CO₂adsorption filter

Abstract

A carbon dioxide adsorption filter according to the present invention is formed by connecting and stacking unit filter members coated with a carbon dioxide adsorbent on the exposed surface, wherein a flow path is formed by a repeating three-dimensional pattern formed using one selected from a liquid photopolymerization process, a powder bed melting process, and an additive manufacturing process, and the filter has a three-dimensional exposed surface exposed to a gas flowing along the flow path.

Description

Technology Field

[0001] The present invention relates to a filter for adsorbing carbon dioxide, and more specifically, to a filter for adsorbing carbon dioxide that increases the adsorption efficiency of carbon dioxide by physically increasing the contact surface area using a shape rheological method for contact with a mixed gas containing carbon dioxide. Background Technology

[0002] In general, carbon dioxide is the primary culprit behind global warming, and active research is underway worldwide to reduce its emissions. In particular, various technologies are being developed to capture the carbon dioxide that increases as a result of using carbon-containing fuels as an energy source.

[0003] To capture carbon dioxide, an absorption method using an amine solution is used. However, since the absorption method has disadvantages such as high energy consumption, low stability, and corrosion of the device, an adsorption method using porous materials is being proposed as an alternative.

[0004] Carbon dioxide adsorbents to be utilized in these processes include activated carbon, zeolites, porous polymer silica, graphene oxide, and metal-organic frameworks (MOFs).

[0005] In addition, sodium hydroxide, potassium hydroxide, and lithium hydroxide are also used as adsorbents for carbon dioxide, and they can efficiently remove carbon dioxide by chemically reacting with it.

[0006] Korean registered patents No. 10-0562020 and No. 10-0879312 disclose a ring carbon dioxide immobilization adsorbent and a method for manufacturing the same. The disclosed adsorbent has a technical configuration for exchanging ions, such as zeolites, to add chemical adsorption performance to a physical adsorbent.

[0007] Korean Patent Publication No. 2022-0095820 discloses a filter for adsorbing carbon dioxide and a method for manufacturing the same. The disclosed method for manufacturing a filter for adsorbing carbon dioxide comprises the steps of: preparing a first mixture by mixing a metal precursor, a coordination complex of an organic acid, and a substance containing the counterion of the coordination complex in a solvent; preparing a porous adsorbent by irradiating the first mixture with microwaves; preparing a second mixture by mixing the porous adsorbent with a polymer; and electrospinning the second mixture.

[0008] These conventional carbon dioxide adsorption filters are manufactured in a mat form by growing a porous adsorbent through electrospinning of a material mixed with a polymer, but there are limitations in increasing the surface area and expanding the capacity.

[0009] Korean Patent Publication No. 2012-0054958 discloses a method for manufacturing a carbon dioxide adsorbent. The disclosed manufacturing method has a configuration in which an alkali metal-based hydroxide is dispersed in an organic solvent, a physical carbon dioxide adsorbent is mixed therein to support the hydroxide on the physical carbon dioxide adsorbent, and then dried.

[0010] These carbon dioxide adsorbents cannot improve the contact efficiency of carbon dioxide conversion due to the simple surface of the adsorbent. Prior art literature

[0011] Republic of Korea Registered Patent No. 10-0562020 Republic of Korea Registered Patent No. 10-0879312 Republic of Korea Published Patent No. 2022-0095820 Republic of Korea Published Patent No. 2012-0054958 The problem to be solved

[0012] The present invention aims to solve the problems described above by providing a carbon dioxide adsorption filter capable of improving the adsorption performance of carbon dioxide by physically increasing the contact surface area with a mixed gas containing carbon dioxide using a shape-rheological method, thereby expanding the contact area with the carbon dioxide.

[0013] Another objective of the present invention is to provide a carbon dioxide adsorption filter capable of improving capacity scalability by continuously arranging unit filter members for carbon dioxide adsorption. means of solving the problem

[0014] The carbon dioxide adsorption filter of the present invention for achieving the above objective is characterized by having a flow path formed by a three-dimensional pattern that is repeatedly formed using one selected from a liquid photopolymerization process, a powder bed melting process, and an additive manufacturing process, and having a three-dimensional exposed surface that is exposed to a mixed gas flowing along the flow path, and having unit filter members formed with a carbon dioxide adsorption layer formed on this exposed surface connected and stacked.

[0015] In the present invention, the unit filter member may be made of one selected from synthetic resin, SUS, and aluminum silicon alloy AlSi10Mg.

[0016] The unit filter element is made of AlSi10Mg, an aluminum silicon alloy, and after pre-treating the exposed surface of the unit filter element using an aqueous sodium hydroxide solution, the aluminum is etched by treating it with an aqueous hydrochloric acid solution to have a structure in which a predetermined silicon pattern is exposed. Effects of the invention

[0017] The carbon dioxide adsorption filter according to the present invention forms a flow path through which a mixed gas containing carbon dioxide (hereinafter abbreviated as mixed gas) flows by means of a repeating three-dimensional pattern, and since a carbon dioxide adsorption layer is formed on the surface of the flow path, that is, on the exposed surface of the three-dimensional shape, the specific surface area for contact with the mixed gas can be relatively increased.

[0018] In addition, since it has a structure in which the three-dimensional pattern forming the flow path is repeated, it is possible to prevent the reduction in adsorption efficiency caused by a partial drop in local pressure due to the flow path being partially blocked.

[0019] In addition, the carbon dioxide adsorption filter of the present invention can increase the contact residence time of the carbon dioxide mixed gas with the carbon dioxide adsorption layer through self-circulation, thereby increasing the carbon dioxide adsorption efficiency per unit area. Brief explanation of the drawing

[0020] FIG. 1 is a separated photograph showing a carbon dioxide adsorption filter according to the present invention, FIG. 2 is a photograph showing an excerpt of the three-dimensional pattern illustrated in FIG. 1. FIG. 3 is a cross-sectional view showing another embodiment of a carbon dioxide adsorption filter according to the present invention. FIG. 4 is a photograph showing the exposed surface of the unit filter member illustrated in FIG. 1 etched and etched. FIGS. 5 to 8 are photographs showing embodiments in which a carbon dioxide adsorption layer is coated on the exposed surface of a carbon dioxide adsorption filter according to the present invention. Specific details for implementing the invention

[0021] The present invention relates to a filter for adsorbing carbon dioxide, and one embodiment is shown in FIGS. 1 to 8.

[0022] Referring to the drawings, the carbon dioxide adsorption filter (10) according to the present invention can increase the adsorption capacity of carbon dioxide from a mixed gas by increasing the specific surface area, and has a structure in which a plurality of unit filter members (20), each having a carbon dioxide adsorption layer (30) formed in a flow path (22) through which the mixed gas passes, are interconnected or stacked, or connected and stacked.

[0023] The above unit filter member (20) has a structure in which a predetermined three-dimensional pattern (25) is repeated, and forms a flow path (22) through which mixed gas passes, thereby having a three-dimensional exposed surface (23) exposed to the flow path (22).

[0024] A unit filter member (20) may have a three-dimensional pattern (25) formed to form a flow path (22) through which a mixed gas passes, using one selected from a liquid photopolymerization process, a powder bed melting process, and an additive manufacturing process. The three-dimensional pattern (25) of the unit filter member (20) may be formed as a porous body having irregular ribs of substantially the same thickness as shown in FIGS. 1 and 2, and the pores of the porous body are interconnected to form a flow path (22).

[0025] However, not limited to this, the unit filter member (20) may have a three-dimensional repeating inner structure (RIS: Repeated Inner structure), and as shown in FIG. 3, the protrusions (26) forming a three-dimensional pattern are formed at predetermined intervals, and the protrusions (26') of the stacked unit filter member (20') are positioned between the protrusions (26), so that the mixed gas may have a self-circulation structure.

[0026] The material of the above unit filter member (20) may be a metal, a metal alloy, a non-ferrous metal such as aluminum, a non-ferrous metal alloy, a synthetic resin, etc., but it is preferable to use stainless steel, a stainless steel alloy, or an aluminum alloy having a chemical composition according to the ASTM (American Society for Testing and Materials) F3318.

[0027] Meanwhile, it is preferable to etch the three-dimensional exposed surface (23) forming the flow path (22) of the unit filter member (20) to increase the specific surface area (surface area / mass, surface area of ​​soil particles per unit volume) of the carbon dioxide adsorption layer (30).

[0028] The etching of the exposed surface (23) of the unit filter member (20) may vary depending on the material of the unit filter member (20).

[0029] According to the inventor's experiment, in order to increase the specific surface area of ​​the exposed surface (23) of a unit filter member (20) manufactured using one selected from 3D printing, liquid photopolymerization, powder bed melting, and additive manufacturing processes using AlSi10Mg material, impurities on the exposed surface are removed using ethanol and deionized water, and etched by pretreatment using an aqueous sodium hydroxide solution.

[0030] And by etching using an aqueous hydrochloric acid solution or an aqueous nitric acid solution, a structure with an etched exposed surface as shown in Fig. 4 could be obtained.

[0031] To explain this in detail, the surface was immersed in a 1 molar aqueous solution of sodium hydroxide (NaOH) at room temperature (25°C) for 1 minute, and then washed with ultrapure water. Afterward, it was immersed in a 3 molar aqueous solution of hydrochloric acid (HCl) at room temperature for about 5 minutes to etch, and then washed again with ultrapure water. The wet surface was dried in a drying oven maintained at 60°C for 20 to 40 minutes.

[0032] Referring to FIG. 4, it can be seen that the exposed surface (23) of the unit filter member (10) is etched and etched by the sodium hydroxide solution and hydrochloric acid solution, thereby exposing silicon of a predetermined pattern and increasing the specific surface area.

[0033] The carbon dioxide adsorption layer (30) coated on the exposed surface (23) exposed to the flow path (22) of the unit filter member (20) is formed by mixing a porous framework, an amine material for adsorbing carbon dioxide, and a solvent by dip coating or spray coating.

[0034] The porous framework may be composed of one selected from carbon nanotubes, graphene, carbon fiber, and MIL-53. The amine material may be an amine containing at least one functional group selected from R1-NH2, R1-N(R2)H, and R1-N(R2)-R3, and may include at least one of Tetraethylenepentamine, Diethanolamine, Monoethanolamine, Tetraethylenepentamine, and N-Methyldiethanolamine. The solvent may be ethanol, isopropyl alcohol, acetone, or distilled water.

[0035] Example 1

[0036] To prepare the solution, a silane coupling agent, tetraethyl orthosilicate, and a surfactant may be added, and the ratio of each material is as follows.

[0037] 50 to 100 wt% of solvent, 0.1 to 5 wt% of framework, 1 to 40 wt% of amine, 0.01 to 3 wt% of cylin coupling agent, 0.01 wt% of tetraethlorthosilicate, and 0.01 to 1 wt% of surfactant were mixed, stirred at a rotational speed of 100 to 500 rpm for 30 to 6 hours, and ultrasonically processed.

[0038] Meanwhile, the method for preparing a coating solution to form a carbon dioxide adsorption layer (30) coated on the exposed surface (23) of a unit filter member (20) is as follows.

[0039] 0.1 parts by weight of at least one selected from carbon nanotubes, graphene, and carbon fiber is mixed with 100 parts by weight of distilled water and ethanol. Then, a solution is prepared by stirring at 300 rpm at 100 degrees, and 0.1 to 40 parts by weight of an imine material is mixed with 100 parts by weight of this solution and mixed by ultrasonic treatment for about 30 minutes, after which it is dried to form a powder.

[0040] Then, in order to form a carbon dioxide adsorption layer (30) on the exposed surface (23) of the unit filter member (20), powder dried in ethanol and isopropyl, a surfactant, and a binder are mixed, and then stirred at 400 rpm for 4 to 8 hours at 150°C to 250°C, and ultrasonically treated for 30 to 60 minutes.

[0041] Example 2

[0042] Another embodiment of the method for preparing a coating solution to form a carbon dioxide adsorption layer coated on the exposed surface of a unit filter member (20) is to mix terephthalic acid, Al(NO3₃)₃₃₅H₂O, dimethylformamide, and distilled water, heat the mixture at 150 degrees for 30 hours, and then wash the mixture twice each with dimethylformamide, methanol, and acetone. After heating at 50 degrees for 24 hours, the mixture is ball-milled to pulverize it.

[0043] Then, in order to form a carbon dioxide adsorption layer on the exposed surface of the unit filter member (20), the powder is mixed with ethanol, distilled water, MIL-53, a curing agent, an interface binder, and a surfactant, and then stirred at 14 to 150°C to 250°C to 400 rpm for 4 to 8 hours, and ultrasonically treated for 30 to 60 minutes.

[0044] A coating solution for forming a carbon dioxide adsorption layer (30) manufactured as in the above embodiment is spray-coated or dip-coated onto the exposed surface of the flow path to form a carbon dioxide adsorption layer (30). The coating state of the carbon dioxide adsorption layer (30) formed in this manner is shown in FIGS. 6 to 8.

[0045] As described above, the carbon dioxide adsorption filter according to the present invention can be manufactured by connecting unit filter members to each other or by connecting and stacking, thereby increasing the expandability of the filter in terms of shape and specifications.

[0046] In particular, the surface area of ​​the exposed surface (23) of the flow path (22) through which the mixed gas mixed with carbon dioxide passes can be expanded to increase the surface area of ​​the carbon dioxide adsorption layer (30) coated thereon, and the unit filter member (20) having a three-dimensional RIS has a structure in which the mixed gas is self-circulated, thereby increasing the contact and residence time with the carbon dioxide adsorption layer and improving carbon dioxide adsorption.

[0047] In addition, since the above flow path can be uniformly formed by a repeating three-dimensional pattern, it is possible to prevent the flow path of the unit filter from being partially blocked and the flow pressure of the mixed gas from rising.

[0048] The present invention has been described with reference to the embodiments illustrated in the drawings, but this is merely illustrative, and those skilled in the art will understand that various modifications and equivalent alternative embodiments are possible therefrom. Accordingly, the true technical scope of protection of the present invention should be determined by the technical spirit of the appended claims.

Claims

Claim 1 A carbon dioxide adsorption filter characterized by having a flow path formed by a repeating three-dimensional pattern formed using one selected from a liquid photopolymerization process, a powder bed melting process, and an additive manufacturing process, and having a three-dimensional exposed surface exposed to a mixed gas flowing along the flow path, wherein unit filter members coated with a carbon dioxide adsorption layer on the exposed surface are connected and stacked, wherein the exposed surface of the unit filter member has a three-dimensional repeating inner structure (RIS), wherein the three-dimensional repeating inner structure has protrusions forming a three-dimensional pattern formed at predetermined intervals, and the protrusions of the unit filter member stacked thereon are positioned between the protrusions, thereby having a structure in which the mixed gas self-circulates. Claim 2 A carbon dioxide adsorption filter according to claim 1, characterized in that the unit filter member is made of one of aluminum silicon alloy, stainless steel, stainless steel alloy, or synthetic resin. Claim 3 A carbon dioxide adsorption filter according to claim 2, characterized in that the unit filter member is made of AlSi10Mg, an aluminum silicon alloy. Claim 4 A carbon dioxide adsorption filter according to claim 3, characterized in that the aluminum on the surface is etched and a predetermined silicon pattern is exposed by pre-treating the unit filter member using an aqueous sodium hydroxide solution and then etching it using an aqueous hydrochloric acid solution. Claim 5 delete Claim 6 delete Claim 7 delete

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