Patent Application
20240082815
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.
Certain industrial systems may produce a variety of fluids, such as water and carbon dioxide (CO2), during operation of the industrial systems. In certain instances, the fluids may be vented off as an exhaust gas, or otherwise not utilized. Certain components (e.g., substrates) of the industrial systems may include a coating capable of capturing or extracting the fluids.
Certain embodiments commensurate in scope with the originally filed claims are summarized below. These embodiments are not intended to limit the scope of the present technology, but rather these embodiments are intended only to provide a brief summary of possible forms of the technology. Indeed, the present system and method may encompass a variety of forms that may be similar to or different from the embodiments set forth below.
In one embodiment, the present disclosure relates to a system. The system includes a substrate and a fluid capture material formed on one or more surfaces of the substrate. The fluid capture material includes a sorbent material that binds one or more fluids including water, carbon dioxide, sulfur oxides, or a combination thereof. The fluid capture material includes one or more binder materials and the binder material is at least partially cross-linked.
In one embodiment, the present disclosure relates to a method. The method includes providing a sorbent material that binds one or more fluids comprising water, carbon dioxide, sulfur oxides, or a combination thereof. The method also includes providing one or more binder materials, wherein the one or more binder materials includes a component capable of forming a cross-linked polymer. Additionally, the method includes providing a cross-linking agent. Further, the method includes generating a sorbent-binder material based on the sorbent material, the one or more binder materials, and the cross-linking agent. Further still, the method includes applying the sorbent-binder material to a substrate, and forming a fluid capture material using the sorbent-binder material applied to the substrate, wherein the fluid capture material comprises the cross-linked polymer.
In one embodiment, the present disclosure relates to a system. That system includes a fluid capture material that binds one or more fluids. The fluid capture material includes a sorbent material configured to bind one or more fluids comprising water, carbon dioxide, sulfur oxides, or a combination thereof. The fluid capture material also includes a binder material, wherein the binder material is at least partially cross-linked. Further, the fluid capture material includes an air contactor having one or more surfaces coated with the fluid capture material.
These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:
One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, all features of an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation, as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.
When introducing elements of various examples of the present disclosure, the articles “a,” “an,” “the,” and “said” are intended to mean that there are one or more of the elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements. Additionally, it should be understood that references to “one example” or “an example” of the present disclosure are not intended to be interpreted as excluding the existence of additional examples that also incorporate the recited features.
In the present context, the term “about” or “approximately” is intended to mean that the values indicated are not exact and that the actual value may vary from those indicated in a manner that does not materially alter the operation concerned. For example, the term “about” or “approximately” as used herein is intended to convey a suitable value that is within a particular manufacturing or operating tolerance (e.g., ±10%, ±5%, ±1%, ±0.5%), as would be understood by one skilled in the art.
As generally discussed herein, certain systems (e.g., gas turbines) that produce one or more fluids (e.g., water and/or CO2) may include one or more substrates having a surface coating that binds the one or more fluids, thereby extracting or capturing the one or more fluids from a source fluid (e.g., an exhaust gas flow, an ambient air flow, and the like). For example, the systems may include combustion systems that utilize a fuel source (e.g., fossil fuels). Accordingly, one or more substrates of the combustion systems may include a surface coating capable of extracting carbon dioxide. As another non-limiting example, the systems may include a water capture system that generally includes a surface coating capable of extracting water from ambient air. In certain embodiments, it may be desirable to capture at least a portion of the fluids, such as to address guidance by certain entities (e.g., government regulation) and/or to utilize the one or more fluids rather than otherwise not capturing the fluids, such as by venting or otherwise releasing the fluids into a surrounding airspace or other proximate environment.
The present disclosure is directed to techniques for improving the efficiency of capturing or extracting certain fluids from a fluid flow by forming a fluid capture material or fluid capture coating using a sorbent material (e.g., sorbent component) and a binder material that is capable of cross-linking, and cross-linking the binder material (e.g., using a cross-linking agent). As described in more detail herein, the sorbent material generally includes materials capable of binding certain fluids, such as carbon dioxide (CO2), water (H2O), oxygen (O2), or other gas molecules that may form as result of a decomposition reaction (e.g., combustion). For example, the sorbent materials may include metal organic frameworks (MOFs) and/or covalent-organic frameworks (COFs). In some embodiments, the sorbent materials may include polymeric resins, silicas, zeolites, and the other materials capable of capturing fluids as discussed herein. The binder material may include one or more materials that may block, reduce, or mitigate decomposition or dissolution (i.e., improve the stability) of the sorbent materials. As described in further detail herein, it is presently recognized that forming a fluid capture material using a sorbent material and a cross-linked binder material may provide an improved capacity for binding fluids (e.g., in a reversible or irreversible manner) as compared to conventional fluid binding materials or coatings.
More specifically, the disclosed fluid capture material or coating may be formed by cross-linking a binder material that is capable of forming a cross-linked polymer. At least in some instances, the disclosed fluid capture material may include a portion (e.g., a mass percentage) that is a cross-linked polymer (e.g., a cross-linked binder material). By way of 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 capture material. In general, the cross-linked polymer may be formed using thermal techniques, radiation techniques (e.g., illumination with ultraviolet (UV) light) and/or chemical techniques (e.g., using cross-linking agents via radical polymerization or condensation reactions). In embodiments where a cross-linking agent is used, the fluid capture material may also include the cross-linking agent. That is, the cross-linking agent may be present in the fluid capture material. It is presently recognized that a fluid capture material that includes a cross-linked polymer (e.g., the fluid capture material is formed using the cross-linked polymer) may result in a fluid capture material that has a relatively higher amount of the sorbent (e.g., a relatively lower amount of the binder material (e.g., less than 15%, less than 12% by mass, less than 10% by mass, less than 8% by mass, less than 5% by mass) as compared to a fluid capture material formed using a binder or polymer that is not cross-linked and/or is incapable of cross-linking. Accordingly, increasing the amount of the sorbent material improves the fluid binding capacity of the fluid capture material by having a higher amount of the sorbent material in the fluid capture material. Furthermore, by forming the fluid capture material with a cross-linked polymer, the disclosed fluid capture material may have improved adherence or binding to a substrate (e.g., a metal substrate, polymeric substrate (e.g., a glass-filled nylon), polymer composite substrate, and the like) and stability or resistance to dissolution.
With this in mind,
In certain embodiments, the fluid capture system 12 may be provided as part of a gas turbine system, a chemical production system, or other systems that produce a fluid flow (e.g., a gas flow, an exhaust gas flow) having gas molecules that may be desirable to capture. As illustrated, the fluid capture system 12 may include one or more substrates 16. As described herein, the substrates 16 may include a coating formed of a semi-permeable material or materials (e.g., capable of letting certain gases permeate through the substrates) that is capable of binding certain fluids (i.e., the target fluid 18 or gas). For example, the coating may be a fluid capture material formed using a sorbent material and a binder material that is capable of forming a cross-linked polymer.
As described herein, the fluid capture material may improve the amount of target fluid 18 extracted from the fluid source 14 and/or may have improved stability as compared to certain coatings used to extract fluids from a fluid source 14. To illustrate this,
To start the process 30, at block 32, a sorbent material 34, a binder material 36, and a cross-linking agent 37 are used to generate a sorbent-binder material 38. In general, using the sorbent material 34, the binder material 36, and the cross-linking agent may include forming a mixture, such as a solution or slurry including the sorbent material 34 and the binder material 36 in a suitable solvent that is capable of dissolving at least a portion of the sorbent material and/or the 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, the cross-linking agent 37 may include certain chemical cross-linking agents. As such, the cross-linking agents 37 may also be added to the mixture of the sorbent material 34 and the binder material 36. In some embodiments, cross-linking agent 37 may be added after forming the mixture of the sorbent material 34 and the binder material 36. For example, in an embodiment where the binder material 36 is a polymeric material, the cross-linking agent 37 may be added after a time period corresponding to a suitable degree of polymerization of the binder material 36 (e.g., after initiation of polymerization of the binder material 36). However, in certain embodiments, the cross-linking agent 37 may be added prior to polymerization of the binder material 36 being initiated.
The sorbent material 34 is generally a material capable of adsorbing fluids such as water and/or CO2. In some embodiments, the sorbent material 34 may include metal-organic frameworks (MOFs) and/or covalent-organic frameworks (COFs). For example, the sorbent material may include MOFs 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), zeolitic imidazolate frameworks (ZIFs), amine-containing MOFs, other MOFs, amine-containing COFs, ZIFs, silicas, and the like, that are capable of adsorbing fluids as described herein. In some embodiments, the sorbent material 34 may include polymeric resins, silicas, zeolites, or a combination thereof.
The binder material 36 may include one or more oligomeric or polymer materials, monomeric or oligomeric material capable of polymerizing, or a combination thereof. At least in some instances, the binder material 36 may improve the affinity of the sorbent material 34 for binding a certain gas or gases and/or improve the stability (e.g., thermostability) of the sorbent material 34. In some embodiments, the binder material 36 may include materials that form polymers having a thermostability about 200° C. In some embodiments, the binder material 36 may include silicon-containing polymers or binders (e.g., siloxanes or silanes, such as aminopropylsilsesquioxane, aminoethylaminopropylsilsesquioxane, alkyoxysilane), vinyl polymers (e.g., polyvinyl esters, such as polyvinyl acetate; polyvinyl alcohol) and copolymers thereof like polyvinyl butyral. In some embodiments, the binder material 36 may include polysaccharides (e.g., ethyl cellulose, starch, and alkyl cellulose), nitrogen-containing polymers (e.g., polyethyleneimine (PEI)). In some embodiments, the binder material 36 may include combinations of the previously described polymers (i.e., 2, 3, 4, or more than 4 of the polymers). For example, the binder material 36 may be a “hybrid binder mixture.” As referred to herein, a “hybrid binder mixture” may include mixtures or blends of different types of binder materials, such as a mixture of organic polymers and silsesquioxane binders, or other combinations of binder materials described herein. At least in some instances, the binder material 36 may be selected to enhance the adsorption of the target fluid onto a coating (e.g., the fluid capture material) produced using the sorbent material 34. For example, in an embodiment where PEI is used as a binder material, the PEI may include PEI-low (e.g., Mw between approximately 20,000 g/mol and 25,000 g/mol, and Mn between approximately 8,000 g/mol to 12,000 g/mol) or PEI-high (e.g., Mw between approximately 70,000 g/mol and 80,000 g/mol, and Mn between approximately 55,000 g/mol to 65,000 g/mol).
As described herein, the binder material 36 may be a polymer material that is capable of cross-linking. That is, it is presently recognized that forming a fluid capture material where at least a portion of a polymer portion of the sorbent-binder material 38 is a cross-linked polymer may reduce the likelihood of decomposition and/or dissolution of the sorbent material 34. Further, using a cross-linked polymer may enable the fluid capture material to have a relatively higher amount of the sorbent material that binds to the target fluid 18, and thus may have a higher fluid binding capacity as compared to a coating formed without cross-linked polymers. Put differently, conventional techniques of combining of sorbent material 34 and a binder material 36 may result in a fluid binding material that has a relatively lower fluid binding capacity as compared to the sorbent material (e.g., due to a dilution effect or knockdown effect). It is presently recognized that cross-linking the binder material 36 may generate a fluid capture coating or fluid capture material that has a relatively higher binding capacity as compared to not cross-linking the binder material 36. Further, the binding capacity of the disclosed fluid capture coating or material (i.e., including a cross-linked binder material) may have a binding capacity that is approximately equal to the binding capacity of the sorbent material 34 by itself (e.g., the sorbent material 34 in powder form).
In one embodiment, the binder material 36 includes materials that are capable of self-cross-linking. For example, the binder material 36 may include silanol (SiOH) functional groups and/or alkoxysilane (SiOR) functional groups. It should be noted that binder materials 36 that include such functional groups may undergo intermolecular condensation reactions that cause the binder materials 36 to crosslink upon heating. For example, it is presently recognized that an amine-containing component (e.g., an amine-containing MOF) may cause certain binder materials 36 (e.g., epoxy resins) to cross-link. As another non-limiting example, an amine-containing component may cross-link certain Si—O polymeric structures, such as silsesquioxane, thereby forming a cross-linked Si—O polymeric structure (e.g., amine-impregnated silica).
In one embodiment, the binder material comprises a polyvinyl alcohol polymer. Suitable polyvinyl alcohol polymers include, without limitation polyvinyl alcohol homopolymers, and polyvinyl alcohol copolymers. In one embodiment, the binder polymer composition comprises a polyvinyl alcohol-polyvinyl amine copolymer (PVA-PVAm) comprising a first crosslinkable functional group and a second crosslinkable functional group. Although derivatives of polyvinyl alcohol are suitable for the practice of the present invention, other polymeric materials may be used in the binder polymer composition, including without limitation, polyacrylates, polymethacrylates, polyhydroxyethyl methacrylates, functionalized polyarylenes containing amine, carboxylic acid, amide, hydroxyl moieties, and the like. In one embodiment, the binder polymer composition used in the preparation of the fluid capture material comprises at least one polymer having a number average molecular weight greater than about 2500 Daltons. In another embodiment, the binder polymer composition used in the preparation of the fluid capture material comprises at least one polymer having a number average molecular weight in a range of from greater than 2500 Daltons to about 500,000 Daltons. In yet another embodiment, the binder polymer composition used in the preparation of the fluid capture material comprises at least one hydrophilic polymer having a number average molecular weight in a range of from about 75,000 Daltons to about 250,000 Daltons. Number average molecular weights may be determined by a variety of techniques known to those of ordinary skill in the art including 1H-NMR spectroscopy and gel permeation chromatography (GPC).
As described above, the binder material 36 may include a mixture of polymer materials that are capable of cross-linking. For example, the binder material 36 may include a mixture of polyvinyl alcohol (PVA) and polyacrylic acid (PAA). For example, the mixture may include 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.
In some embodiments, the binder material 36 may be dissolved in a solvent to a particular viscosity. For example, in an embodiment where the binder material 36 includes ethyl cellulose, the binder material 36 may include a 7-15 cP solution in 6% toluene in ethanol solution. The resulting slurry may include 30% solids, 11% binder, when dissolved in a 1:1 toluene 2-(2-butoxyethoxy) ethyl acetate solvent. As another non-limiting example, in an embodiment where the binder material 36 includes ethyl cellulose, the binder material 36 may include an approximately 300 cP solution in 5% toluene in ethanol solution.
In general, the amount of cross-linking agent 37 may be less than the amount of binder material 36. In some embodiments, the ratio of cross-linking agent 37 added to the binder material 36 to form the sorbent binder composite 38 may be less than approximately ⅓, less than approximately ¼, less than approximately ⅕, or less than approximately ⅙. For example, the sorbent binder composite 38 may be formed by combining a 10% by mass solution of a binder material 36 and a 2% by mass solution of a cross-linking agent 37 (i.e., the ratio of the cross-linking agent 37 to the binder material 36 is ⅕).
It should be noted that, at least in some instances, the cross-linking agent 37 may also be a binder material 36. That is, the cross-linking agent 37 may be a polymer that is capable of cross-linking. For example, PAA may be used as a cross-linking agent for PVA.
As described herein, the cross-linking agent 37 cross-links the binder material 36. In some embodiments, the degree of cross-linking (i.e., cross-linking density, which refers to the density of chains or segments that connect two parts of a polymer network, rather than the density of cross-link junctures) 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%.
With respect to the sorbent-binder material 38 (e.g., the sorbent-binder composite), the amount of binder material 36 and sorbent material 34 may be such that the sorbent-binder material 38 includes greater than 50%, of the sorbent material, greater than 60% of the sorbent material, greater than 70% of the sorbent material, greater than 80% of the sorbent material 34, greater than 85% of the sorbent material 34, or greater than 90% of the sorbent material 34.
A wide variety of cross-linking agents can be used to react with the binder, and these cross-linking agents may be monomers, oligomers, or polymers, or a combination of the foregoing. In some embodiments, the cross-linking agent 37 may include chemical cross-linking agents such as epoxies, anhydrides, and the like. In some embodiments, the cross-linking agent 37 may include one or more materials such as nanoparticles, micron-sized particles, or larger sized particles, or molecular precursors that can form particles. For example, the cross-linking agent may include silica particles, such as colloidal silica; or tetraalkoxysilane that can form silica particles. In some embodiments, the cross-linking agent 37 may include particles having different size distributions. That is, the cross-linking agent 37 may include particles of a first size distribution and a second size distribution. For example, the cross-linking agent 37 may have a micron-size distribution. In some embodiments, the cross-linking agent 37 may have a nano-size distribution and a micron-size distribution (i.e., a bimodal size distribution). At least in some instances, a bimodal size distribution may improve wear resistance. In an embodiment where the cross-linking agent 37 includes particles having different size distributions, the mixture of the particles may vary. For example, the mixture may include 10%, 20%, 30%, 40%, 50%, 60%, 70%, and the like, by weight, of the nano-sized particles and 90%, 80%, 70%, 60%, 50%, 40%, 30%, and the like, by weight, of the micron-sized particles. In an embodiment where the cross-linking agent 37 includes particles (e.g., micron-sized particles, nanoparticles, or larger particles), the particles may have a distribution of shapes. For example, the cross-linking agent 37 may include micron-sized particles that are 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% 90%, or 95% spherical. At least in some instances, the combination of particle shape (e.g., spherical) and different size distributions may improve the properties of the resulting fluid capture material discussed herein.
In some embodiments, the cross-linking agent 37 comprises a functional group susceptible to the formation of a free radical resulting from exposure to high energy irradiation (e.g., ultraviolet light or electron beam) and/or heat. Those of ordinary skill in the art will appreciate that the structure of a free radical is understood to determine its reactivity and that the structures of the cross-linking agent may be selected to provide for a higher or lower level of chemical reactivity of free radicals generated from such crosslinkable functional groups under irradiation or heat exposure. In one embodiment, the cross-linking agent comprises a functional group capable of forming a secondary or tertiary aliphatic or cycloaliphatic radical. In another alternate embodiment, the cross-linking agent comprises a functional group capable of forming an aromatic radical, for example a benzyl radical. Other crosslinkable functional groups include methacrylates, acrylates, acrylamides, vinylketones, styrenics, vinyl ethers, vinyl groups, allyl groups, benzyl groups, and groups containing tertiary carbon-hydrogen bonds, for example isobutyl groups.
Suitable cross-linking agents 37 include but are not limited to methacrylates, acrylates and vinyl ketone reagents. These reagents can be covalently bound to a binder material or form crosslinked polymers themselves upon exposure to high energy irradiation or heat. For example, suitable cross-linking agents include without limitation the 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, 2-isocyanatoethyl methacrylate, methacrylic acid, methacrylic anhydride, methacryloyl chloride, glycidyl methacrylate, 2-ethylacryloyl chloride, 3-methylenedihydro-2(3H)-furanone, 3-methyl-2(5H)-furanone, methyl 2-methylacrylate, methyl trans-2-methoxyacrylate, citraconic anhydride, itaconic anhydride, methyl (2E)-2-methyl-2-butenoate, ethyl 2-methylacrylate, ethyl 2-cyanoacrylate, dimethylmaleic anhydride, allyl 2-methylacrylate, ethyl (2E)-2-methyl-2-butenoate, ethyl 2-ethylacrylate, methyl (2E)-2-methyl-2-pentenoate, 2-hydroxyethyl 2-methylacrylate, methyl 2-(1-hydroxyethyl)acrylate, 3-(methacryloyloxy)propyltrimethoxysilane, 3-(diethoxymethylsilyl)propyl methacrylate, 3-(trichlorosilyl)propyl 2-methylacrylate, 3-(trimethoxy silyl)propyl 2-methylacrylate, 3-tris(trimethylsiloxy) silylpropyl methacrylate, 6-dihydro-1H-cyclopenta(c)furan-1,3(4H)-dione, methyl 2-cyano-3-methylcrotonate, trans-2,3-dimethylacrylic acid, and N-(hydroxymethyl)acrylamide.
Suitable vinyl and allyl reagents which may serve as a cross-linking agent include, without limitation, allyl bromide, allyl chloride, diketene, 5-methylenedihydro-2(3H)-furanone, 3-methylenedihydro-2(3H)-furanone, 2-chloroethyl vinyl ether, and 4-methoxy-2(5H)-furanone.
Suitable isocyanate reagents which may serve as cross-linking agent include, without limitation, vinyl isocyanate, allyl isocyanate, furfuryl isocyanate, 1-ethyl-4-isocyanatobenzene, 1-ethyl-3-isocyanatobenzene, 1-(isocyanatomethyl)-3-methylbenzene, 1-isocyanato-3,5-dimethylbenzene, 1-bromo-2-isocyanatoethane, (2-isocyanatoethyl)benzene, 1-(isocyanatomethyl)-4-methylbenzene, 1-(isocyanatomethyl)-3-methylbenzene, 1-(isocyanatomethyl)-2-methylbenzene, and the like.
Suitable styrenic reagents which may serve as a cross-linking agent include, without limitation, 3-vinylbenzaldehyde, 4-vinylbenzaldehyde, 4-vinylbenzyl chloride, trans-cinnamoyl chloride, phenylmaleic anhydride, 4-hydroxy-3-phenyl-2(5H)-furanone, and the like.
Suitable epoxide reagents which may serve as the cross-linking agent 37 include, without limitation, glycidyl methacrylate, glycidyl vinyl ether, 2-(3-butenyl)oxirane, 3-vinyl-7-oxabicyclo[4.1.0]heptane, limonene oxide, and the like.
In some embodiments, the cross-linking agent 37 may include multiple (e.g., two, three, or more than three) different types of functional groups that may facilitate formation of the fluid capture material 44. In general, the cross-linking agent 37 may include a first functional group that reacts with the binder material 36 and a second functional group that may cross-link. For example, the cross-linking agent 37 may include an anhydride functional group and an acrylate functional group, an epoxide functional group and an acrylate functional group, an isocyanate functional group and a methacrylate functional group, and the like. As one non-limiting example, the binder material 36 may include poly(vinyl alcohol) and the cross-linking agent 37 may include 2-isocyanato ethylmethacrylate (2-IEM), which includes both an isocyanate functional group and a methacrylate functional group. As another non-limiting example, the binder material 36 may include poly(vinyl butyral) and the cross-linking agent 37 may include 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane.
In some embodiment, one or more additives may be added to form the sorbent-binder material 38. For example, the additives may include dispersants to facilitate forming a suspension, such as anionic dispersants, cationic dispersants, non-ionic dispersants, defoamers, wetting agents, adhesion promoters, or any combination thereof. For example, suitable anionic dispersants may include polymeric alkoxylate or phosphate ester. For example, suitable non-ionic dispersants may include polyurethane. For example, suitable cationic dispersants may include polyoxyethylene fatty ammonium sulfate. In general, the amount of dispersant added may be less than the amount of the binder material 36. For example, the sorbent-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 greater than 1% by weight of dispersant. As another non-limiting example, the sorbent-binder material 38 may include 15% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or greater than 5% by weight of dispersant. As another non-limiting example, the sorbent-binder material 38 may include 13% by weight of binder material 36 and 1% by weight of dispersant, 3% by weight of dispersant, or greater than 5% by weight of dispersant. For example, in an example sorbent-binder material 38 where the binder material 36 is aminopropylsilsesquioxane, the 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., Mw between approximately 20,000 and 25,000 g/mol, and Mn between approximately 8,000 to 12,000) or PEI-high (e.g., Mw between approximately 70,000 and 80,000 g/mol, and Mn between approximately 55,000 to 65,000).
At block 40, the sorbent-binder material 38 is deposited onto, applied to, formed integrally with (e.g., during manufacture), or otherwise coupled to the substrate 16, such as to one or more surfaces of the substrate 16, thereby forming a fluid capture coated substrate 42. In some embodiments, the substrate may include certain metal substrates (e.g., aluminum, titanium) or 3-D printed metal substrates. For example, the substrate 16 may include a fluid contactor with a metal surface. In some embodiments, the substrate 16 comprises metal alloys (e.g. Inconel or stainless steel). As referred to herein, a “fluid contactor” or “direct fluid contactor” refers to a structure configured to receive a fluid flow, and the structure may include a porous and/or semi-porous material, such that a portion of the fluid flow may 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 an exhaust gas flow from power generating equipment (e.g., a gas turbine). As such, the binder material 36 may be selected to have a relatively high binding to the metal surface.
In some embodiments, the substrate 16 can be a polymer or polymer composite. Polyolefins (e.g., polyethylene, polypropylene, polymethylpentene, polystyrene, substituted polystyrenes, poly(vinyl chloride) (PVC), polyacrylonitriles), polyamide, polyester, polysulfone, polyether, acrylic and methacrylic polymers, polystyrene, polyurethane, polycarbonates, polyesters (e.g., polyethylene terephthalic ester, polybutylene terephthalic ester), polyether sulfones, polypropylene, polyethylene, polyphenylene sulfone, cellulosic polymer, polyphenylene oxide, polyamides (e.g., nylon, polyphenylene terephthalamide), and combinations of two or more of the foregoing polymers may be utilized as substrates. Fluoropolymers, which may be used as the substrate include, without limitation, ePTFE, polyvinylidene difluoride (PVDF), poly(tetrafluoroethylene-co-hexafluoropropylene (FEP), poly(ethylene-alt-tetrafluoroethylene) (ETFE), polychlorotrifluoroethylene (PCTFE), poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA), poly(vinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP), and polyvinyl fluoride (PVF).
In general, depositing the sorbent-binder material 38 onto the substrate 16 may include curing the sorbent-binder material 38, which includes the cross-linking agent 37, thereby forming a fluid capture material 44 or coating that is a polymer and sorbent composite material. Put differently, the fluid capture material 44 refers to the sorbent-binder material 38 where the binder material 36 is cross-linked via one or more cross-linking agents 37. As described herein, cross-linking the sorbent-binder material 38 may provide a material and/or coating (i.e., the fluid capture material 44) that has relatively higher structural integrity as compared to not cross-linking the sorbent-binder material 38. Further, cross-linking the sorbent-binder material 38 may provide a material and/or coating that has a relatively higher binding capacity to fluids.
It should be noted that, at least in some instances, the sorbent-binder material 38 may be deposited multiple times on the substrate 16. It is presently recognized that, at least in some instances, depositing a relatively thick layer (e.g., greater than 1 mm, greater than 2 mm, or greater than 5 mm) may result in fluid capture material 44 (e.g., a fluid capture material or a fluid capture coating) having one or more cracks. Therefore, to reduce, prevent, or mitigate cracking (e.g., mudcracking), it may be advantageous to deposit multiple layers to ultimately form the fluid capture material 44 having a desired thickness (e.g., between 0.1 mm and 0.9 mm, between 1.1 mm and 1.3 mm, between 0.1 and 2.0 mm, between 2.5 mm and 3.5 mm). For example, the fluid capture material 44 may include 3 layers and have a total thickness of 1.2 mm. As another non-limiting example, the fluid capture material may include 6 layers and have a total thickness of 3 mm. For example, to deposit multiple layers, the process 30 may include depositing a first amount of the sorbent-binder material 38, curing the first amount of the sorbent-binder material to form a first layer, and repeating the process one or more times to form one or more additional layers, thereby forming a fluid capture material having multiple layers (e.g., 2, 3, 4, 5, 6, 7). In some embodiments, the first layer of the fluid capture material 44 may be pre-wetted before adding a second layer. In general, pre-wetting includes providing a suitable solvent to first layer, such as toluene, ethanol, water or a combination thereof. After pre-wetting the first layer, a second layer may be formed on top of the pre-wet first layer. In general, the second layer may be formed in a generally similar manner as described with respect to the first layer.
In some embodiments, the total thickness of the fluid capture material or coating may be less than 1 mm. For example, the total thickness may be between 0.1 mm and 0.9 mm, 0.2 mm and 0.8 mm, 0.2 and 0.7 mm, 0.3, and 0.6 mm, or between 0.4 mm and 0.5 mm. In some embodiments, each layer of the fluid capture material 44 may have the same thickness, such that the thickness formed for each layer (e.g., as described with respect to
As described herein, the fluid capture material 44 may be deposited onto one or more surfaces of the substrate 16, such as an air contactor. To illustrate this,
As illustrated, each channel 46 generally includes a wall 48 that has the fluid capture material 44 bound to its surface. As such, a gas flow that flows through the channels of the fluid capture coated substrate 42 may contact the fluid capture material 44, and thus, facilitate the binding of a target fluid (e.g., a CO2) with the fluid capture material 44.
As described herein, the disclosed fluid capture material 44 may have a relatively high fluid-binding capacity (e.g., water capacity and/or CO2 capacity). Table 1 shows results of CO2 capacity measurements for certain substrates coated with a fluid capture material 44. In general, the fluid capture materials 44 corresponding to Table 1 were doctor blade coated onto 2 in.×2 in. Inconel 718 coupons and evaluated for CO2 capture performance (e.g., CO2 capacity) at 0.04 kPa. A sampling of MOF-binder composites have been evaluated in aluminum weighing pans to establish film curing conditions, preliminary structural integrity of the films, and ambient sorption measurements. An example process for coating coupons with the slurry (i.e., the sorbent-binder material 38) entails mixing a MOF powder (i.e., a sorbent material 34) with an appropriate binder material 36, wetting agent, additive, and solvent in a container. The mixture may be vortexed for 1-2 min and then sonicated in an ultrasonic bath for 20 min at 72 kHz. The slurry is then coated onto the substrate 16 using a doctor blade of the appropriate gap (10-50 mil, 254-1270 μm) and left to dry in ambient conditions. For coatings in aluminum pans, the slurry may be added to the pan using a plastic pipet, the pan may be tilted to cover the bottom, and left to dry in ambient conditions. Once dry, pans or coupons are cured and activated using the appropriate conditions.
Table 1 shows examples of fluid capture materials 44 that may be used to capture CO2. Generally, table 1 shows the CO2 capacity of a control (e.g., example 1) as compared to samples that include a fluid capture material 44 formed using a sorbent material (i.e., MOF-808-Gly) and a binder material (e.g., examples 2 and 3) that is capable of cross-linking. More specifically, example 1 includes sorbent material, MOF-808-Gly, in powder form, without being deposited on a coupon. The CO2 capacity of example 1 at 400 ppm CO2 in N2 at 20° C. and 20% RH is 0.3 mmol/g.
Examples 2 and 3 illustrate fluid capture materials 44 formed using a sorbent material and a binder material that is, ultimately, cross-linked. More specifically, example 2 is a fluid capture material 44 with a sorbent material 34 (e.g., MOF-808-Gly) and a binder material 36 (e.g., aminopropylsilsesquioxane) that is capable of cross-linking. To prepare example 2, a slurry was prepared by mixing 2.44 g of a 25% aqueous solution of aminopropylsilsesquioxane, 17.6 g deionized water, 0.12 g of Triton™ X-100, and 5.1 g of MOF-808-Gly. After mixing, the slurry was coated on 2″ by 2″ Inconel coupons, dried, and cured overnight at 120° C. under vacuum. A high-quality coating was obtained that had an equilibrium CO2 uptake (e.g., CO2 capacity) of 0.37 mmol/g when exposed to 400 ppm CO2 in N2 gas stream at 20° C. and 20% RH.
Example 3 is a fluid capture material 44 with a sorbent material 34 (e.g., MOF-808-Gly), a binder material 36 (e.g., PVA), and a cross-linking agent 37 (e.g., PAA). To prepare example 3, a slurry was prepared by mixing 1.55 g of an aqueous solution of 15% PVA (e.g., 88% hydrolyzed) and 3% PAA, 5.2 g deionized water, ˜3 mg of Triton™ X-100, and 2.5 g of MOF-808-Gly. After mixing, the slurry was coated on 2″ by 2″ Inconel coupons, dried, and cured overnight at 125° C. under vacuum. The fluid capture material was obtained which scored a 3B on the ASTM D3359-17 adhesion test and which had an equilibrium CO2 uptake of 0.38 mmol/g when exposed to 400 ppm CO2 in N2 gas stream at 20° C. and 75% RH. In general, examples 2 and 3 illustrate two cross-linked aqueous binder formulations utilized with MOF-808-Gly to form a fluid capture material 44, which have CO2 binding capacity that is approximately equal to that of example 1. Further, examples 2 and 3 of the fluid capture materials have good adhesion to a substrate.
In some embodiments, the fluid capture material 44 may be formed using non-aqueous solvents. For example, another example (i.e., example 4) of a fluid capture material 44 generally includes a sorbent material 34 (e.g., MOF-808-Gly) and a silicon-containing binder material 36 capable of cross-linking. First, 1.2 mL of a 0.2 g/mL solution of SPR100 in methyl ethyl ketone (MEK) was mixed with 94 mg of disilanol PDS-1615, 53 μL alkoxysilane SIB1140.0, and 69 mg Hypermer™-KD1 in a vial. Separately, 3.0 g MOF-808-Gly was mixed with 5 mL isopropanol (IPA). The SPR100 containing solution 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 IPA to obtain a viscosity amenable to coating. Then, 38 μL of trihexylamine was added to this slurry and the mixture was coated on 2″ by 2″ Inconel coupons, dried, and cured at 90° C. under vacuum for 1 hr. A high-quality coating was obtained which scored a 4A on the ASTM D3359-17 adhesion test.
As described above, the fluid capture material 44 may be capable of binding water in certain embodiments. Several examples of fluid capture materials 44 in accordance with the present disclosure, as well as the performance of such fluid capture materials 44 are described below.
A first example of a water-binding fluid capture material 44 may include a sorbent material 34 (i.e., MOF-303), a binder material 36 (i.e., PVA), and a cross-linking agent (i.e., PAA) deposited on a metal substrate. More specifically, the first example of the water-binding fluid capture material 44 may be prepared by forming a slurry via 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 deionized water, ˜3 mg AGITAN 351, 1.0 g of MOF-303 and 0.02 g Tergitol 15-S-7. After mixing, the slurry was coated on 2″ by 2″ Inconel coupons and cured overnight at 125° C. A high-quality coating was obtained that was well adhered and had an equilibrium water uptake of 26-28% when tested in a humidity chamber set at 20% RH and 25° C.
A second example of a water-binding fluid capture material 44 includes a sorbent material 34 (e.g., MOF-303), a binder material 36 (e.g., PVA), and a cross-linking agent (e.g., PAA) deposited on a glass filled nylon coupon (e.g., a glass filled nylon substrate). More specifically, the second example of the water-binding fluid capture material 44 may be prepared by forming a similar slurry as described with respect to the first example of the water-binding fluid capture material 44 above and coating the slurry on a 2″ by 2″ glass-filled polyamide (PA12) nylon coupon. The coated sample was dried at room temperature and then cured overnight at 120° C. Once cooled to room temperature the sample was immersed in water to release air bubbles and then patted dry. A second layer of slurry was then coated as before. This process was repeated an additional time. After the final cure at 120° C. the coating weighed 0.9216 g, and adhered well to the substrate. The equilibrium water uptake at 20% RH/25° C. was 28%.
A third example of water-binding fluid capture material 44 includes multiple binder materials 36. For example, the third example of the water binding fluid capture material 44 may include binder materials 36 such as PVA, PAA, and poly(methyl/phenylsilsesquioxane). More specifically, the third example of the water-binding fluid capture material 44 may 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 deionized water, 0.02 g DISPERBYK 190, ˜3 mg AGITAN 351, and 2.0 g of MOF-303. A solution of 0.08 g Wacker MP-50E silicone emulsion diluted with 0.5 g deionized water was added to this mixture. After mixing, the slurry was coated on a 2″ by 2″ glass-filled PA12 nylon coupon. After drying at room temperature, the samples were cured at 120° C. for 4 hours. After cooling, the sample was immersed in water to release air bubbles, patted dry and then coated with another layer of slurry. The drying/curing process was then repeated as before. Two more layers of slurry were then coated on top of the first two using the same procedure. The weight of dried/cured coating at the end of this process was 1.4946 g. The coating was well adhered and had no cracks. The equilibrium water uptake at 20% RH/25° C. was 31-32%.
A fourth example of a water-binding fluid capture material 44 includes a sorbent material 34, such as MIL-160. To prepare the fourth example of the water-binding fluid capture material, 2.44 g of an aqueous solution of 13.5% PVA [88% hydrolyzed] and 4.5% PAA were mixed with 5.9 g deionized water, 0.040 g DISPERBYK 190, 0.030 g AGITAN 351, 4.34 g MIL-160 and 0.050 g Tergitol 15-S-7. After mixing, the slurry was coated on a 2″ by 2″ Inconel coupon. The sample was dried at room temperature and then overnight at 120° C. After cooling the sample was immersed in water to release bubbles and then was patted dry. A second layer of slurry was applied and cured as before. The second layer did not adhere to the first layer and subsequently flaked off.
A fifth example of a water-binding fluid capture material 44 includes multiple binder materials 36, such as silicon-containing binder materials, PVA, and PAA. It is presently recognized that utilizing hybrid binder materials 36 (i.e., two, three, four, or more than four different or distinct binder materials) may improve the adherent properties of the fluid capture material 44 or layer to a substrate and/or the adherent properties for each layer of multi-layer coatings. To prepare the fifth example of the water-binding fluid capture material, 8.0 g of an aqueous solution of 7.5% PVA [80% hydrolyzed) and 1.5% PAA were mixed with 9.0 g deionized water, 0.10 g DISPERBYK 2055, 0.015 g AGITAN 351, and 8.0 g of MIL-160. To this was added a solution of 0.08 g Wacker MP-50E silicone emulsion diluted with 2.0 g deionized water. After mixing, this slurry was used to coat a small Inconel heat exchanger. After drying at room temperature, the samples were cured at 120° C. for 2 hours. After cooling, the sample was immersed in water to release air bubbles, patted dry and then coated with another layer of slurry. The drying/curing process was then repeated as before. Finally, a third layer was applied as before. After final curing overnight at 120° C., 3.1 g of well adhered coating was obtained. The equilibrium water uptake at 20% RH/25° C. was 30-32%.
It is further recognized that cross-linking the composite coating may improve the structural integrity of the fluid capture material 44 or coating. To illustrate the improved structural integrity based on the addition of a cross-linking agent 37, two compositions of sorbent materials 34 and binder materials 36 were prepared. The first composition is in accordance with the disclosed fluid capture material 44, and thus is formed by cross-linking the binder material 36 (i.e., via addition of PAA). In the second composition, the binder material 36 is not cross-linked (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 deionized water, 0.02 g DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated on a 1″ by 1″ Inconel coupon, dried at room temperature and cured overnight at 125° C. in a vacuum oven. The coupon was cooled to room temperature in a vacuum desiccator and then quickly weighed. It was then submersed in 10 mL of deionized water and put in a 90° C. oven for 2 hours. At the end of this time the coupon was removed and dried at 90° C. for an hour followed by 2 hours in the 125° C. vacuum oven. Finally, the sample was cooled in a vacuum desiccator and reweighed as before. The weights were: (1) uncoated coupon: 5.0038 g; (2) coated coupon after cure: 5.3206 g (i.e., the coating weight was 0.3168 g); (3) coated coupon after water immersion/drying: 5.3087 g (i.e., the coating was 0.3049 g); and (4) coating weight retained after water immersion: 96.2%.
To prepare the second composition (i.e., prepared without using a cross-linking 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 deionized water, 0.02 g DISPERBYK 190, and 1.0 g of MIL-160. After mixing, the slurry was coated on a 1″ by 1″ Inconel coupon, dried at room temperature and cured overnight at 125° C. in a vacuum oven. The coupon was cooled to room temperature in a vacuum desiccator and then quickly weighed. It was then submersed in 10 mL of deionized water and put in a 90° C. oven for 2 hours. Soon after immersion in water the coating started to fall apart and come off the coupon. At the end of this time the coupon was removed and dried at 90° C. for an hour followed by 2 hours in the 125° C. vacuum oven. Finally, the sample was cooled in a vacuum desiccator and reweighed as before. The weights were: (1) uncoated coupon: 5.0320 g; (2) coated coupon after cure: 5.1974 g (i.e., the coating weight was 0.1654 g); (3) coated coupon after water immersion/drying: 5.0573 g (i.e., the coating was 0.0253 g); and (4) coating weight retained after water immersion: 15.3%. In particular, the first composition (i.e., the example of the fluid capture material 44 including a cross-linked binder) contains PAA and the cured film obtained in this case retained 96% of its mass after 2 hours in 90° C. water. In contrast, using the second composition (i.e., when PVA was used without any cross-linker), only 15% of the mass was retained after testing the same way.
As described herein, the fluid capture material 44 may be formed using a cross-linking agent 37 that has different types of functional groups that may facilitate formation of the fluid capture material 44. To prepare an example of such a composition, 0.30 g poly(vinyl butyral) was dissolved in 6.0 g of isopropanol. Further, 0.065 g 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, 3.0 g of an amine treated silica sorbent, and 0.07 g BYK9076 were then mixed in. The resulting slurry was coated on aluminum coupons using a doctor blade. After drying at room temperature, the samples (e.g., the aluminum coupons coated with the slurry) were placed in a 90° C. oven for an hour to cure. The CO2 uptake was measured under dry conditions at 25 C using 400 ppm CO2 in nitrogen. The average value was determined to be 0.734 mol CO2/kg coating (0.032 g/g).
As described herein, the fluid capture material 44 may be capable of capturing a target fluid, such as H2O. In such embodiments, it is presently recognized that it may be advantageous to form a fluid capture material 44 that is capable of releasing the capture fluid. To illustrate this,
Referring to the method 60, at block 62, a gas flow 64 is provided to the substrate 16 coated with the fluid capture material 44. Water in the gas flow 64 binds to the capture coating, thereby generating a dry gas flow 66. At block 68, a heat exchanger 70 is heated (e.g., using a hot air at a temperature greater than 80° C., greater than 85° C., greater than 90° C., or greater than 95° C.). In any case, the water bound to the fluid capture material 44 may be released as steam 72. At block 74, a condenser 76 may receive the steam 72 and cool the steam 72, thereby producing water 78. At block 80, the heat may be recovered. In this way, the fluid capture material 44 may be utilized to extract a fluid and, in certain embodiments, release the fluid.
As described herein, the fluid capture material 44 may include a cross-linking agent 37 (i.e., used to cross-link the polymer forming the fluid capture material 44). In some embodiments, the cross-linking agent 37 may include colloidal silica.
Accordingly, the present disclosure relates to a fluid capture material or fluid capture material that provides improved fluid binding capacity and stability. The fluid capture material or coating generally includes a sorbent material and a binder material. As described herein, the resulting fluid capture material or coating may include a cross-linked polymer formed of one or more binder materials and certain cross-linking agents such as UV light, silica, polyacrylic acid, heat, or a combination thereof.
Technical effects of the invention include, and are not limit to, improving the capacity and/or capture efficiency of a substrate via a fluid capture material. By providing the disclosed fluid capture material, the amount of certain gases that remain in an exhaust gas flow may be reduced. Moreover, by forming a fluid capture material that includes a cross-linked polymer, a relatively higher amount of sorbent material compared to binder material may be used, thereby improving the fluid binding capacity of the fluid capture material.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
