, approximately 3 / 8, approximately 5 / 16). As another non-limiting example, the fluid trapping material 44 may have a mass ratio of approximately... 2 The mass ratio of silicone-containing adhesive material to vinyl adhesive material is approximately 5 / 5 (e.g., approximately 0.3, approximately 0.35, approximately 0.4, approximately 0.45, approximately 0.5). 1 The solvent to adsorbent material mass ratio is 3 / 3 (e.g., approximately 0.3, approximately 0.35, approximately 0.38, approximately 0.4).

[0089] Therefore, this disclosure relates to a fluid trapping material or a fluid trapping material that provides improved fluid binding capacity and stability. The fluid trapping material or coating typically comprises an adsorbent material and a binder material. As described herein, the resulting fluid trapping material or coating may comprise a crosslinked polymer formed from one or more binder materials and certain crosslinking agents such as ultraviolet light, silica, polyacrylic acid, heat, or combinations thereof.

[0090] The technical effects of this invention include, but are not limited to, improving the capacity and / or capture efficiency of a substrate through a fluid-capturing material. By providing the disclosed fluid-capturing material, the amount of certain gases retained in the exhaust gas stream can be reduced. Furthermore, by forming a fluid-capturing material comprising a cross-linked polymer, a relatively larger amount of adsorbent material can be used compared to a binder material, thereby improving the fluid binding capacity of the fluid-capturing material.

[0091] This written description uses examples to disclose the invention, including the best mode, and also enables any person skilled in the art to practice the invention, including making and using any device or system and performing any combined methods. The patentable scope of the invention is defined by the claims and may include other examples that will occur to those skilled in the art. Such other examples are contemplated within the scope of the claims if they have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims.

Claims

1. A gas capture system, the gas capture system comprising: Substrate; and A gas trapping material formed on one or more surfaces of the substrate, wherein the gas trapping material comprises: An adsorbent material, said adsorbent material being configured to bind one or more gases; and One or more silicone-containing adhesive materials, wherein the one or more silicone-containing adhesives are at least partially crosslinked.

2. The gas capture system according to claim 1, wherein the adsorbent material comprises an amine-containing metal-organic framework (MOF).

3. The gas capture system of claim 1, wherein the one or more silicon-containing binder materials are at least partially crosslinked with the vinyl binder material.

4. The gas capture system of claim 3, wherein the mass ratio of the one or more silicon-containing binder materials to the vinyl binder material is between 1 / 2 and 1 / 10.

5. The gas capture system of claim 1, wherein the one or more silicon-containing binder materials comprise silane reagents.

6. The gas capture system according to claim 1, wherein the adsorbent material is functionalized using an amino-organosilicon functional group.

7. The gas capture system of claim 1, wherein the silicon-containing binder material comprises three or fewer Si-O bonds.

8. The gas capture system according to claim 1, wherein the thickness of the fluid capture material is between 0.1 mm and 3.5 mm.

9. The gas capture system of claim 1, wherein the gas capture material comprises more than 90% by weight of the adsorbent material.

10. A method, the method comprising: An adsorbent material is provided, the adsorbent material being configured to bind one or more gases; A variety of adhesive materials are provided, wherein the variety of adhesive materials includes silicone-containing adhesive materials; The adsorbent-binder material is generated using the adsorbent material, the various binder materials, and the solvent; as well as The fluid trapping material is formed by applying the adsorbent-binder material to a substrate, wherein the fluid trapping material comprises a cross-linked composite material.

11. The method of claim 10, wherein the silicon-containing binder material comprises at least one cyclic ether functional group.

12. The method of claim 10, wherein the mass ratio of the adsorbent material to the solvent is greater than 1 / 6.

13. The method of claim 10, wherein the mass ratio between the solvent and the adsorbent material is greater than 1 / 3.

14. The method of claim 10, wherein generating the adsorbent-binder material based on the one or more silicon-containing binder materials comprises: Crosslinking of the one or more silicon-containing adhesive materials.

15. The method of claim 10, wherein forming the fluid trapping material comprises: The first layer of the fluid trapping material is formed using the adsorbent-binder material; Pre-wet the first layer; as well as A second layer is formed on the pre-wetted first layer.

16. The method of claim 10, wherein the plurality of adhesive materials comprises 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and vinyl reagents.

17. The method of claim 16, wherein the solvent is denatured 200 proof ethanol.

18. The method according to claim 17, wherein the adsorbent-binder material is an amine-containing adsorbent material.

19. A gas capture system, the gas capture system comprising: A fluid trapping material configured to bind one or more fluids, wherein the fluid trapping material comprises: Adsorbent material, the adsorbent material being configured to bind to one or more fluids, said fluids including water, carbon dioxide, sulfur oxides, or combinations thereof; and A variety of adhesive materials, including silicone-containing adhesive materials and vinyl-based adhesive materials, wherein the various adhesive materials are at least partially crosslinked; and A fluid contactor having one or more surfaces coated with the fluid trapping material.

20. The gas capture system of claim 19, wherein the mass ratio of the one or more silicon-containing binder materials to the vinyl binder material is less than ¼.

21. The gas capture system of claim 19, wherein the mass ratio of the one or more silicon-containing binder materials to the vinyl binder material is less than 1 / 8.

22. The gas capture system of claim 19, wherein the adsorbent material comprises a metal-organic framework (MOF), a covalent organic framework (COF), a polymer resin, silica, zeolite, or a combination thereof.

23. The gas capture system of claim 19, wherein the silicon-containing binder material is at least partially crosslinked with the vinyl binder material.

24. The gas capture system of claim 19, wherein the mass ratio of the silicon-containing binder material to the vinyl binder material is... 1 / 5 to 3 Between 1 / 5 and 1 / 5 by mass, and wherein the mass ratio of the solvent to the adsorbent material is between 1 / 4 and 1 / 5 by mass. 1 Between / 2.

25. The gas capture system of claim 19, wherein the mass ratio of the silicon-containing binder material to the vinyl binder material is approximately 2 / 5, and wherein the mass ratio between the solvent and the adsorbent material is approximately 1 / 3.

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