JP2015514011A - Impervious polymer coatings on selected honeycomb channel surfaces - Google Patents

Abstract

The adsorbent structure for CO2 recovery has a honeycomb substrate having partition walls, and the partition walls penetrate the honeycomb substrate. The partition wall has a channel surface that defines a plurality of individual channels including a plurality of reaction channels and a plurality of heat exchange channels. The reaction channels and heat exchange channels are arranged to transfer heat between the individual reaction channels and the individual heat exchange channels. The surface of the reaction channel surface includes an adsorbent material, and the surface of the heat exchange channel surface has a coating layer. The covering layer includes an impermeable layer formed of a polymer material. The polymer material of the impermeable layer does not substantially penetrate into the adsorbent material of the partition walls or reaction channel surfaces. The method of forming the adsorbent structure includes coating the surface of the heat exchange channel with a polymeric material using a liquid composition such as an aqueous polymer emulsion.

Description

Explanation of related applications

  This application claims the benefit of priority under 35 USC 119 of US Provisional Patent Application No. 61/620673, filed April 5, 2012. The present specification depends on the content of the specification of the provisional patent application, and the content of the specification of the provisional patent application is incorporated herein by reference in its entirety.

The present specification relates generally to an adsorbent structure for recovering carbon dioxide (CO ₂ ) from a gas stream, and more particularly with a designated reaction flow channel having an adsorbent surface and an impermeable barrier layer. It relates to an adsorbent structure having designated heat exchange channels.

Carbon dioxide is a greenhouse gas associated with global warming. Carbon dioxide is often a byproduct of various consumer and industrial processes, such as fossil fuel combustion, natural gas refining and oil recovery systems. From an economic point of view, carbon emissions trading and future emission regulations and carbon emission regulations from other CO ₂ point sources inspire the development of CO ₂ capture technology.

Carbon dioxide recovery by a solid adsorbent can be realized by a process such as a temperature swing adsorption method, a pressure swing adsorption method, or a vacuum swing adsorption method. For example, in a temperature swing adsorption process, CO ₂ from a process gas is adsorbed on a solid adsorbent at a low temperature and then released from the adsorbent by heating the adsorbent to a high temperature to become an exhaust gas stream. When CO ₂ is released from the adsorbent, to start a new adsorption cycle, the sorbent must be cooled again. In large scale applications with temperature swing processes, the technical challenge remains to perform temperature cycling quickly and uniformly over large amounts of solid adsorbent.

Accordingly, there remains a need for alternative methods and apparatus that can be used in a temperature swing adsorption process to recover CO ₂ from a process gas stream.

According to various embodiments, the sorbent structure for CO ₂ recovery is provided. The adsorbent structure includes a honeycomb substrate, and the honeycomb substrate has partition walls penetrating the honeycomb substrate in the axial direction from the inflow surface of the honeycomb substrate to the outflow surface of the honeycomb substrate opposite to the inflow surface. The partition wall has a channel surface that defines a plurality of individual channels. The plurality of individual channels include a plurality of reaction channels and a plurality of heat exchange channels, so that the channel surface of the reaction channel is a reaction channel surface, and the channel surface of the heat exchange channel is an exchange channel surface. The reaction channels and heat exchange channels are arranged so that heat is transferred between the individual reaction channels and the individual heat exchange channels. The reaction channel surface includes an adsorbent material and the heat exchange channel surface has at least one coating layer. In a non-limiting embodiment, the at least one coating layer comprises, for example, poly (vinyl butyral) resin, polyacrylates, polynitriles (including carboxylated acrylonitrile-butadiene copolymers), polychloroprenes, poly ( Water impermeable layers formed of polymer materials such as vinyl chloride), poly (vinylidene fluoride), polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof and composite materials thereof Can be included. The polymer material of the impermeable layer does not substantially penetrate into the partition walls forming the exchange channel surface.

According to another embodiment, a method for forming an adsorbent structure for CO ₂ capture is provided. The method can include providing a honeycomb substrate formed of an adsorbent. The honeycomb substrate has partition walls penetrating the honeycomb substrate in the axial direction from the inflow surface of the honeycomb substrate to the outflow surface of the honeycomb substrate opposite to the inflow surface. The partition wall has a channel surface that defines a plurality of individual channels. The plurality of individual channels include a plurality of reaction channels and a plurality of heat exchange channels, so that the channel surface of the reaction channel is a reaction channel surface, and the channel surface of the heat exchange channel is an exchange channel surface. The method can further include shielding each inflow end and outflow end of the reaction channel to form a shield reaction channel. The method allows each of the heat exchange channels to flow through the aqueous polymer emulsion and does not allow the shield reaction channels to flow, and thus forms an aqueous polymer emulsion emulsion film that covers only the exchange channel surface. A step of feeding an aqueous polymer emulsion (for example, latex) or an aqueous polymer dispersion may be further included. The method can further include the step of drying the emulsion coating to form an impermeable layer on the exchange channel surface. The water-impermeable layer may be, for example, poly (vinyl butyral) resin, polyacrylates, polynitriles (including carboxylated acrylonitrile-butadiene copolymer), polychloroprenes, poly (vinyl chloride), poly (fluorinated) Polymeric materials such as vinylidene), polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof and composite materials thereof may be included.

According to another embodiment, another method is provided for forming an adsorbent structure for CO ₂ capture. The method can include providing a honeycomb substrate formed of a ceramic material. The honeycomb substrate has partition walls penetrating the honeycomb substrate in the axial direction from the inflow surface of the honeycomb substrate to the outflow surface of the honeycomb substrate opposite to the inflow surface. The partition wall has a channel surface that defines a plurality of individual channels. The plurality of individual channels include a plurality of reaction channels and a plurality of heat exchange channels, so that the channel surface of the reaction channel is a reaction channel surface, and the channel surface of the heat exchange channel is an exchange channel surface. The method can further include shielding each inflow end and outflow end of the reaction channel to form a shield reaction channel. The method allows each of the heat exchange channels to flow through the aqueous polymer emulsion and does not allow the shield reaction channels to flow, and thus forms an aqueous polymer emulsion emulsion film that covers only the exchange channel surface. The method may further include feeding the aqueous polymer emulsion on top. The method can further include the step of drying the emulsion coating to form an impermeable layer over the exchange channel surface. The water-impermeable layer may be, for example, poly (vinyl butyral) resin, polyacrylates, polynitriles (including carboxylated acrylonitrile-butadiene copolymer), polychloroprenes, poly (vinyl chloride), poly (fluorinated) Polymeric materials such as vinylidene), polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof and composite materials thereof may be included.

  Additional features of the embodiments described herein will be set forth in the detailed description that follows. These additional features and advantages will be, to some extent, readily apparent from the description to those skilled in the art, or implement the embodiments described in the following description, including the accompanying drawings and claims. Will be easily recognized.

  Both the foregoing general description and the following detailed description are intended to illustrate various embodiments and to provide an overview or framework for understanding the nature and nature of the claimed subject matter. Is natural. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.

FIG. 1 is a perspective view of an adsorbent structure according to an embodiment of the present specification, showing a honeycomb substrate having partition walls defining reaction channels and heat exchange channels. FIG. 2 is a partial view of one embodiment of the adsorbent structure of FIG. 1 in which the reaction channels are defined by the adsorption surfaces of the honeycomb substrate partition walls and the heat exchange channels are coated with an impermeable layer. FIG. 3 shows the adsorbent structure of FIG. 1 in which the reaction channel is defined by the adsorption surface of the partition walls of the honeycomb substrate and the heat exchange channel is coated with a water impermeable layer and another layer covering the water impermeable layer. FIG. 4 is a partial view of an embodiment. FIG. 4 is a schematic diagram of a film formation method according to some embodiments described herein of a method for forming an adsorbent structure according to embodiments described herein.

Reference will now be made in detail to an embodiment of an adsorbent structure for CO ₂ recovery from a gas stream and a method for forming the same, each example shown in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like elements. One embodiment of the adsorbent structures for CO ₂ recovery from gas streams is shown schematically in Figure 1, another embodiment is shown in Figures 2 and 3. The adsorbent structure generally has a honeycomb substrate, and the honeycomb substrate has partition walls penetrating the honeycomb substrate in the axial direction from the inflow surface of the honeycomb substrate to the outflow surface of the honeycomb substrate opposite to the inflow surface. The partition wall has a channel surface that defines a plurality of individual channels. The plurality of channels includes a plurality of reaction channels and a plurality of heat exchange channels, so that the channel surface of the reaction channel is a reaction channel surface, and the channel surface of the heat exchange channel is an exchange channel surface. The reaction channels and heat exchange channels are arranged so that heat is transferred between the individual reaction channels and the individual heat exchange channels. The reaction channel surface includes an adsorbent material, and the heat exchange channel surface has at least one impermeable coating layer formed of a polymer material. The polymer material of the impermeable coating does not penetrate from the exchange channel surface into the adsorbent material on the reaction channel surface. Thus, in a CO ₂ capture process from a gas stream, the gas stream can flow through the reaction channel and a heat exchange medium such as water can flow through the heat exchange channel, but the heat exchange medium is impermeable. can not enter the reaction channel is blocked by the covering layer will CO ₂ loading capacity of the adsorbent decreases otherwise. The adsorbent structure and the method of forming the adsorbent structure will now be described in further detail with particular reference to the accompanying drawings.

With reference to FIGS. 1 and 2, an adsorbent structure 100 for CO ₂ recovery from a gas stream according to some embodiments can include a honeycomb substrate 110, and the honeycomb substrate 110 can flow into the honeycomb substrate 110. The partition wall 120 penetrates the honeycomb substrate 110 in the axial direction 90 from the surface 130 to the outflow surface 140 of the honeycomb substrate 110. Outflow surface 140 is on the opposite side of the inflow surface. The partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150 and 160. The plurality of individual channels 150 and 160 include a plurality of reaction channels 150 and a plurality of heat exchange channels 160. Accordingly, the channel surface 125 of the reaction channel 150 is the reaction channel surface 155, and the channel surface 125 of the heat exchange channel 160 is the exchange channel surface 165. The reaction channel 150 and the heat exchange channel 160 are arranged such that heat is transferred between the individual reaction channels 150A and 150B and the individual heat exchange channels 160A and 160B. Reaction channel surface 155 includes an adsorbent material. The exchange channel surface 165 has at least one covering layer that covers the exchange channel surface 165. At least one coating layer includes an impermeable layer 170 formed of a polymeric material. The polymer material of the impermeable layer 170 does not substantially penetrate into the adsorbent material of the partition 120 forming the exchange channel surface 165 or into the adsorbent region of the reaction channel surface 155.

The honeycomb substrate 110 may be any suitable porous material including, for example, glass, ceramic, non-oxide ceramic (eg, carbide, nitride), carbon, alloy, metal, polymer, composite, and mixed materials thereof. Can be formed. In some embodiments, the honeycomb substrate 110 may be, for example, zeolite, MOF (metal organic structure), clay, layered double hydroxide, solid amine, and alkali / alkaline earth oxide or zeolite, MOF (metal composite containing an organic structure) or cordierite, SiC, mullite, alumina and aluminum titanate, and such as carbon, the CO ₂ can be formed by the adsorbent material capable of adsorbing. In other embodiments, the honeycomb substrate 110 can be formed of a ceramic support material in which an adsorbent material is embedded. In other embodiments, the honeycomb substrate 110 can be formed of a non-adsorbent material and subsequently loaded with the adsorbent material by a suitable method, such as, for example, wash coating. The honeycomb substrate 110 can be made by any suitable method, but in general, such as by extrusion, mold or 3D printing, or shaping of an appropriate material and optionally, for example, by heating or firing the material. It can be made by finishing the material.

In general, an adsorbent material according to embodiments described herein is from a process gas stream comprising CO ₂ and one or more other gases such as methane, nitrogen, hydrogen, hydrogen sulfide or mixtures thereof. It is a material capable of reversibly adsorbing CO ₂ . As used herein, “capable of reversibly adsorbing CO ₂ from a process gas stream” means that the adsorbent material is CO ₂ from the process gas stream in a first operating parameter set (eg, initial temperature). Can be adsorbed, and by changing to the second operating parameter set (for example, by increasing the temperature), this means that the adsorbed CO ₂ can be released. In a non-limiting embodiment, the process gas stream containing CO ₂ includes, for example, natural gas, flue gas, air, biogas, water gas conversion mixture from a hydrogen gas production system, and exhaust gas from a combustion process. can do. In some embodiments, the honeycomb substrate 110 is formed of an adsorbent material or a non-adsorbent material to which the adsorbent material is added during formation of the honeycomb substrate 110. In other embodiments, the adsorbent material is loaded into the pores of the honeycomb substrate 110 formed of a non-adsorbent material.

  According to some embodiments, suitable adsorbent materials from which the honeycomb substrate 110 can be made (eg, by casting, extrusion or molding) include, but are not limited to, zeolites, zeolite-like imidazole structures Body, metal organic structure, carbon, mesoporous alumina and mesoporous silica, including SBA-15 and the like, and combinations of the above materials, and any of the above materials functionalized with amine or amino groups. In other embodiments, the honeycomb substrate 110 can be formed of a ceramic support material embedded with one or more of the adsorbent materials described above. In such embodiments, the ceramic support material can be cast or coextruded with the adsorbent material, for example, to form a honeycomb substrate.

  According to some embodiments, suitable adsorbent materials that can be applied on at least the reaction channel surface 155 of the honeycomb substrate 110 include zeolites, zeolite-like imidazole structures, metal organic structures, carbon, mesoporous alumina. And any of the above materials functionalized with amines or amino groups, including but not limited to mesoporous silica and combinations of the above materials, including SBA-15 and the like. In accordance with the embodiments described herein, the adsorbent material can be applied by any suitable technique, such as by wash coating.

  The honeycomb substrate 110 of the embodiment of FIG. 1 is cylindrical, but according to other embodiments, the honeycomb substrate 110 may be of any desired shape, such as a triangular solid, a rectangular solid, a square solid, or a hexagonal solid. It can have any shape of. Furthermore, the honeycomb substrate 110 can have any suitable length in the axial direction 90, such as 1 cm to 10 m.

In general, the material from which the honeycomb substrate 110 is formed is porous. In some embodiments, the honeycomb substrate 110 can be formed of an adsorbent material. In other embodiments, the honeycomb substrate is applied with an adsorbent material during formation of the honeycomb substrate 110 (eg, by coextrusion) or after formation of the honeycomb substrate 110 (eg, by wash coating), such as a ceramic support. Can be made of non-adsorbent material. The material of the honeycomb substrate 110 may have a medium pore size of 1.0 μm to 15 μm in some embodiments. In some embodiments, the adsorbent material and honeycomb substrate 110 can have some pores with a pore size of less than 1 μm and some pores with a pore size of more than 1 μm. For example, the adsorbent material and honeycomb substrate 110 can have pores with more than 50% of the pores having a diameter less than 1 μm. As used herein, “pore diameter” refers to the cross-sectional diameter, or, if the pore has a non-circular cross-section, the diameter of a virtual circle having the same cross-sectional area as the non-circular pore cross-sectional area. Point to. In general, the pore size of any given material is within the statistical distribution. Thus, the “median pore diameter” or “d ₅₀ ” is based on the statistical distribution of all pores, where 50% of the pore diameter is above and 50% of the pore diameter is Refers to the length measurement below it. However, embodiments of the adsorbent structure 100 described herein are not limiting and include other pore median values, including honeycomb substrates with pore median values less than 1.0 μm or greater than 15 μm. Needless to say, the honeycomb substrate 110 can also be used.

  In some embodiments, the honeycomb substrate 110 can have a porosity of 35% to 60% as measured by mercury intrusion porosimetry. However, embodiments of the adsorbent structure 100 described herein include, but are not limited to, a honeycomb substrate 110 having another porosity, including a honeycomb substrate with a porosity less than 35% or greater than 60%. Of course, it can also be used.

  While the shape of the individual channels 150, 160 is shown as a square in the honeycomb substrate 110 of FIGS. 1 and 2, the shape of the individual channels in the embodiment of the adsorbent structure 100 described herein is shown in FIGS. Of course, the shape is never limited. Rather, the individual channels 150 and 160 in the honeycomb substrate 110 are not limited, but are rectangular, square, circular, oval, hexagonal, triangular, pentagonal, regular polygons having 3 to 20 sides, or irregular polygons, and the like. Can have any desired cross-section, including combinations of The cross-sectional areas of the individual channels 150 and 160 are preferably selected so as to maximize the ratio of the cross-sectional area of the individual channels 150 and 160 to the cross-sectional area of the honeycomb substrate 110 sliced in the direction perpendicular to the axial direction 90. Thus, it should be readily appreciated that numerous space filling options are possible, such as planar filling of channels made into one or more types of geometric shapes. Furthermore, it is a win that the reaction channel 150 and the heat exchange channel 160 need not be the same shape or size, and the number need not be equal within the honeycomb substrate 110. In some embodiments, for example, reaction channel 150 and heat exchange channel 160 may comprise a plurality of (eg, 2, 3, 4, 5, or more than 5) rows of reaction channels 150 of heat exchange channel 160. They can be arranged in rows so that they are arranged between each row.

The individual channels 150 and 160 in the honeycomb substrate 110 have a cell density defined as the number of individual channels 150 and 160 existing in the honeycomb substrate 110 per square inch of the inflow surface 130. In some embodiments, the honeycomb substrate 110 can have a cell density of about 100 to about 2000 (about 15.5 to about 310 / cm ² ) individual channels per square inch of the inflow surface. In a preferred embodiment, the honeycomb substrate 110 can have a cell density of about 300 to about 1500 (about 46.5 to about 232.5 / cm ² ) individual channels per square inch of the inflow surface 130. In a further preferred embodiment, the honeycomb substrate 110 can have a cell density of about 600 to about 1500 (about 93.0 to about 232.5 / cm ² ) individual channels per square inch of the inflow surface. In general, the cell density of the honeycomb substrate 110 can be selected to match the viscosity of the aqueous polymer emulsion used to coat the exchange channel surface 165, as described in more detail below. That is, in some embodiments, the reaction channel 150 is a cell of about 100 to about 2000, about 300 to about 1500, or about 600 to about 1500 reaction channels per square inch of the inflow surface 130. The cell density and geometry of the heat exchange channels 160 that can have a density and are dispersed between the reaction channels 150 is sufficient for the heat exchange channels 150 with at least one coating layer including the water-impermeable layer 170. It can be limited only to cell densities that allow coverage.

  Referring to FIGS. 1 and 2, as described above, the reaction channel 150 and the heat exchange channel 160 are arranged such that heat is transferred between the individual reaction channels 150A and 150B and the individual heat exchange channels 160A and 160B. Of course, numerous channel geometries and layout configurations are possible, but an example of heat transfer is shown in the embodiment of FIG.

There are other heat transfer routes that may exist in the embodiment of FIG. 2, but the most obvious routes are between reaction channel 150A and heat exchange channel 160A and between reaction channel 150B and heat exchange channel 160B. In either example, heat transfer between the reaction channels 150A and 150B and the respective heat exchange channels 160A and 160B occurs directly between the adjacent channels through the partition wall 120. Thus, if a heat transfer medium or heat transfer fluid, such as water, flows through the heat exchange channels 160A, 160B, the temperature of the reaction channels 150A, 150B will be the temperature of the heat transfer medium relative to the temperature of the reaction channels 150A, 150B. Can be affected by. For example, if the heat transfer medium is cooler than the temperature of the reaction channels 150A, 150B, the reaction channel is cooled, which is advantageous for CO ₂ adsorption. Similarly, if the heat transfer medium is warmer than the temperature of the reaction channels 150A, 150B, the reaction channel is warmed, favoring CO ₂ emissions. Thus, the adsorbent in the adsorbent structure 100 such that heat transfer between the reaction channels 150A, 150B and the respective heat exchange channels 160A, 160B would be required during the temperature swing adsorption cycle. It should be understood that a rapid and uniform adjustment of the temperature of the material may be possible.

Next, an example embodiment of the adsorbent structure 100 of FIG. 1 will be described with reference to FIGS. In all such embodiments, the reaction channel surface 155 includes an adsorbent material and the exchange channel surface 165 has at least one coating layer. At least one covering layer on the exchange channel surface 165 includes an impermeable layer 170 formed of a polymeric material, described in more detail below. Further, in all embodiments, the polymer material of the impermeable layer 170 does not substantially penetrate into the partition 120 forming the exchange channel surface 165, the adsorbent material of the partition 120 or the adsorbent material of the reaction channel surface 155. . As used herein, "substantially infiltration" is the water-impermeable layer 170 can be slightly penetrate into the partition walls 120, CO ₂ in the slight penetration of the behavior of the adsorbent structure 100 This means that the pores of the adsorbent material that must be adsorbed must not be blocked. Should the polymer material of the water-impermeable layer 170 penetrate through the partition wall 120 and reach the reaction channel surface 155, at least one surface of the individual reaction channels 150A and 150B can possibly adsorb CO _2. Disappear. In the illustrated embodiment, the polymeric material of the impermeable layer 170 is less than 25%, less than 10% or less than 5% of the thickness of the septum 120 between adjacent heat exchange channels 160 and reaction channels 150. It can penetrate into the adsorbent material of the partition wall 120.

Referring to FIG. 2, a partial view of the honeycomb substrate 110 (see FIG. 1) is shown. In some embodiments, the honeycomb substrate 110 is formed of an adsorbent material as described above. Therefore, the partition 120 having the reaction channel surface 155 and defining the reaction channels 150A and 150B is also formed of the adsorbent material. When the honeycomb substrate 110 is formed of a non-adsorbent ceramic material (that is, a material that does not reversibly absorb CO ₂ ) to which an adsorbent material is added during or after the formation of the honeycomb substrate 110. In other embodiments, such as, adsorbent material is exposed on each of the reaction channel surfaces 155. The exchange channel surface 165 has at least one coating layer. The at least one covering layer in the embodiment of FIG. 2 is an impermeable layer 170 formed of a polymer material, which will be described in more detail below. The polymer material of the impermeable layer 170 does not substantially penetrate into the partition 120 forming the exchange channel surface 165, the adsorbent material of the partition 120 or the adsorbent material of the reaction channel surface 155.

  In general, the honeycomb substrate 110 is formed with an adsorbent material or with a non-adsorbent material to which adsorbent material is added to produce the covering shape of the embodiment of FIG. The reaction channel 150 of the substrate 110 is shielded or otherwise shielded, and the coating material is introduced only into the heat exchange channel 160. The coating material can be dried by heating, if necessary, to form at least one coating layer including the water-impermeable layer 170 only on the heat exchange channel 160. After completion of the coating process, the shield can be removed from the reaction channel 150.

Referring to FIG. 3, a partial view of the honeycomb substrate 110 (see FIG. 1) is shown. In some embodiments, the honeycomb substrate 110 is formed of an adsorbent material as described above. Therefore, the partition 120 having the reaction channel surface 155 and defining the reaction channels 150A and 150B is also formed of the adsorbent material. When the honeycomb substrate 110 is formed of a non-adsorbent ceramic material (that is, a material that does not reversibly absorb CO ₂ ) to which an adsorbent material is added during or after the formation of the honeycomb substrate 110. In other embodiments, such as, adsorbent material is exposed on each of the reaction channel surfaces 155. The exchange channel surface 165 has at least one coating layer. The at least one covering layer in the embodiment of FIG. 3 covers a water-impermeable layer 170 made of a polymer material, which will be described in more detail below, and also covers the water-impermeable layer 170, also described in more detail below. At least one additional layer 180. The polymer material of the impermeable layer 170 does not substantially penetrate into the partition 120 forming the exchange channel surface 165, the adsorbent material of the partition 120 or the adsorbent material of the reaction channel surface 155.

  In general, the honeycomb substrate 110 is formed with an adsorbent material or with a non-adsorbent material to which adsorbent material is added to produce the covering shape of the embodiment of FIG. The reaction channel 150 of the substrate 110 is shielded or otherwise shielded, and the first coating material is introduced only into the heat exchange channel 160. The first coating material can be introduced only into the heat exchange channel 160 and, if necessary, dried by, for example, heating, to form the water-impermeable layer 170. Subsequently, the second coating material can be introduced only into the heat exchange channel 160 and, if necessary, dried, for example by heating, to form at least one additional layer 180 covering the impermeable layer 170. it can. After the coating formation process is complete, the shield can be removed from the reaction channel 150.

  Next, referring generally to the sorbent structure 100 illustrated in FIG. 1 and further illustrated in FIGS. 2 and 3, the exchange channel surface 165 of the honeycomb substrate 110 has at least one coating layer. The at least one coating layer includes a water-impermeable layer 170 (FIGS. 2 and 3) formed of a polymer material, and optionally further includes at least one additional layer 180 (FIG. 3) covering the water-impermeable layer 170. Including. FIG. 2 or 3 shows at least one coating layer as a single layer (FIG. 2) or two layers (FIG. 3), but the at least one coating layer sequentially on the partition 120 defining the exchange channel surface 165 It can be composed of a plurality of coating layers to be deposited. Similarly, in some embodiments, at least one coating layer can include exactly one impermeable layer 170 formed of a single polymer material, or each can be formed of a different polymer material. More than one impermeable layer 170 can be included. In all embodiments, as described above, the polymer material of the impermeable layer 170 is substantially within the partition 120 forming the exchange channel surface 165, the adsorbent material of the partition 120, or the adsorbent material of the reaction channel surface 155. Do not enter.

According to some embodiments, the impermeable layer 170 can include a water-impermeable polymer material. Thus, when water is used as the heat transfer medium in the heat exchange channel 160 during the CO ₂ recovery process, the water is adsorbed with CO ₂ (either within the partition 120 or on the reaction channel surface 155). It cannot penetrate into the adsorbent material (with or without). Without wishing to be bound by theory, the presence of the heat transfer medium, such as water adsorbent in the material is considerably CO ₂ removal capacity from the process gas stream containing the adsorbent structure 100, the CO ₂ It can be lowered. In some embodiments, the polymeric material is impermeable and hydrophobic.

The polymer material of the water-impermeable layer 170 can form a uniform film on the material of the honeycomb substrate 110, but can be applied to any region of the honeycomb substrate 110 made of an adsorbent material necessary for CO ₂ capture. Any polymer material that does not substantially penetrate can be selected. In the illustrated embodiment, polymeric materials that are particularly well suited for this purpose include, for example, poly (vinyl butyral) resins, polyacrylates, polynitriles (including carboxylated acrylonitrile-butadiene copolymers), polychloroprene. (Neoprene), poly (vinyl chloride), poly (vinylidene fluoride), polyolefins such as polyethylene or polypropylene, poly (tetrafluoroethylene), silicones, polyurethanes, composite materials containing one or more of these and these However, the present invention is not limited to these. The material of the illustrated embodiment is a honeycomb made of, for example, zeolite, cordierite, silicon carbide (SiC), aluminum titanate, mullite, spinel, perovskite, silicate, carbon or alumina and mixtures thereof. Particularly well suited for use on a substrate.

In some embodiments, the impermeable layer 170 of at least one covering layer on the exchange channel surface 165 can be formed on the partition wall 120 or deposited directly. As described in more detail below with respect to the method for forming the sorbent structure 100, in some embodiments, the water impermeable layer 170 contains a selected cured or uncured polymeric material. It can be applied by introducing an aqueous polymer emulsion or dispersion into the honeycomb substrate 110. The polymer material in the aqueous polymer emulsion has a particle size suitable to prevent intrusion into any adsorbent material, and the viscosity of the aqueous polymer emulsion provides suitable casting and coating uniformity. You can choose to. Especially when the honeycomb substrate 110 has a cell density higher than 800 (124 / cm ² ) individual channels per square inch of the inflow surface 130, it is hindered by, for example, surface tension of the aqueous polymer emulsion into the individual channels 150, 160. The viscosity of the aqueous polymer emulsion can also be chosen to be low enough to allow entry. When the exchange channel surface 165 is sufficiently covered by the polymeric material, the aqueous vehicle in the aqueous polymer emulsion can be removed, for example, by heating or drying by heating, and if necessary, the impermeable layer can be removed. The polymeric material can be cross-linked or cured to form.

  In another embodiment, for example, as in the embodiment of FIG. 3, the at least one coating layer can further include at least one additional layer 180 covering the impermeable layer 170. In such embodiments, the at least one additional layer 180 can function as a topcoat layer that increases the water impermeability of the exchange channel surface 165 than is achieved with the impermeable layer 170 alone. In other embodiments not shown, at least one additional layer 180 may be disposed between the exchange channel surface 165 and the impermeable layer 170. In such an embodiment, the at least one additional layer 180 may be substantially incorporated into the adsorbent material of the septum 170 of the polymer material of the impermeable layer, for example, when the impermeable layer 170 is applied or applied. Can act as a primer layer that reduces the porosity of the exchange channel surface 165 to the extent necessary to prevent intrusion. In some embodiments, the at least one additional layer 180 can include a polymeric material that is different from the polymeric material of the impermeable layer 170. In a non-limiting illustrative embodiment, the at least one covering layer of the exchange channel surface 165 includes the above-described impermeable layer 170 and the addition of at least one polymeric material below or above the impermeable layer 170. Layer 180 can be included. In a non-limiting embodiment, the polymeric material of the at least one additional layer 180 can be, for example, polystyrenes, epoxy resins, polyesters, polycarbonates, nylons, poly (vinyl butyral) resins, polyacrylates, (carboxylated acrylates). Polynitriles (including nitrile-butadiene copolymers), polychloroprene (neoprene), poly (vinyl chloride), poly (vinylidene fluoride), polyolefins such as polyethylene or polypropylene, poly (tetrafluoroethylene), silicones And polymers such as polyurethanes, composite materials containing one or more of these, and mixed materials of two or more of these.

  Generally, in the sorbent structure 100 according to some embodiments described above, the exchange channel surface 165 includes at least one coating layer that includes an impermeable layer 170. If desired, it can be coated with at least one additional layer 180. In all cases, the thickness of the one or more layers covering the exchange channel surface 165 varies depending on the cell density of the honeycomb substrate 110. In some embodiments, the total thickness of the coating on the exchange channel face 165 is less than 50% based on the area of the individual heat exchange channel 160 in a cross section perpendicular to the axial direction 90 of the heat exchange channel 160 that includes the coating. , Less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, or less than 1% can be constrained by all coating layers in each heat exchange channel 160. In some embodiments, the total thickness of the at least one coating layer (including the water-impermeable layer 170 and, optionally, at least one additional layer 180) is 0, such as from about 3 μm to about 50 μm. The thickness may be from about 0.01 μm to about 600 μm.

Having described various embodiments of the sorbent structure 100 of FIG. 1 with reference to FIGS. 2 and 3, a method for making the sorbent structure 100 will now be described. In some embodiments, the method includes providing a honeycomb substrate 110 formed of an adsorbent material. In other embodiments, the method is formed of a support material other than the adsorbent material used for CO ₂ adsorption, including, for example, a non-adsorbent material, and the adsorbent material is added during or after formation of the honeycomb material 110. Providing the honeycomb substrate 110. In the following description of the method, the structural aspect of the adsorbent structure of FIGS. 1-3 is also a schematic illustration of FIG. Sometimes referred to.

According to some embodiments, a method for forming an adsorbent structure 100 for CO ₂ capture includes providing a honeycomb substrate 110 formed of an adsorbent material. Adsorbent materials suitable for making the honeycomb substrate 110 include, by way of non-limiting example, zeolites, zeolite-like imidazole structures, metal organic structures, carbon, mesoporous alumina, and mesoporous silica, including SBA-15 and the like, And combinations of the above materials, as well as any of the above materials functionalized with amine or amino groups.

  The honeycomb substrate 110 formed of the adsorbent material has partition walls 120 penetrating the honeycomb substrate 110 in the axial direction 90 from the inflow surface 130 of the honeycomb substrate 110 to the outflow surface 140 of the honeycomb substrate 110 opposite to the inflow surface 130. Can do. The partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150 and 160. The plurality of individual channels 150 and 160 include a plurality of reaction channels 150 and a plurality of heat exchange channels 160. Accordingly, the channel surface 125 of the reaction channel 150 is the reaction channel surface 155, and the channel surface 125 of the heat exchange channel 160 is the exchange channel surface 165.

  The method including the honeycomb substrate 110 made of the adsorbent material may further include shielding each inflow end and outflow end of the reaction channel 150 to form a shielding reaction channel. In some embodiments, the reaction channel 150 can be shielded, for example, by occluding the reaction channel 150 with foreign material or a removable material. In other embodiments, the reaction channel 150 can be shielded with a mask that covers only the ends of the reaction channel 150 and leaves the ends of the heat exchange channel 160 open. These allow solutions such as emulsions or dispersions to be introduced only into the heat exchange channel 160. The reaction channel 150 can be unshielded after the coating process is complete, for example, by removing the mask.

  When the reaction channel 150 is shielded, the liquid composition is fed onto the inflow surface 130 of the honeycomb substrate 110, and the liquid composition is allowed to flow through each of the heat exchange channels 160. Can not. Liquid delivery of the liquid composition according to one embodiment of the liquid delivery configuration 200 is illustrated schematically in FIG. In this embodiment, the liquid composition 220 can be poured from the container 210 into the funnel 230. The funnel 230 is coupled to the inflow surface 130 of the honeycomb substrate 110 to form a leak-proof seal that prevents the liquid composition 220 from flowing laterally out of the funnel 230 without flowing into the channels of the honeycomb substrate 110. can do. The liquid composition 220 is then drawn, for example by gravity, through the channels of the honeycomb substrate 110 toward the outflow surface 140. Excess amount of the liquid composition 220 can exit the honeycomb substrate 110 through the inflow surface 140 and can be received, for example, in any suitable liquid receiving tank 240. In another embodiment not shown, the liquid composition can be drawn through the honeycomb substrate 110 with the aid of a vacuum device attached to the outflow surface 140, for example. Those skilled in the art will readily appreciate that there are numerous variations in the processes involved in delivering a liquid composition to the heat exchange channel 160.

  In some embodiments, the liquid composition can be an emulsion or dispersion containing particles of a polymeric material. The emulsion or dispersion can be aqueous or non-aqueous. In other embodiments, the emulsion or dispersion may contain uncured monomers that when cured form a polymeric material. Delivery of the aqueous polymer emulsion to the heat exchange channel 160 results in the formation of an emulsion film of the aqueous polymer emulsion that covers only the exchange channel surface 165. The emulsion coating can be dried by forming an impermeable layer 170 on the exchange channel surface 165, thus obtaining the configuration of FIG. 2, for example by heating or blowing air over the exchange channel surface 165. .

  Liquid compositions, especially when the liquid composition is an aqueous polymer emulsion or dispersion, are vinyl butyrals, acrylic monomers, carboxylated acrylonitriles, butadienes, nitriles, chloroprenes, vinyl chlorides, vinylidene fluorides , Olefins such as ethylene or propylene, tetrafluoroethylene, siloxanes, urethanes, or uncured monomers such as mixtures of any of these. Thus, impermeable layers formed with such monomers include, for example, poly (vinyl butyral) resins, polyacrylates, polynitriles (including carboxylated acrylonitrile-butadiene copolymers), polychloroprenes, Polyolefins such as poly (vinyl chloride), poly (vinylidene fluoride), polyethylene or polypropylene or copolymers thereof, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof, and composites thereof A polymeric material selected from the materials can be included.

In embodiments where the liquid composition contains particles, such as in an aqueous polymer emulsion, the particles can be particles of a polymeric material having a median particle size of 0.1 μm to 20 μm. In another embodiment, the median particle size can be 0.1 μm to 2.0 μm. The aqueous polymer emulsion can have a wide range of viscosities, such as from 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. Unless stated otherwise, viscosity herein refers to the viscosity measured at 25 ° C. using a Brookfield viscometer, rotating an LVF No. 3 spindle at 30 rpm. It may be preferable to select the viscosity of the aqueous polymer emulsion based on the cell density of the honeycomb substrate 110. Accordingly, in some embodiments, the honeycomb substrate 110 has about 100 (about 15.5 / cm ² ) to about 2000 (about 310 / cm ² ) individual channels per square inch of the inflow surface 130. 150,160, about 300 (about 46.5 / cm ² ) to about 1500 (about 232.5 / cm ² ) individual channels 150,160, or about 600 (about 93.0 / cm ² ) ² ) to a cell density of about 1500 individual channels 150,160, and the aqueous polymer emulsion can have a viscosity of 50 cP to 5000 cP at 25 ° C. In some embodiments, the aqueous polymer emulsion can contain 10% to 50% solids by weight, based on the total weight of the aqueous polymer emulsion.

  In some embodiments, a method comprising a honeycomb substrate 110 made of an adsorbent material can be used to remove excess aqueous polymer emulsion from the heat exchange channel 160 after formation of the emulsion coating, such as through air. Alternatively, the method may further include blowing a gas such as nitrogen.

  In accordance with some embodiments, a method that includes a honeycomb substrate 110 made of an adsorbent material includes at least one additional layer 180 as an overcoat layer on an impermeable layer 170 on the exchange channel surface 165. The method may further include the step of forming. In order to form an overcoat layer, the second aqueous polymer emulsion is fed onto the inflow surface of the honeycomb substrate 110, and each of the heat exchange channels 160 is allowed to flow through the second aqueous polymer emulsion. 150 can be prevented from flowing through. Thereby, an emulsion film of the second aqueous polymer emulsion is formed covering the water-impermeable layer. This emulsion coating can be dried, for example by heating or gas blowing, to form at least one additional layer 180 as an overcoat on the impermeable layer 170. In a non-limiting illustrative embodiment, the overcoat layer can be formed of polystyrene or epoxy resin.

According to some embodiments, a method for forming an adsorbent structure 100 for CO ₂ capture can include providing a honeycomb substrate 110 formed of a ceramic material. The ceramic material can be an adsorbent material or a non-adsorbent material. The honeycomb substrate 110 made of a ceramic material has partition walls 120 penetrating the honeycomb substrate 110 in the axial direction 90 from the inflow surface 130 of the honeycomb substrate 110 to the outflow surface 140 of the honeycomb substrate 110 opposite to the inflow surface. The partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150 and 160. The plurality of individual channels 150 and 160 include a plurality of reaction channels 150 and a plurality of heat exchange channels 160, so that the channel surface 125 of the reaction channel 150 is the reaction channel surface 155 and the channel surface of the heat exchange channel 160. Reference numeral 125 denotes an exchange channel surface 165.

  The method including the honeycomb substrate 110 formed of the ceramic material may further include the step of loading the adsorbent material to the ceramic material before the step of feeding the aqueous polymer emulsion. In some embodiments, the adsorbent material is added to the dough ceramic material to form a dough composition, and then the honeycomb substrate 110 is formed from the dough composition, for example, by coextrusion, thereby forming the adsorbent material on the ceramic material. Can be loaded. The honeycomb substrate 110 formed from the dough composition can be processed, for example, by firing, into a honeycomb substrate 110 made of a ceramic material and loaded with an adsorbent material. In other embodiments, the ceramic material feeds the adsorbent precursor to the inflow surface 130 of the honeycomb substrate 110, causing the adsorbent precursor to flow at least the reaction channel 150, and at least the adsorbent precursor on the reaction channel surface 155. The adsorbent material can be loaded by forming a body precursor film. In some embodiments, the step of sending the adsorbent precursor causes the adsorbent precursor to flow on the inflow surface 130 of the honeycomb substrate 110 such that both the reaction channel 150 and the heat exchange channel 160 flow through the adsorbent precursor. A feeding step may be included. In other embodiments, the inlet and output ends of each heat exchange channel 160 can be shielded to form a shielded heat exchange channel prior to sending the adsorbent precursor. The step of sending the adsorbent precursor then causes the adsorbent precursor to flow through the reaction channel 150 and not the shielded heat exchange channel 160 to flow through, so the adsorbent precursor precursor only on the reaction channel surface 155. The method may include feeding an adsorbent precursor onto the inflow surface 130 of the honeycomb substrate 110 such that a coating is formed.

  The adsorbent precursor can be any compound that forms an adsorbent material as described above, for example when heated or dried. The conversion of the adsorbent precursor to the adsorbent material used to load the honeycomb substrate 110 does not involve any chemical conversion and can only be a physical conversion. For example, the adsorbent precursor can contain a liquid doubled adsorbent material, such as water or an organic solvent, and the evaporation of the solvent can adsorb the adsorbent material itself without any chemical conversion. An adsorbent film of the adsorbent material contained in the adsorbent precursor is obtained.

  After forming the precursor coating, the honeycomb substrate can be heated to a suitable temperature, such as 50 to 100 ° C., to convert the precursor coating to at least the adsorbent coating on the reaction channel surface 155. The adsorbent coating can include an adsorbent material different from the ceramic material on which the honeycomb substrate 110 is formed.

  The method including the honeycomb substrate 110 formed of a ceramic material may further include forming an impermeable layer 170 that covers the exchange channel surface 165. In order to form the impermeable layer 170 on the exchange channel surface 165, as described above, the inflow end and the outflow end of each of the reaction channels 150 are shielded to form a shielded reaction channel. The aqueous polymer emulsion is then pumped over the inflow surface 130 of the honeycomb substrate 110 as described above so that each of the heat exchange channels 160 flows through the aqueous polymer emulsion and the shield reaction channel 150 does not flow through. Can do. This forms an emulsion film of an aqueous polymer emulsion that covers only the exchange channel surface 165. The impervious layer 170 and the coating composition used to form the emulsion coating can be any of the liquid compositions described above with respect to the method when the honeycomb substrate 110 is formed of an adsorbent material. . The emulsion coating can be dried, heated or cured to form an impermeable layer that covers the exchange channel surface 165. Optionally, at least one additional layer 180 covering the water-impermeable layer 170 can be formed according to one or more of the above-described embodiments in which the honeycomb substrate 110 is formed of an adsorbent material. .

  As described above, the heat exchange channel 160 is the adsorbent structure 100 including the honeycomb substrate 110 covered with the water-impermeable layer 170 and, if necessary, at least one coating layer including at least one additional layer 180, An adsorbent structure 100 has been described that can use the adsorbent structure 100, for example, to enable rapid, efficient and uniform thermal management during a temperature swing adsorption process. Furthermore, a method for forming an adsorbent structure has also been described.

  The embodiments described herein will be further clarified by the following examples.

Example 1
As shown schematically in FIG. 4, a honeycomb substrate was coated. Butvar aqueous dispersion RS-261 (available from Butvar, 40% to 43% by weight, plasticized poly (vinyl butyral) containing solids with a particle size of 0.5 μm to 1.5 μm, milky white A stable aqueous polymer emulsion) was prepared. Both ends of the channel scheduled to be the reaction channel were plugged, and the channel scheduled to be the heat exchange channel was left open. The polymer emulsion was poured into the open heat exchange channel from the upper surface of the honeycomb substrate, and the heat exchange channel was allowed to flow and flow out from the bottom surface of the honeycomb substrate. After film formation, an air knife was used to blow off excess polymer emulsion to avoid blockage of the channel and leave the polymer emulsion layer attached to the channel surface. The reaction channel was unplugged. The polymer-coated substrate was placed in an oven preheated to 70 ° C. and dried overnight at room temperature.

  Following the same basic procedure, a second polymer layer on the first polymer layer was obtained. In two separate examples, a second polymer layer was formed. In one example, polystyrene (Aldrich, 10% toluene solution) was used. In the other example, an epoxy resin was used. The epoxy resin coating was made up of Erisys GE22 (1,4-cyclohexanedimethanol diglycidyl ether alicyclic bifunctional epoxy reactive diluent available from CVC Thermoset Specialties) and 4,4'-methylenebiscyclohexaneamine (from Air Products). Of Amicure PACM) was introduced into the heat exchange channel. The mixed solution for coating the epoxy resin was prepared as a 50% (weight ratio) ethanol solution having an epoxy to amine ratio of 1: 1.

Example 2
A polymer coated surface prepared according to Example 1 on a honeycomb substrate, including a first layer of Butvar emulsion and a second layer of polystyrene, is cut parallel to its axial length to expose the polymer coating. Was evaluated by Water was dropped on the polymer surface using an eye dropper, and the honeycomb substrate was placed in a Petri dish for observation. The water permeability on the polymer coating was evaluated by observing water droplets. Observations made after 2 hours and again after 6 hours revealed no significant change in the shape and size of the water droplets on the polymer-coated surface.

In a first aspect, the present disclosure provides an adsorbent structure 100 for CO ₂ capture. The adsorbent structure 100 includes a honeycomb substrate 110, and the honeycomb substrate 110 penetrates the honeycomb substrate 110 in the axial direction 90 from the inflow surface 130 of the honeycomb substrate 110 to the outflow surface 140 of the honeycomb substrate 110 opposite to the inflow surface 130. 120. The partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150 and 160. The plurality of individual channels 150 and 160 include a plurality of reaction channels 150 and a plurality of heat exchange channels 160, so that the channel surface 125 of the reaction channel 150 is the reaction channel surface 155 and the channel surface of the heat exchange channel 160. Reference numeral 125 denotes an exchange channel surface 165. The reaction channel 150 and the heat exchange channel 160 are arranged such that heat is transferred between the individual reaction channels 150A and 150B and the individual heat exchange channels 160A and 160B. The reaction channel surface 155 has an adsorbent material and the exchange channel surface 165 has at least one coating layer. At least one coating layer is made of poly (vinyl butyral) resin, polyacrylates, carboxylated acrylonitrile-butadiene copolymer, polynitriles, latexes, polychloroprenes, poly (vinyl chloride), poly (vinylidene fluoride). ), Polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof and polymer materials selected from the group consisting of composite materials thereof. The polymer material of the impermeable layer 170 does not substantially penetrate into the partition 120 forming the exchange channel surface 165, the adsorbent material of the partition 120 or the adsorbent material of the reaction channel surface 155.

  In a second aspect, the present disclosure provides an adsorbent structure 100 according to the first aspect, wherein the honeycomb substrate 110 is formed of an adsorbent material.

  In a third aspect, the present disclosure provides an adsorbent structure 100 according to the first or second aspect, wherein the adsorbent material is selected from the group consisting of zeolite, cordierite, alumina, silica and mixtures thereof. provide.

  In a fourth aspect, the present disclosure is directed to the first or third aspect, in which the honeycomb substrate 110 is formed of a ceramic material other than the adsorbent material, and the reaction channel surface 155 is covered with an adsorbent coating including the adsorbent material. An adsorbent structure 100 according to the present invention is provided.

  In a fifth aspect, the present disclosure provides the first or third embodiment in which the honeycomb substrate 110 is formed of a ceramic material other than the adsorbent material, and the adsorbent material is loaded on the ceramic material during or after the formation of the honeycomb substrate 110. An adsorbent structure 100 according to the embodiment is provided.

  In a sixth aspect, the present disclosure provides an sorbent structure 100 according to the first or fifth aspect, wherein the ceramic material is a non-absorbent ceramic material.

In a seventh aspect, the present disclosure provides that the honeycomb substrate 110 has from about 100 (about 15.5 / cm ² ) to about 2000 (about 310 / cm ² ) individual channels 150 per square inch of the inflow surface 130. , 160 cell density according to any of the first to sixth aspects.

In an eighth aspect, the present disclosure provides for the honeycomb substrate 110 to have from about 300 (about 46.5 / cm ² ) to about 1500 (about 232.5 / cm ² ) individual per square inch of the inflow surface 130. An adsorbent structure 100 according to any of the first to seventh aspects having a cell density of channels 150, 160 is provided.

In a ninth aspect, the present disclosure provides from about 600 (about 93.0 / cm ² ) to about 1500 (about 232.5 / cm ² ) individual honeycomb substrates 110 per square inch of the inflow surface 130. An adsorbent structure 100 according to any of the first to eighth aspects having a cell density of channels 150, 160 is provided.

  In a tenth aspect, the present disclosure further includes at least one additional layer 180 in which at least one coating layer covers the water-impermeable layer 170, wherein the at least one additional layer 180 is a polymer material of the water-impermeable layer 170. An adsorbent structure 100 according to any of the first to ninth aspects is provided that includes different polymeric materials.

  In an eleventh aspect, the present disclosure provides an adsorbent structure 100 according to any of the first to tenth aspects, wherein the impermeable layer 170 is a poly (vinyl butyral) resin.

In a twelfth aspect, the present disclosure provides a method for forming an adsorbent structure 100 for CO ₂ capture according to any of the first to third aspects or the seventh to eleventh aspects. The method includes providing a honeycomb substrate 110 formed of an adsorbent material, the honeycomb substrate 110 having an axial direction 90 from an inflow surface 130 of the honeycomb substrate 110 to an outflow surface 140 of the honeycomb substrate 110 opposite the inflow surface 130. Partition wall 120 penetrating through the honeycomb substrate 110, the partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150, 160, and the plurality of individual channels 150, 160 include a plurality of reaction channels 150 and a plurality of channels. The channel surface 125 of the reaction channel 150 is the reaction channel surface 155, and the channel surface 125 of the heat exchange channel 160 is the exchange channel surface 165. The method further includes shielding each entry and exit end of reaction channel 150 to form a shield reaction channel. The method causes the aqueous polymer emulsion to flow over the inflow surface 130 of the honeycomb substrate 110 and each of the heat exchange channels 160 to flow through the aqueous polymer emulsion and the shield reaction channel 150 does not flow through, thus covering only the exchange channel surface 165. The method further includes a step of feeding so as to form an emulsion film of the aqueous polymer emulsion. The method can further include drying the emulsion coating to form an impermeable layer 170 on the exchange channel surface 165. The water-impermeable layer 170 is made of poly (vinyl butyral) resin, polyacrylates, carboxylated acrylonitrile-butadiene copolymer, polynitriles, latexes, polychloroprenes, poly (vinyl chloride), poly (vinylidene fluoride). ), Polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof, and polymeric materials selected from the group consisting of composite materials thereof.

  In a thirteenth aspect, the present disclosure provides a method according to the twelfth aspect, comprising uncured monomers or particles of polymer material that form a polymer material when the aqueous polymer emulsion is cured.

  In a fourteenth aspect, the present disclosure provides a method according to the twelfth or thirteenth aspect, wherein the aqueous polymer emulsion comprises particles of polymeric material having a median particle size of 0.1 μm to 20 μm.

  In a fifteenth aspect, the present disclosure provides a method according to any of the twelfth to fourteenth aspects, wherein the aqueous polymer emulsion has a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. I will provide a.

  In a sixteenth aspect, the present disclosure is according to any of the twelfth to fifteenth aspects, wherein the aqueous polymer emulsion has 10% to 50% solids by weight, based on the total weight of the aqueous polymer emulsion. Provide a method.

In a seventeenth aspect, the present disclosure provides that the honeycomb substrate 110 has from about 100 (about 15.5 / cm ² ) to about 2000 (about 310 / cm ² ) individual channels 150 per square inch of the inflow surface 130. A method according to any of the twelfth to sixteenth embodiments, wherein the aqueous polymer emulsion has a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. provide.

In an eighteenth aspect, the present disclosure provides that the honeycomb substrate 110 has about 300 (about 46.5 pieces / cm ² ) to about 1500 (about 232.5 pieces / cm ² ) individual per square inch of the inflow surface 130. According to any of the twelfth to seventeenth aspects, having a cell density of channels 150, 160 and the aqueous polymer emulsion having a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. Provide a method.

In a nineteenth aspect, the present disclosure provides from about 600 (about 93.0 / cm ² ) to about 1500 (about 232.5 / cm ² ) individual honeycomb substrates 110 per square inch of the inflow surface 130. According to any of the twelfth to eighteenth aspects, having a cell density of channels 150, 160 and an aqueous polymer emulsion having a viscosity of from 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. Provide a method.

  In a twentieth aspect, the present disclosure further includes blowing a gas through the heat exchange channel 160 to remove excess aqueous polymer emulsion from the heat exchange channel 160 after the emulsion coating is formed. Provide a way to follow either.

  In a twenty-first aspect, the present disclosure allows a second aqueous polymer emulsion to flow over the inflow surface 130 of the honeycomb substrate 110, and each of the heat exchange channels 160 to flow through the second aqueous polymer emulsion, and the shield reaction channel 150 is At least one additional layer as a topcoat layer on the water-impermeable layer 170 and a liquid-feeding step so as to form an emulsion film of the second water-based polymer emulsion that does not flow and thus covers the water-impermeable layer 170 A method according to any of the twelfth to twentieth aspects is provided, further comprising the step of drying the emulsion coating of the second aqueous polymer emulsion to form 180.

  In a twenty-second aspect, the present disclosure provides a method according to the twenty-first aspect, wherein the at least one additional layer 180 functioning as an overcoat layer comprises a polymer material selected from the group consisting of polystyrene and epoxy resins.

In a twenty-third aspect, the present disclosure provides a method for forming an adsorbent structure 100 for CO ₂ capture according to any of the first or fourth to eleventh aspects. The method includes the steps of providing a honeycomb substrate 110 formed of a ceramic material and loaded with an adsorbent material, wherein the honeycomb substrate 110 is formed from an inflow surface 130 of the honeycomb substrate 110 opposite the inflow surface 130. The partition wall 120 penetrates the honeycomb substrate 110 in the axial direction 90 to the outflow surface 140, the partition wall 120 has a channel surface 125 that defines a plurality of individual channels 150 and 160, and the plurality of individual channels 150 and 160 include a plurality of individual channels 150 and 160. Reaction channel 150 and a plurality of heat exchange channels 160, so that channel surface 125 of reaction channel 150 is reaction channel surface 155 and channel surface 125 of heat exchange channel 160 is exchange channel surface 165. The method further includes shielding each inflow and outflow end of reaction channel 150 to form a shielded reaction channel. The method causes the first aqueous polymer emulsion to flow over the inflow surface 130 of the honeycomb substrate 110, and each of the heat exchange channels 160 to flow through the first aqueous polymer emulsion, and the shield reaction channel 150 does not flow, and therefore exchanges. The method further includes the step of delivering a liquid so as to form a first emulsion film of the first aqueous polymer emulsion covering only the channel surface 165. The method further includes drying the first emulsion coating to form an impermeable layer 170 that covers the exchange channel surface 165. The water-impermeable layer 170 is made of poly (vinyl butyral) resin, polyacrylates, carboxylated acrylonitrile-butadiene copolymer, polynitriles, latexes, polychloroprenes, poly (vinyl chloride), poly (vinylidene fluoride). ), Polyolefins, poly (tetrafluoroethylene), silicones, polyurethanes, mixed materials thereof, and polymeric materials selected from the group consisting of composite materials thereof.

  In a twenty-fourth aspect, the present disclosure contains uncured monomers that form a polymer material when the first aqueous polymer emulsion is cured or particles of a polymer material having a median particle size of 0.1 μm to 20 μm. A method according to the twenty-third aspect is provided.

  In a twenty-fifth aspect, the present disclosure further includes a step of wash-coating the adsorbent material onto the honeycomb substrate to load the adsorbent material onto the honeycomb substrate before the step of feeding the first aqueous polymer emulsion. A method according to the twenty-third or twenty-fourth aspect is provided.

  In a twenty-sixth aspect, the present disclosure allows the second aqueous polymer emulsion to flow on the inflow surface of the honeycomb substrate, the heat exchange channel to flow to the second aqueous polymer emulsion, and the shield reaction channel to not flow. Thus, at least one coating layer covering the water-impermeable layer and, optionally, at least one overcoat layer so as to form a second emulsion film of the second water-based polymer emulsion covering the water-impermeable layer. There is provided a method according to any of the twenty-third to twenty-fifth aspects, further comprising the step of drying the second emulsion coating of the second aqueous polymer emulsion to form an additional layer.

  In a twenty-seventh aspect, the present disclosure relates to the twenty-third to the twenty-sixth aspects, wherein the first and / or second aqueous polymer emulsion contains particles of uncured monomer or polymer material that forms a polymer material when cured. Provide a way to follow one of the following:

  In a twenty-eighth aspect, the present disclosure relates to the twenty-third to twenty-seventh aspects, wherein the first and / or second aqueous polymer emulsion contains particles of polymeric material having a median particle size of 0.1 μm to 20 μm. Provide a way to follow either.

  In a twenty-ninth aspect, the disclosure provides that the first and / or second aqueous polymer emulsion has a viscosity of from 50 cP (0.05 Pa · second) to 5000 cP (5 Pa · second) at 25 ° C. A method according to any of the embodiments is provided.

  In a thirtieth aspect, the present disclosure relates to the twenty-third to the thirty-first, wherein the aqueous polymer emulsion has 10% to 50% solids by weight, based on the total weight of the first and / or second aqueous polymer emulsion. A method according to any of the 29 aspects is provided.

In a thirty-first aspect, the present disclosure provides that the honeycomb substrate 110 has from about 100 (about 15.5 / cm ² ) to about 2000 (about 310 / cm ² ) individual channels 150 per square inch of the inflow surface 130. , 160, and the first and / or second aqueous polymer emulsion has a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. A method according to any of the aspects is provided.

In a thirty-second aspect, the present disclosure provides from about 300 (about 46.5 pieces / cm ² ) to about 1500 (about 232.5 pieces / cm ² ) individual honeycomb substrates 110 per square inch of the inflow surface 130. The cell density of the channels 150, 160, and the first and / or second aqueous polymer emulsion has a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. A method according to any of the 31 aspects is provided.

In a thirty-third aspect, the present disclosure provides from about 600 (about 93.0 / cm ² ) to about 1500 (about 232.5 / cm ² ) individual honeycomb substrates 110 per square inch of the inflow surface 130. The cell density of the channels 150, 160, and the first and / or second aqueous polymer emulsion has a viscosity of 50 cP (0.05 Pa · sec) to 5000 cP (5 Pa · sec) at 25 ° C. A method according to any of the 32 aspects is provided.

  In a thirty-fourth aspect, the present disclosure provides for heat exchange channel 160 to remove excess first and / or second aqueous polymer emulsion from heat exchange channel 160 after first and / or second emulsion coating formation. A method according to any of the twenty-third to thirty-third aspects is further provided, further comprising blowing gas through.

  In a thirty-fifth aspect, the present disclosure provides a method according to any of the twenty-third to thirty-fourth aspects, wherein the overcoat layer comprises a polymeric material selected from the group consisting of polystyrene and epoxy resins.

  It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments disclosed herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover such modifications and variations as come within the scope of the appended claims and their equivalents to the various embodiments described herein. The

DESCRIPTION OF SYMBOLS 100 Adsorbent structure 110 Honeycomb substrate 120 Partition 125 Channel surface 130 Inflow surface 140 Outflow surface 150,150A, 150B Reaction channel 155 Reaction channel surface 160,160A, 160B Heat exchange channel 165 Exchange channel surface 170 Impermeable layer 180 Additional layer 200 Liquid feeding configuration 210 Container 220 Liquid composition 230 Funnel 240 Liquid receiving tank

Claims (5)

In an adsorbent structure for CO ₂ capture,
A honeycomb substrate having partition walls penetrating the honeycomb substrate in an axial direction from an inflow surface of the honeycomb substrate to an outflow surface of the honeycomb substrate on the opposite side of the inflow surface, and the partition walls include a plurality of individual channels. A honeycomb substrate having a defined channel surface;
Have
The plurality of individual channels include a plurality of reaction channels and a plurality of heat exchange channels, the channel surface of the reaction channel is a reaction channel surface, and the channel surface of the heat exchange channel is an exchange channel surface. ,
The reaction channel and the heat exchange channel are arranged to transfer heat between the individual reaction channel and the individual heat exchange channel;
The reaction channel surface comprises an adsorbent material;
The exchange channel surface has at least one coating layer;
The at least one coating layer is made of poly (vinyl butyral) resin, polyacrylates, polynitriles, polychloroprenes, poly (vinyl chloride), poly (vinylidene fluoride), polyolefins, poly (tetrafluoroethylene), silicone A water-impermeable layer formed of a polymer material selected from the group consisting of:
The polymeric material of the impermeable layer does not substantially penetrate into the partition walls forming the exchange channel surface;
An adsorbent structure characterized by that.   The adsorbent structure according to claim 1, wherein the honeycomb substrate is formed of the adsorbent material.   The adsorption according to claim 1, wherein the honeycomb substrate is formed of a ceramic material other than the adsorbent material, and the adsorbent material is loaded on the ceramic material during or after the formation of the honeycomb substrate. Agent structure.   The at least one coating layer further includes at least one additional layer covering the water-impermeable layer, and the at least one additional layer includes a polymer material different from the polymer material of the water-impermeable layer. The adsorbent structure according to claim 1, wherein   The adsorbent structure according to claim 1, wherein the water-impermeable layer is a poly (vinyl butyral) resin, and the polymer material of the at least one additional layer includes polystyrene or an epoxy resin.

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