Hollow fiber module

Abstract

A hollow fiber module 1 comprises a hollow fiber bundle 3 composed of a plurality of hollow fibers 2, and an adhesive fixing layer 4 for adhesively fixing the hollow fiber bundle 3 at both ends thereof, wherein: the hollow fibers 2 each include an adsorption substance 5 and a barrier layer 6 covering a hollow fiber lumen; at an end part of the adhesive fixing layer 4, a hollow part of the hollow fiber bundle 3 is opened; and in the hollow fiber bundle 3 existing in a cross section of the adhesive fixing layer 4, when a straight line, along which a distance between the hollow fibers 2, 2 is maximum, is defined as a straight line A, and a straight line, which is orthogonal to the straight line A and along which the distance is maximum, is defined as a straight line B, the length of the straight line A is greater than that of the straight line B.

Description

Hollow fiber module

[0001] Various embodiments of the present disclosure relate to a hollow fiber module and a method of flowing a gas therethrough, etc. More specifically, it relates to the recovery of carbon dioxide (CO ２ ), etc. by the hollow fiber module.

[0002] In recent years, the realization of a carbon-neutral and decarbonized society has attracted attention. For example, the Japanese government declared in October 2020 that it aims to achieve carbon neutrality by 2050.

[0003] Toward achieving carbon neutrality, technologies for efficiently recovering CO ２ from low-concentration carbon dioxide (CO ２ ) gas with low energy are required. In particular, the direct recovery of CO ２ from the atmosphere is expected as a negative emission technology.

[0004] For the industrial practical application of CO ２ recovery, technologies that can efficiently recover CO ２ at low cost are required because low-cost CO ２ recovery is required. For example, Patent Document 1 discloses a technology capable of efficiently adsorbing and desorbing CO ２ at high speed by a CO ２ adsorption / desorption method using a hollow fiber adsorbent. Also, Non-Patent Document 1 available from the homepage of ARPA-E (https: / / arpa-e.energy.gov / sites / default / files / 2024-08 / 7_Realff_FLECCS%202024%20Mtg%20-%20Presentation.pdf) illustrates the concept of a system for directly recovering CO ２ from the air using a hollow fiber adsorbent.

[0005] U.S. Patent Application Publication No. 2009 / 00255SS

[0006] ARPA-E Project: Positive Power with Negative Emissions - Flexible NGCC Enabled by Modular Direct Air Capture. Georgia Tech Research Corporation, etc (August 14, 2024)

[0007] Patent Document 1 and Non-Patent Document 1 do not describe the specific shape of the module that directly contacts air. When actually flowing air through the hollow fiber module described in both documents, depending on the shape of the module, there may be a problem of one-way air flow, and it may not be possible to efficiently recover carbon dioxide (CO ２ ).

[0008] In view of the above circumstances, an object of the present disclosure is to provide a hollow fiber module capable of efficiently recovering CO ２ and a method of flowing a gas therethrough.

[0009] Examples of the present disclosure are listed below: (1) A hollow fiber module comprising a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers comprise an adsorbent and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, and the length of the line A is greater than the length of the line B when the line A is the line with the maximum distance between the hollow fibers in the cross-section of the adhesive fixing layer, and the line B is the line perpendicular to line A with the maximum distance. (2) The hollow fiber module according to item 1, wherein the aspect ratio of line A to line B (ratio of the length of line A to the length of line B) is greater than 1.0 and less than 1,000. (3) The hollow fiber module according to item 1 or 2, wherein the adsorbent is silica particles impregnated with an amine. (4) A hollow fiber module according to any one of items 1 to 3, wherein the hollow fiber module is provided with one or more core rods at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer to support the adhesive fixing layer at both ends of the hollow fiber module. (5) A hollow fiber module according to any one of items 1 to 4, wherein the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer is rectangular or has a rounded portion. (6) A hollow fiber module according to any one of items 1 to 5, wherein the hollow fiber module is a bare module that does not have an outer covering body that covers the module. (7) A hollow fiber module comprising a hollow fiber bundle consisting of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the hollow fiber bundle at both ends, wherein the hollow fibers include an adsorbent and a barrier layer that covers the hollow fiber cavity, the hollow portion of the hollow fiber bundle is open at the end of the adhesive fixing layer, and the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer is rectangular or substantially rectangular. (8) The hollow fiber module according to item 7, wherein the adsorbent is silica particles impregnated with an amine. (9) The hollow fiber module according to item 7 or 8, wherein one or more core rods are provided at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer, supporting the adhesive fixing layer at both ends of the hollow fiber module.(10) The hollow fiber module according to any one of items 7 to 9, wherein the hollow fibers are randomly arranged in the substantially rectangular shape, and the outer circumference of the substantially rectangular shape has bumps and dips. (11) The hollow fiber module according to any one of items 7 to 9, wherein the bundle of hollow fibers present in the cross-section of the adhesive fixing layer includes a region of hollow fibers located apart from the rectangle or the substantially rectangular shape, in addition to the rectangle or the substantially rectangular shape. (12) The hollow fiber module according to any one of items 7 to 9, wherein the substantially rectangular shape has multiple regions where the bundle of hollow fibers exists, and there are gaps between them. (13) The hollow fiber module according to any one of items 7 to 9, wherein the substantially rectangular shape has a rounded (R) portion. (14) The hollow fiber module according to any one of items 7 to 9, wherein the rectangle or the substantially rectangular shape is hollow in the middle. (15) The hollow fiber module according to any one of items 7 to 14, wherein the hollow fiber module is a bare module that does not have an outer covering that covers the module. (16) A method for flowing gas through a hollow fiber module, which includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, and the aspect ratio (ratio of length of line A / length of line B) of the bundle of hollow fibers present in the cross-section of the adhesive fixing layer is greater than 1.0 and less than 1,000 when line A is the line where the distance between the hollow fibers is greatest and line B is the line perpendicular to line A with the greatest distance, and the gas is directed toward the longer side of the outer shape of the cross-section of the bundle of hollow fibers, or the gas is flowed perpendicular to the longer side of the outer shape. (17) A method for flowing gas through a hollow fiber module, which includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer that covers the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, the outer shape of the bundle of hollow fibers in the cross-section of the adhesive fixing layer is rectangular or substantially rectangular, and the gas is directed toward the longer side of the rectangle or substantially rectangular shape, or the gas is flowed perpendicular to the longer side of the outer shape of the cross-section of the bundle of hollow fibers.(18) The method according to item 16 or 17, wherein the adsorbent is silica particles impregnated with an amine. (19) The method according to any one of items 16 to 18, wherein one or more core rods are provided at the center of the cross-section of the adhesive-fixed layer, inside the adhesive-fixed layer, or on the outer periphery of the adhesive-fixed layer, supporting the adhesive-fixed layer at both ends of the hollow fiber module. (20) The method according to any one of items 16 to 19, wherein a gas is flowed through the hollow fiber module and the adsorbed component is adsorbed at the same time.

[0010] According to this disclosure, efficiently carbon dioxide (CO2) ２ We can provide a hollow fiber module that can recover CO2, and a method for flowing gas through it, and thereby suppress one-sided flow when wind is applied from the outside of the module. ２ By improving recovery efficiency, CO2 can be directly extracted from the gas with low energy consumption, low cost, and high efficiency. ２ It can be recovered.

[0011] Figure 1 is a partial perspective side view of a hollow fiber module. Figure 2A is a perspective cross-sectional view of a hollow fiber. Figure 2B is a schematic top view of a hollow fiber. Figure 3 is a schematic diagram illustrating the method for calculating the aspect ratio of the present disclosure, illustrating a circle (a), an ellipse (b), a rectangle with an aspect ratio of 3 (c), and a rectangle with an aspect ratio of 2 (d). Figure 4A is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4B is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4C is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4D is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4E is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4F is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4G is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4H is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4I is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4J is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4K is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4L is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4M is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4N is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4O is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4P is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module. Figure 4Q is a schematic diagram illustrating the external shape of a hollow fiber bundle present in a cross-section of the adhesive fixing layer of a hollow fiber module.Figure 4R is a schematic diagram illustrating the external shape of the hollow fiber bundle present in the cross-section of the adhesive fixed layer of the hollow fiber module. Figure 5A is a schematic diagram illustrating the relationship between the shape of the hollow fiber bundle present in the cross-section of the adhesive fixed layer and the direction of gas flow in a method of flowing gas through a hollow fiber module. Figure 5B is a schematic diagram illustrating the relationship between the shape of the hollow fiber bundle present in the cross-section of the adhesive fixed layer and the direction of gas flow in a method of flowing gas through a hollow fiber module. Figure 6 shows CO2 obtained in basic experiments. ２ Figure 7 is the adsorption breakdown curve. Figure 8 is the integrated adsorption amount curve obtained in the basic experiment. Figure 9 is the graph of the linear velocity versus the time to reach 0.5 mmol / g. Figure 9 is a schematic diagram to explain the setting of the module, velocity inlet, pressure outlet, and plane of symmetry relative to both walls. Figure 10 is a schematic diagram to explain the arrangement of hollow fibers in the analysis of the hollow fiber module. Figure 11 is a graph showing the effect of the module shape on the distance from the inlet and the pressure. Figure 12 is the wind velocity distribution map obtained by analysis according to the module shape. Figure 13 is the in-module wind velocity distribution obtained by obtaining the wind velocity between hollow fibers according to the module shape. Figure 14 is the in-module wind velocity histogram obtained by analysis according to the module shape.

[0012] <Terminology> The following describes in detail the embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments"). The present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0013] This disclosure describes typical embodiments in detail with reference to the drawings. In the drawings, similar reference numerals indicate components having similar functions across multiple drawings. Components, modules, apparatus, processes and methods relating to this disclosure can be understood by reference to the accompanying drawings. The drawings are schematic diagrams intended to facilitate understanding of this disclosure and are not intended to define or limit the relative dimensions, actual dimensions, and / or the scope of exemplary embodiments of the apparatus or its components.

[0014] Throughout this disclosure, various components may be identified by specific values ​​or parameters or functions in typical embodiments, but this does not limit the various aspects and concepts of this disclosure, as do the comparative parameters, dimensions, ranges, and / or values ​​that may actually be implemented.

[0015] The modifier "approximately," used in combination with a number or quantity, may include not only the specific value being stated but also the degree of error associated with that measurement. When used in reference to a range of numbers, the modifier "approximately" also discloses the range defined by the absolute values ​​of the two endpoint values.

[0016] The term "multiple" refers to anything greater than one. When there are multiple numerical ranges with the same meaning, the ends of each numerical range can be specified individually or combined.

[0017] The term "includes" implies that the presence of the element being described is essential, and that other elements may also be present; therefore, the term "consist of" should also be interpreted as including this term. The term "consist of" means that only the element being described is present, but may include any impurities that may arise from the manufacture of the element being described.

[0018] In this disclosure, the term "hollow fiber" means a hollow fiber comprising a continuous, flexible filamentous material, wherein the ratio of its length to its mean longest cross-section is significantly greater than 1.

[0019] In this disclosure, the terms “adsorption” or “adsorbent” mean that they encompass both adsorption and absorption. Throughout this disclosure, adsorption and related compositions, substances, and processes will be described, but it should be understood that these descriptions will encompass both adsorption and absorption.

[0020] In this disclosure, unless otherwise noted, the term “selectivity” is based on a binary comparison (e.g., a pairwise comparison) between the molar concentration of a certain component adsorbed by a particular adsorbent during an adsorption process under specific system operating conditions and the molar ratio of a certain component in the feed flow medium. For example, for a medium containing component A, component B, and additional components, an adsorbent having greater selectivity for component A than for component B will exhibit the following formula in the final adsorption step of a swing adsorption process cycle: U Ａ The ratio U is expressed as = (total number of moles of A in the adsorbent) / (molar concentration of A in the combustion exhaust gas in contact with the adsorbent). Ａ The following formula: U Ｂ The ratio U is expressed as = (total number of moles of B in the adsorbent) / (molar concentration of B in the combustion exhaust gas in contact with the adsorbent). Ｂ Larger than, here, U Ａ This refers to "adsorption and absorption of component A," and U Ｂ The terms and represent the "adsorption and absorption of component B". Therefore, for a substance that has greater selectivity for component A than for component B, the following formula applies: Selectivity = U A / U B {In the formula, U A >U B This is expressed as}. In a comparison of different components in the feed flow medium, the component whose total number of moles captured by the adsorbent is the smallest in ratio to the molar ratio in the feed flow is the “least abundant component” in the swing adsorption process. The least abundant component does not need to have the lightest molecular weight, but for example, in the case of CO2 and N2, the “lightest” component in the sense used here is N2. This means that the molar concentration of the lightest component in the flow effluent during the adsorption process is greater than the molar concentration of the lightest component in the feed flow.

[0021] Media separation is used in a variety of industries, including, but not limited to, the manufacture of fuels, chemicals, petrochemicals, and specialty products. In this disclosure, the term “media” is used for convenience and generally means a fluid, liquid, gas, solution, turbidity, powder, gel, dispersion, emulsion, vapor, fluid material, multiphase substance, or a combination thereof. A media may include a feed flow. A media may include a mixture of multiple components.

[0022] Media separation can generally be achieved by taking advantage of the differences in the physical and / or chemical properties of multiple components to be separated, with the assistance of heat, solids, gases, fluids, or other means. For example, gas separation can be achieved with respect to a gas mixture by partial liquefaction or by using an adsorbent that preferentially retains or adsorbs components that are more readily retained or adsorbed than the components to be adsorbed.

[0023] A commercially implemented gas separation process is, for example, thermal swing adsorption (TSA). TSA involves a step in which an adsorption bed of adsorbent material is used to separate one or more components of a medium, and then the adsorbent material is regenerated (released) by increasing the temperature of the adsorption bed.

[0024] The TSA process involves the selective adsorption of at least one component (including the first component) of a medium by an adsorbent, relative to a second component or other components in the medium. Since both pressure and temperature can affect the adsorption filling of the medium components, the total amount of at least one component adsorbed from the medium (e.g., the adsorption capacity of the adsorbent) and the selectivity of the adsorption of the first component relative to other components in the medium may be improved by operating the adsorption process under specific pressure and temperature conditions.

[0025] The adsorbed components of the medium can be desorbed from the adsorbed material. Since the desorption of components occurs because the adsorption isothermal process is strongly influenced by temperature, high-purity components of the medium can be obtained by adsorption at low temperatures. Because adsorption is strong at low temperatures, the release of strongly retained components is possible by raising the temperature or heating for desorption. Compared to pressure swing adsorption (PSA), TSA can be operated by isothermal saturation control and has advantages in terms of the capacity and usefulness range of the adsorbed material. In the TSA process, the heat of desorption can be supplied to the adsorbed material directly by flowing a high-temperature desorption medium through the floor, or indirectly through something that has a close relationship with the adsorption medium, such as a heat coil, electric heat source, electric heating medium, or heat exchanger.

[0026] The TSA process includes, but is not limited to, direct heating TSA processes and indirect heating TSA processes, which can be carried out by direct heating TSA systems and indirect heating TSA systems, respectively.

[0027] <Hollow Fiber Module> In one aspect of the present disclosure, a hollow fiber module is provided which includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity, and the hollow portion of the hollow fiber bundle is open at the ends of the adhesive fixing layer.Optionally, the hollow fiber module may include one or more core rods.

[0028] Figure 1 is a partial perspective side view of the hollow fiber module, Figure 2A is a perspective cross-sectional view of the hollow fiber, and Figure 2B is a schematic top view of the hollow fiber.

[0029] As illustrated in Figure 1, the hollow fiber module (1) includes, but is not limited to, a hollow fiber bundle (3) made up of a plurality of hollow fibers (2), and adhesive fixing layers (4, 4) that adhesively fix the hollow fiber bundle (3) at both ends, and the hollow portion of the hollow fiber bundle (3) is open at the ends of the adhesive fixing layers (4, 4).

[0030] From the viewpoint of supporting the adhesive fixing layers (4, 4) at both ends, it is preferable that the hollow fiber module (1) is provided with one core rod (7) or multiple core rods (not shown) at the center of the cross-section of the adhesive fixing layer (4), inside the adhesive fixing layer (4), or on the outer periphery of the adhesive fixing layer (not shown).

[0031] As illustrated in Figures 2A and 2B, the hollow fiber (2) may include, but is not limited to, an adsorbent substance (5) and a barrier layer (6) covering the lumen of the hollow fiber (2).

[0032] As illustrated in Figures 1, 2A, and 2B, the hollow fiber module of this disclosure is made of carbon dioxide (CO2). ２ It can be used as a hollow fiber type exposed module (hereinafter sometimes referred to as "bare module") for adsorbing gases such as CO2, for example, swing adsorption, combustion exhaust gas, and CO2 from the air. ２It can be suitably used in applications such as separation and efficient use of heat generated during the adsorption process.Optionally, the hollow fiber module may be equipped with an outer casing (chamber) that covers the bare module, gas inlets and outlets in the outer casing, etc.

[0033] In the first embodiment, in the cross-section of the adhesive fixing layer of the hollow fiber module, when the straight line where the distance between hollow fiber bundles is maximum is defined as straight line A, and the straight line perpendicular to straight line A with the maximum distance is defined as straight line B, the length of straight line A is greater than the length of straight line B.

[0034] In the first embodiment, it is preferable that the aspect ratio of line A and line B (the ratio of the length of line A to the length of line B) is greater than 1.0 and less than 1,000.

[0035] In the first embodiment, although we do not wish to be bound by theory, assuming that the number of fibers is the same, in a perfectly cylindrical bare module (i.e., aspect ratio = 1), one-sided gas flow occurs, worsening absorption efficiency. In contrast, in the hollow fiber module, the length of straight line A of the hollow fiber bundle present in the cross-section of the adhesive fixed layer is greater than the length of straight line B, and preferably the aspect ratio (ratio of the length of straight line A / the length of straight line B) is greater than 1.0 and less than 1,000, so that the gas flows efficiently within the module, increasing the gas flow rate within the module and CO ２ This could potentially increase the adsorption efficiency.

[0036] From the viewpoint of increasing adsorption efficiency, the aspect ratio of the hollow fiber module is more preferably greater than 1.0, or 1.5 or greater, or 3.0 or greater, or 10 or greater, or 50 or greater. From the viewpoint of module durability and handling, it is more preferably less than 1,000, or less than 500, or less than 100.

[0037] The hollow fiber module according to the first embodiment improves the efficiency of gas flow within the module or increases the gas flow rate, and CO ２From the viewpoint of improving adsorption efficiency, it is preferable that the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixed layer be rectangular or have a rounded (R) portion. A rectangle refers to a quadrilateral (excluding a square) with right angles at each corner, and is sometimes called a rectangular or strip-shaped shape. The outer shape having a rounded (R) portion is not limited to this, but examples include an ellipse with an aspect ratio greater than 1.0 and less than 1,000.

[0038] Figure 3 is a schematic diagram illustrating the method for calculating the aspect ratio in this disclosure. As shown in Figure 3, the aspect ratio is defined as the ratio = A / B, where line A is the line with the longest distance between hollow fibers in the cross-section of the hollow fiber bundle, and line B is the line perpendicular to line A that takes the longest distance.

[0039] In Figure 3(a), if the outer shape of the region where the hollow fibers exist in the cross-section of the hollow fiber bundle is approximately circular, the aspect ratio is A / B = 1.

[0040] Figure 3(b) illustrates a case where the outer shape of the region where the hollow fibers exist in the cross-section of the hollow fiber bundle is elliptical and the aspect ratio is A / B = 2.

[0041] Figure 3(c) illustrates the case where the outer shape of the region where the hollow fibers exist in the cross-section of the hollow fiber bundle is rectangular and the aspect ratio is A / B = 3. As shown in Figure 3(d), the aspect ratio of the rectangle is the same as the ratio of the long side to the short side and the length of line A to the length of line B. Figure 3(d) illustrates the case where the outer shape of the region where the hollow fibers exist in the cross-section of the hollow fiber bundle is rectangular and the aspect ratio is A / B = 2, and the ratio of the long side to the short side and the length of line A to the length of line B are calculated according to the following formula.

[0042] In the second embodiment, the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer of the hollow fiber module is rectangular or substantially rectangular.

[0043] In the second embodiment, although we do not wish to be bound by theory, assuming the same number of fibers, in conventional cylindrical bare modules, one-sided gas flow occurs, worsening absorption efficiency. In contrast, by making the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer of the hollow fiber module rectangular or roughly rectangular, gas flows efficiently within the module, increasing the gas flow rate within the module and reducing CO2 absorption. ２ This could potentially increase the adsorption efficiency.

[0044] Figures 4A to 4R are schematic diagrams illustrating the external shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer of the hollow fiber module according to the second embodiment. The external shape of the hollow fiber bundle can be determined by the main area where the hollow fibers are located in the cross-section of the adhesive fixing layer, and may be, for example, a rectangle as illustrated in Figure 4A, or a roughly rectangular shape. A roughly rectangular shape may have irregularities on its outer periphery, rounded corners, etc., as illustrated in Figures (4)B to 4F. Furthermore, a roughly rectangular shape can be a combination of multiple rectangles or roughly rectangular shapes, or a shape in which hollow fibers are arranged in an arbitrary shape, as illustrated in Figures (4)G to 4R.

[0045] As illustrated in Figure 4B, in a roughly rectangular shape, hollow fibers are arranged randomly, and the outer perimeter of the roughly rectangular shape may have bumps and irregularities.

[0046] As illustrated in Figure 4C, the hollow fiber bundles present in the cross-section of the adhesive fixing layer may include regions of hollow fibers (referred to as "enclaves" in this disclosure) that are spaced apart from the main rectangular or substantially rectangular area of ​​existence.

[0047] As illustrated in Figure 4D, in a roughly rectangular area, there can be multiple regions where hollow fiber bundles exist, and gaps can exist between them.

[0048] As illustrated in Figure 4E, a roughly rectangular shape can have rounded corners or an R-shaped section.

[0049] As illustrated in Figure 4F, the main area of ​​existence, whether rectangular or roughly rectangular, can be hollow.

[0050] As illustrated in Figures 4G to 4J, the main area of ​​existence of a rectangle or a roughly rectangular shape can be a combination of two or more rectangles or roughly rectangular shapes.

[0051] As illustrated in Figures 4K to 4R, the main rectangular or roughly rectangular area can be formed by arranging hollow fibers in any shape.

[0052] In the second embodiment, among the external shapes of the hollow fiber bundles present in the cross-section of the adhesive fixing layer illustrated above, the efficiency of gas flow within the module or the increase in gas flow rate, and CO ２ From the viewpoint of improving adsorption efficiency, a rectangular shape is preferred.

[0053] Hollow fiber modules can be designed to efficiently bring a medium (e.g., air or a mixture of combustion exhaust gases) into contact with at least one adsorbent that selectively removes at least one component from the medium. Efficient contact can minimize the amount of adsorbent required, the module's capacity, and the energy required for regeneration. Efficiently designed hollow fiber modules also minimize pressure drops in the air or combustion exhaust gases, and the fluid used to heat or cool the module. Similarly, efficiently designed hollow fiber modules can minimize energy losses from pressure drops in the air or combustion exhaust gases passing through the module, and the energy required for the expansion or compression of the fluid used to heat or cool the module.

[0054] The configurations of the hollow fiber modules according to the first and second embodiments are interchangeable and can be combined. The configuration and use of the hollow fiber modules, as well as the manufacturing method of the hollow fiber modules, will be described below.

[0055] <Hollow Fiber> The hollow fiber may include at least one adsorbent (5) and a barrier layer (6) to prevent fluid communication between the lumen of the hollow fiber (2) and the at least one adsorbent (5), as illustrated in Figures 2A and 2B. The adsorbent (5) may include an adsorbent, and the hollow fiber (2) may include an adsorbent or an adsorbent composition.

[0056] The hollow fiber may contain a polymer network, and the polymer network may contain multiple meandering pathways. The hollow fiber may optionally contain various types of materials, which are continuous and flexible filaments or separate elongated fragments similar in length to the fiber.

[0057] Hollow fibers can contain, and are not limited to, a large number of polymers, including, for example, cellulose, cellulose acetate, polyvinylpyrrolidone, polysulfone, polyethersulfone, polyacrylonitrile, epichlorohydrin, polyetheramide block copolymer, polyimide, polyetherimide, polyolefin, polypropylene, polyethylene, polyamide, polytetrafluoroethylene, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), polyethylene-tetrafluoroethylene copolymer, polystyrene, polyisobutylene, polybutadiene, polyurethane, elastomer, polyetherketone, polyetheretherketone, poly-4-methylpentene, copolymers of multiple monomers to constitute these, or combinations thereof. Hollow fibers 110 can also contain glass or ceramic materials. Hollow fibers can contain a combination of polymers and glass or ceramic materials.

[0058] Since hollow fibers can contain polymers or polymer networks, adsorbent substances, etc., they can be formed using compositions containing these components (hereinafter sometimes referred to as "adsorbent compositions").

[0059] The adsorbent composition may further comprise a polymer matrix containing a polymer and a plurality of meandering pathways passing through hollow fibers. The plurality of meandering pathways contain a plurality of pores, where at least some of the pores are in fluid communication with each other.

[0060] Multiple meandering paths may include one or more mesopores, macropores, and micropores, where at least some of the mesopores, macropores, and micropores are in fluid communication with one another.

[0061] In one embodiment, the ratio of the length of the hollow fiber to the average longest cross-section is greater than 1, for example, about 4 or more, about 10 or more, about 100 or more, or about 1,000 or more.

[0062] Hollow fibers can have a variety of cross-sectional shapes, and are not limited to these, but may include, for example, rectangles, circles, semicircles, squares, pentagons, triangles, hexagons, octagons, star shapes, star-shaped shapes, U-shaped shapes, shallow cracks, multiple shallow cracks, irregular shapes, or combinations thereof, or intermediate shapes. Depending on the cross-sectional shape of the hollow fiber, the average longest cross-sectional dimension of the hollow fiber can be determined. In one example, the average longest cross-sectional dimension of a hollow fiber with a circular cross-sectional shape may be the diameter of the hollow fiber. In another example, the average longest cross-sectional dimension of a hollow fiber with a rectangular cross-sectional shape may be the diagonal between the length and width of the rectangular cross-section of the hollow fiber. In yet another example, the average longest cross-sectional dimension of a hollow fiber with a star-shaped cross-section may be the distance between the two furthest points of the star-shaped cross-section of the hollow fiber.

[0063] The hollow fiber may have an average longest cross-sectional dimension of at least about 100 μm, at least about 500 μm, or at least about 1,000 μm. In one embodiment, the hollow fiber has an average longest cross-sectional dimension of about 1,200 μm. In a typical example, a hollow fiber with a circular cross-section has an average diameter of about 1,200 μm. The hollow fiber may include diameters in the range of about 800 μm to about 2,000 μm.

[0064] The lumen of a hollow fiber can have a number of cross-sectional shapes, and is not limited to them, but may include, for example, rectangles, circles, semicircles, squares, pentagons, triangles, hexagons, octagons, star shapes, star-shaped shapes, U-shaped shapes, shallow fissures, multiple shallow fissures, irregular shapes, or combinations thereof, or intermediate shapes thereof. Depending on the cross-sectional shape of the lumen, the average longest cross-sectional dimension of the lumen can be determined. In one example, the average longest cross-sectional dimension of a lumen with a circular cross-sectional shape may be the diameter of the lumen. In another example, the average longest cross-sectional dimension of a lumen with a rectangular cross-sectional shape may be the diagonal between the length and width of the lumen. In yet another example, the average longest cross-sectional dimension of a lumen with a star-shaped cross-sectional shape may be the distance between the two furthest points in the star-shaped cross-section of the lumen.

[0065] The lumen of the hollow fiber can have an average longest cross-sectional dimension of at least about 50 μm, at least about 200 μm, or at least about 500 μm. In one embodiment, the lumen has an average longest cross-sectional dimension of about 300 μm. In a typical example, a lumen with a circular cross-section has an average diameter of about 300 μm. The lumen can include diameters in the range of about 200 μm to about 1000 μm.

[0066] In one embodiment, the hollow fiber may have the same or similar cross-sectional shape as its lumen. In another embodiment, the hollow fiber may have a different cross-sectional shape from its lumen, specifically, the ratio of the average longest cross-sectional dimension of the hollow fiber to the average longest cross-sectional dimension of the lumen may be greater than about 1.5, greater than about 2, greater than about 4, or greater than about 4. In a typical example, the ratio of the average longest cross-sectional dimension of the hollow fiber to the average longest cross-sectional dimension of the lumen may be about 4.

[0067] <Adsorbent Substances> In various embodiments, the hollow fiber contains at least one adsorbent substance. As illustrated in Figures 2A and 2B, the hollow fiber (2) may contain at least one adsorbent substance (5), or at least two adsorbent substances (5,5). At least one adsorbent substance is used in the hollow fiber from the viewpoint of selectively adsorbing at least one component of the medium.

[0068] The above-mentioned components can include, and are not limited to, many substances as adsorbed substances, but for example, carbon dioxide (CO2). ２ ), it may contain hydrogen, nitrogen, oxygen, water, etc.

[0069] The adsorbent material may include, for example, zeolites, silicon aluminophosphate (SAPO) materials, aluminosilicates, aluminophosphate (ALPO) materials, activated carbon, activated alumina, silicon dioxide, silicates, amine-grafted silica, organometallic skeletons, conjugated organic skeletons, organometallic polyhedra, zeolite-imidazolate skeletons, polymer-based adsorbents, or combinations thereof.

[0070] Furthermore, in addition to the adsorbent, the material may contain amines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenehexamine, monoethanolamine, diethanolamine, triethanolamine, polyethyleneimine, polypropyleneimine, or combinations thereof.

[0071] Adsorbent substances absorb CO from the air and combustion exhaust gases. ２ It can be used to selectively adsorb CO. Large amounts of nitrogen are present in the air and in the combustion exhaust gas where air is used in the combustion process. Therefore, the adsorbent used can selectively adsorb CO. ２ It is preferable that it has high selectivity.

[0072] In various embodiments, the adsorbent composition for constructing the hollow fiber may have, with respect to the selectivity defined above, a selectivity of at least 5 for the first component (e.g., component A) relative to the second component, at least 10 for the first component relative to the second component, or at least 25 for the first component relative to the second component.

[0073] The gas supply flow is CO ２ From the perspective of recovering CO2, a CO2 greater than approximately 5 relative to nitrogen in the gas mixture is used. ２ It has adsorption selectivity, or is greater than about 10 O with respect to nitrogen in the gas mixture. ２ It is brought into contact with an adsorbent having adsorption selectivity. In one embodiment, the adsorbent is a CO2 adsorbent with a CO2 adsorption rate of about 10 to 60 relative to nitrogen. ２ It can have selectivity.

[0074] The amount of CO2 packed into the adsorbent material can be greater than approximately 0.25 mmol of CO2 per gram (g) of adsorbent material, greater than approximately 0.75 mmol of CO2 per gram of adsorbent material, or greater than approximately 1.5 mmol of CO2 per gram of adsorbent material.

[0075] The adsorbed substance is approximately -25 kJ / (mol CO2). ２ ) ~ approx. -90kJ / (mol CO ２ ) may contain the heat of adsorption. ２Examples of adsorbent materials that can remove CO from nitrogen-containing gas mixtures and achieve the desired packing amount include, but are not limited to, microporous materials such as zeolites, cationic zeolites, ALPO materials, and SAPO materials. Non-limited examples of zeolites suitable for use include zeolites 4A, 5A, Bx, NaX, and NaY. Non-limited examples of cationic zeolites are zeolites with a Si / Al ratio of less than about 5, such as faujasite, beta, and mordenite. Also, siliceous zeolites such as MFI can remove CO from nitrogen-containing mixtures. ２ It can be used for removal. Additional adsorbents may include, for example, hydrotalcite, microporous materials containing a skeleton of a component other than silicon (Si) or aluminum (Al) (e.g., phosphorus (P)), carbon, microporous sol-gel derived materials, silica, silica particles impregnated with amines, and amines grafted onto mesoporous silica. These adsorbents can be used alone or in combination with other materials. In particular, a bundle of hollow fibers containing an adsorbent and a barrier layer covering the hollow fiber lumen is subjected to alternating flow of room temperature water or cold and hot water to remove CO2. ２ From the viewpoint of efficiently recovering these materials, amine-impregnated silica particles and amines grafted onto mesoporous silica are preferred, and amine-impregnated silica particles are more preferred. Examples of amine-impregnated silica particles include polyethyleneimine (PEI)-impregnated silica particles.

[0076] The content of adsorbent material in the hollow fiber can be approximately 30% or more by weight of the dry hollow fiber, or 40% or more by weight of the dry hollow fiber, from the viewpoint of exhibiting high adsorption performance. The content of adsorbent material in the hollow fiber can be less than approximately 80% by weight of the dry hollow fiber, less than approximately 75% by weight of the dry hollow fiber, or less than approximately 70% by weight of the dry hollow fiber, or less than 60% or less than 55% of the dry hollow fiber. In a typical example, the adsorbent material is approximately 50% by weight of the dry hollow fiber.

[0077] The adsorbent material may include an adsorbent layer, adsorbent particles, adsorbent components, multiple adsorbent particles, multiple adsorbent components, adsorbent particles, adsorbent components, multiple adsorbent particles, or multiple adsorbent components.

[0078] The adsorbent material may have, for example, an average longest cross-sectional dimension of less than approximately 100 μm, less than approximately 50 μm, less than approximately 10 μm, or less than approximately 2 μm.

[0079] In this disclosure, the adsorbent is associated with a polymer matrix, but the multiple adsorbent particles are not necessarily highly bound to the polymer matrix. For example, the relationship between the adsorbent and the polymer matrix can be described as a "sieve in a cage." Typically, a hollow fiber may include multiple adsorbent particles that are in fluid communication with at least some of multiple meandering pathways. Even if multiple adsorbent substances are dispersed through the hollow fiber, some of the meandering pathways may not contain the adsorbent substances associated with them.

[0080] <Barrier Layer> The hollow fiber may include a barrier layer covering its lumen. As illustrated in Figures 2A and 2B, the hollow fiber (2) may include a barrier layer (6) covering its lumen to prevent fluid communication between its lumen and the adsorbent (5). The components of the barrier layer may be included, for example, in an adsorbent composition.

[0081] The barrier layer can contain, and is not limited to, numerous materials, including, for example, polyvinylidene chloride (PVDC), polyacrylonitrile, epichlorohydrin (hydrin), polyetheramide block copolymers, glass, silica, alumina, metals, metal oxides, latex, other high-barrier polymers, copolymers of multiple monomers comprising these, or combinations thereof.

[0082] The barrier layer may have an average thickness of less than approximately 50 μm, or less than approximately 30 μm. The lower limit of the average thickness of the barrier layer is not limited, but may be, for example, greater than 0 μm, or about 1 μm or more.

[0083] The diffusion coefficient of the barrier layer is preferably less than about 1 / 50, more preferably less than about 1 / 10,000, of the average diffusion coefficient of the polymer matrix, from the viewpoint of its function as a diffusion barrier. The diffusion barrier can be configured so that the supply flow of fluid passing through the lumen of the hollow fiber does not enter the polymer matrix, or so that a desired adsorbent substance, such as CO2, does not flow into the lumen and is lost.

[0084] <Adhesive Fixing Layer> The hollow fiber module may include an adhesive fixing layer. As illustrated in Figure 1, the hollow fiber module (1) may be provided with adhesive fixing layers (4, 4) to adhesively fix the hollow fiber bundle (3) at both ends, and the hollow portion of the hollow fiber bundle (3) may be open at the ends of the adhesive fixing layers (4, 4).

[0085] The components of the adhesive fixing layer may include, for example, adhesives, adhesive substances, and binding substances. The ends of the hollow fiber bundles may be embedded in or incorporated into the components of the adhesive fixing layer. The angle at which the ends of the hollow fiber bundles are embedded in or incorporated into the adhesive fixing layer can be set arbitrarily, for example, to be perpendicular or oblique to the cross-section of the adhesive fixing layer. From the viewpoint of effectively interconnecting adjacent hollow fibers, it is preferable that the adhesives, adhesive substances, binding substances, etc., fix the hollow fibers in a substantially parallel arrangement.

[0086] The adhesive fixing layer can take any form, for example, in the form of an end cap that fits the end of the hollow fiber bundle. The end cap can be designed so as not to obstruct the fluid flow through the lumen of the hollow fiber. The end cap can prevent fluid communication between the meandering path of the longitudinal end of the hollow fiber and the environment surrounding the longitudinal end of the hollow fiber.

[0087] Examples of adhesive and fixing layers include polymer materials such as epoxy resin, urethane resin, epoxy acrylate resin, and silicone resin.

[0088] In a hollow fiber module, the packing density of the hollow fibers can be at least 30%, 35%, or 40% from the viewpoint of achieving high adsorption performance, and can be 60% or less, 55% or less, or 50% or less from the viewpoint of increasing the gas flow velocity inside. In a typical example, the packing density of the hollow fibers in a hollow fiber module is 45%.

[0089] The filling rate of hollow fibers is a value calculated from the area of ​​the hollow fibers and the area of ​​the adhesive fixing layer, which will be described later. Hollow fiber cross-sectional area = (Average diameter of hollow fibers / 2)^2 × Pi × Number of fibers = Hollow fiber cross-sectional area / (Hollow fiber cross-sectional area + Adhesive fixing layer cross-sectional area)

[0090] <Core Rods> The hollow fiber module may optionally be provided with one or more core rods at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer. As illustrated in Figure 1, one core rod (7) can be positioned at the center of the cross-section of the adhesive fixing layer (4) or inside the adhesive fixing layer (4) from the viewpoint of supporting the adhesive fixing layer (4, 4) at both ends of the hollow fiber module (1). From a similar viewpoint, one core rod can be positioned on the outer periphery of the adhesive fixing layer (not shown). From a similar viewpoint, multiple core rods (not shown) can be positioned at the center of the cross-section of the adhesive fixing layer (4), inside the adhesive fixing layer (4), or on the outer periphery of the adhesive fixing layer (not shown).

[0091] The core rod can contain any known material as long as it can support the adhesive fixing layer at both ends of the hollow fiber module, and may include, for example, synthetic resins, synthetic fibers, natural fibers, inorganic materials, engineering plastics, elastic materials, aluminum, iron, stainless steel (SUS), titanium, other metals, composites thereof, or combinations thereof.

[0092] The ends of the core rod are preferably flat in shape, from the viewpoint of reducing the pressure applied to the adhesive fixing layer of the hollow fiber module.

[0093] The core rod may be in the form of a tube for gas collection, and from the viewpoint of gas collection efficiency, it is preferable that it be in the form of a tube positioned at the center of the cross-section of the adhesive fixing layer (4) or inside the adhesive fixing layer (4).

[0094] The ends of the core rods may be, but are not limited to, solid, impermeable materials, and may include, for example, solid metals, engineering plastics, etc., which allows gases to flow into or out of the hollow fiber module without mixing with the heating or cooling medium.

[0095] A portion of the core rod can be made of a porous material such as a porous metal, a porous polymer, or a woven mesh, thereby enabling the effective collection of gas within the hollow fiber module.

[0096] <Use of Hollow Fiber Modules> Another aspect of the present disclosure provides the use of the hollow fiber modules described above, for example, a method for flowing gas through the hollow fiber modules of the first embodiment and / or the hollow fiber modules of the second embodiment described above.

[0097] Figures 5A and 5B are schematic diagrams illustrating the relationship between the shape of the hollow fiber bundle present in the cross-section of the adhesive fixed layer and the direction of gas flow in a method of flowing gas through a hollow fiber module.

[0098] A method for flowing gas through a hollow fiber module according to the first embodiment is as follows: The hollow fiber module includes a hollow fiber bundle consisting of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the hollow fiber bundle at both ends; the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity; the hollow portion of the hollow fiber bundle is open at the end of the adhesive fixing layer; the hollow fiber bundle present in the cross-section of the adhesive fixing layer has an aspect ratio (ratio of length of line A / length of line B) greater than 1.0 and less than 1,000 when line A is the line where the distance between the hollow fibers is maximum and line B is the line perpendicular to line A with the maximum distance; and the gas can be directed toward the longer side of the outer shape of the cross-section of the hollow fiber bundle, or the gas can be flowed perpendicular to the longer side of the outer shape.

[0099] The method for flowing gas through the hollow fiber module according to the first embodiment, as shown in Figure 5A, involves directing the gas toward the longer side (straight line A) of the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer, where the aspect ratio is greater than 1.0 and less than 1,000, or flowing the gas perpendicular to the longer side (straight line A) of the outer shape. This allows the gas to flow efficiently within the module, increasing the gas flow rate within the module and reducing CO2 levels. ２ This could potentially increase the adsorption efficiency.

[0100] A method for flowing gas through a hollow fiber module according to the second embodiment is as follows: The hollow fiber module includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends; the hollow fibers include an adsorbent and a barrier layer that covers the hollow fiber cavity; the hollow portion of the bundle of hollow fibers is open at the ends of the adhesive fixing layer; the outer shape of the bundle of hollow fibers in the cross-section of the adhesive fixing layer is rectangular or substantially rectangular, and the gas can be directed toward the longer side of the rectangle or substantially rectangular shape, or the gas can be flowed perpendicular to the longer side of the outer shape of the cross-section of the bundle of hollow fibers.

[0101] In the second embodiment, as shown in Figure 5B, a method for flowing gas through a hollow fiber module involves directing the gas toward the long side of a bundle of hollow fibers with a rectangular or substantially rectangular (not shown) outer shape present in the cross-section of the adhesive fixing layer, or flowing the gas perpendicular to the long side. This allows the gas to flow efficiently within the module, increasing the gas flow rate within the module and reducing CO2 emissions. ２ This could potentially increase the adsorption efficiency.

[0102] From the above viewpoint, the method for flowing gas through a hollow fiber module according to this disclosure is preferable in which the gas is flowed through the hollow fiber module and the adsorbed component is adsorbed at the same time.

[0103] In yet another aspect of this disclosure, a method is provided for selectively adsorbing components of a medium using the hollow fiber module according to the first embodiment and / or the hollow fiber module according to the second embodiment described above.

[0104] A method for flowing a gas through a hollow fiber module, or a method for selectively adsorbing components of a medium using a hollow fiber module, includes the steps of bringing the gas or medium into contact with a bundle of hollow fibers consisting of a plurality of hollow fibers as described above, and adsorbing components of the medium.

[0105] In one example, a method for adsorbing a predetermined component includes the steps of bringing a gas or medium into contact with a bundle of hollow fibers, which includes a plurality of meandering pathways, one or more adsorbent substances that are in fluid communication with at least a portion of the plurality of meandering pathways, a lumen disposed within the hollow fibers, and a barrier layer covering the lumen to prevent fluid communication between the lumen and the plurality of meandering pathways, and the predetermined component in the gas or medium, for example, CO ２ The method includes a step of adsorbing such substances. The above method may further include a step of desorbing components in a gas or medium.

[0106] Various embodiments relate to the selective adsorption of components of a gas or medium, which may include combustion flue gas, natural gas, fuel gas, biogas, city gas, waste gas, water, coal gas, air, or carbon dioxide-containing fluids. Typically, the adsorbent compositions for forming hollow fibers or bundles of hollow fibers according to this disclosure can be used, for example, in a temperature swing adsorption process for the recovery of CO2 from combustion flue gas or air.

[0107] One or more hollow fiber modules relating to this disclosure can be used in a TSA process, where they are used as bare modules, and a fan can be used to blow air onto the rectangular or substantially rectangular long side of the adhesive fixing layer of the module. At this time, the fan may be positioned to blow air from the upwind side of the module, or conversely, it may be positioned on the downwind side of the module to blow air in a way that draws it in.

[0108] One or more hollow fiber modules relating to this disclosure can be used in a TSA process, and in a TSA process, they can be mounted in a chamber comprising a supply flow inlet, a supply flow outlet, a heat conduction fluid inlet, and a heat conduction fluid outlet. The chamber can have various shapes, including, but is not limited to, tubular or cylindrical, or rectangular or cubic shapes. The walls of the chamber may have grooves. A barrier layer covering the lumen of the hollow fiber prevents fluid communication between the lumen and at least one adsorbent, so that the heat conduction medium can pass through the lumen of the hollow fiber.

[0109] In the adsorption process, the gas can optionally pass through a chamber or its grooves and flow into the hollow fiber module, coming into contact with the adsorbent material. The polymer matrix containing at least one adsorbent material is CO ２ , and H as desired ２ O, SO Ｘ and NO Ｘ The impurities are removed from the gas. The purified vapor can, if desired, be collected in the highly porous portion of the gas collection tube, which serves as the core. The purified gas passes to the outside of the module, for example, through the impermeable portion of the core connecting the flow control valve and exhaust stack of the module or jacket.

[0110] From the viewpoint of controlling the temperature rise during the adsorption process, a cooling medium (e.g., water) can pass through the lumen of the hollow fiber. After the adsorption process is complete, the gas flow into the module may be stopped by a valve, and a heating medium (e.g., steam) can pass through the lumen of the hollow fiber. CO is released from the polymer matrix of the hollow fiber containing at least one adsorbent. ２ And H upon request ２ O, SO Ｘ and NO Ｘ It can pass outside the module through the core rod, jacket, or groove in the jacket, as desired.

[0111] The hollow fiber module can be recycled through at least two steps, for example, an adsorption step and a regeneration step. Regeneration of the hollow fiber module involves removing the components (e.g., CO2) recovered from the hollow fiber module. ２ This can be done by heating the hollow fiber module to an effective temperature for detachment. The hollow fiber module can then be cooled to allow other adsorption processes to complete.

[0112] In various embodiments, multiple hollow fiber modules can be periodically brought into contact with a thermal conductive medium to promote adsorption and desorption. The thermal conductive medium can include, but is not limited to, many media, including, for example, water, water vapor, steam, or a combination thereof. Typically, water is CO ２ For adsorption, the vapor flows through the lumen of multiple hollow fibers in the hollow fiber module, and the vapor is CO ２ For attachment and detachment, the fluid flows through the lumen of the multiple hollow fibers in the hollow fiber module.

[0113] In one embodiment, the adsorption hollow fiber module (e.g., the first hollow fiber module) approaches saturation, and as a result, CO is removed from the gas. ２ It should be understood that the amount may be less than the desired amount. Therefore, the gas flow to the first hollow fiber module can be diverted into the second hollow fiber module, which has already been regenerated, while the first hollow fiber module can be thermally regenerated. Following regeneration, the first hollow fiber module is prepared for the adsorption process, and the gas mixture flow can be switched from the second hollow fiber module to the first hollow fiber module. The total cycle time is the length of time from when the gaseous mixture is first introduced into the first hollow fiber module in the first cycle until the gaseous mixture is introduced into the first hollow fiber module again in the immediately following cycle, for example, after one bed regeneration. In addition to the first and second hollow fiber modules, the use of multiple hollow fiber modules (e.g., third, fourth, fifth, etc.) enables continuous processing and is particularly suitable when the adsorption time is shorter than the regeneration time.

[0114] A thermal swing adsorption process may include rapid cycles of adsorption and desorption, in which case it is called a fast cycle thermal swing adsorption (RCTSA) process. A fast cycle thermal swing adsorption process is defined in this disclosure as having a cycle time between consecutive adsorption steps of less than about 2 minutes, less than about 1 minute, less than about 0.5 minutes, or less than 0.25 minutes. In one embodiment, a regeneration step may be assisted by partial purging pressure displacement or pressure swing, etc. A combination of these steps is referred to in this disclosure as a thermal swing process insofar as it employs thermal swing at some point between the regeneration steps.

[0115] In many cases, the time required for adsorbent regeneration may be shorter than the time required to fully utilize the adsorption capacity of the hollow fiber modules. In these cases, it is preferable that multiple hollow fiber modules are in the adsorption phase while multiple hollow fiber modules are in the heating / regeneration and recooling phases. In one embodiment, multiple hollow fiber modules involved in adsorption are connected in a series manner such that the unit of the most recently regenerated hollow fiber module is the final bed of the adsorption row, and the first unit of the row can be regenerated next. In another embodiment, the adsorption units are connected in parallel so that each adsorbent handles a portion of the entire supply flow.

[0116] <Method for Manufacturing Hollow Fiber Modules> The hollow fiber modules of the present disclosure can be manufactured, for example, as follows:

[0117] The method for manufacturing a hollow fiber module according to this disclosure may include, for example, the following steps: spinning hollow fibers, incorporating an adsorbent, and covering the lumen of the hollow fibers with a barrier layer; forming a hollow fiber module by bonding and fixing both ends of a bundle of multiple hollow fibers with an adhesive fixing layer; creating an opening in the hollow portion of the hollow fiber bundle at the ends of the adhesive fixing layer; optionally arranging one or more core rods at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer to support the adhesive fixing layer at both ends of the hollow fiber module; optionally attaching a chamber to the hollow fiber module; optionally constructing a system including multiple hollow fiber modules; optionally circulating and regenerating the hollow fiber modules.

[0118] Hollow fibers can be formed by a known non-solvent phase conversion technique, generally known as wet spinning. A polymer solution containing a solvent, a non-solvent, and an additive such as lithium nitrate may be extruded through a die into a non-solvent quenching bath. The non-solvent quenching bath acts as the driving force for mass transfer between the quenching bath and the solvent present in the new fiber, resulting in microphase separation and porous fibers. During the spinning process, excess non-solvent from the solidification bath moves the composition into a two-phase region, resulting in liquid-liquid separation and a continuous polymer pore network.

[0119] In one example, cellulose acetate and / or PVP can be used as the polymer. The polymer is preferably dried, for example, under vacuum at 110°C, to remove water. After drying, the polymer solution can be obtained by dissolving it in a solvent such as N-methylpyrrolidone (NMP).

[0120] In forming a hollow fiber bundle consisting of multiple hollow fibers, each hollow fiber may contain at least one adsorbent capable of absorbing a specific component of the medium, or a mixture of multiple adsorbents capable of absorbing different components of the medium. For example, the first hollow fiber may contain a first adsorbent capable of adsorbing a first component of the medium, and the second hollow fiber may contain a second adsorbent capable of adsorbing a second component of the medium. The use of multiple hollow fibers (e.g., third, fourth, fifth, etc.) in addition to the first and second hollow fibers enables the adsorption of a number of components of the medium.

[0121] A single adsorbent, or a group of different adsorbents, can be incorporated into the hollow fiber. The adsorbents can be selected for the desired removal of specific components of the medium. In one example, a hollow fiber, hollow fiber bundle, or hollow fiber module containing multiple adsorbents allows for the selective removal of multiple components by a single hollow fiber module. In another example, a hollow fiber, hollow fiber bundle, or hollow fiber module may contain a single adsorbent capable of removing multiple components from the medium.

[0122] For example, adsorbents such as zeolite 13X, high-silica MFI, amines grafted onto mesoporous silica, and silicon dioxide can be incorporated into the hollow fibers so that the adsorbent substance accounts for 50% by weight of the hollow fibers. In the case of zeolite, pre-drying is preferable.

[0123] For example, the hollow fibers can be further impregnated with adsorbent substances such as amines. For instance, the hollow fibers can be immersed in a solution in which adsorbent substances such as amines are dissolved in a solvent such as water or methanol, thereby impregnating them with these substances.

[0124] The process of covering the lumen of the hollow fiber with a barrier layer can be carried out in such a way that the lumen does not come into fluid communication with the adsorbed material. Two methods for constructing the barrier layer include, for example, double-layer spinning and post-treatment. Double-layer spinning allows the lumen layer to be formed directly when the hollow fiber is formed. The post-treatment method involves washing the outside of the hollow fiber with a coking polymer. In this design, the post-treatment can be carried out inside the hole of the hollow fiber. Polyvinylidene dichloride (PVDC) latex can be selected as the material for the barrier layer because it has very low water and gas permeability, as well as heat resistance in fast thermal cycles.

[0125] The steps of forming a hollow fiber module by adhesively fixing both ends of a bundle of hollow fibers, which consists of multiple hollow fibers, with an adhesive fixing layer, and / or opening the hollow portion of the hollow fiber bundle at the ends of the adhesive fixing layer, are performed such that the hollow fiber bundle present in the cross-section of the adhesive fixing layer has an aspect ratio greater than 1.0 and less than 1,000 according to the first embodiment described above, and / or has a rectangular or substantially rectangular outer shape according to the second embodiment described above.

[0126] For example, a bundle of hollow fibers consisting of multiple hollow fibers may be one large bundle, or it may be a shape formed by bundling together multiple smaller bundles of hollow fibers.

[0127] Furthermore, in the above process, a core rod may be placed inside the hollow fiber bundle.

[0128] The process of bonding and fixing both ends of a bundle of hollow fibers, which consists of multiple hollow fibers, with an adhesive fixing layer can be carried out by surrounding the ends of the multiple hollow fibers with a binding material that constitutes the adhesive fixing layer, incorporating them into the binding material, or embedding them in the binding material.

[0129] In one example, a polymer resin such as an adhesive is poured into a mold, hollow fiber bundles are immersed in it, and then the polymer resin is cured by heat treatment to bond and fix the bundles in place. At this time, by using a mold with a suitable aspect ratio or rectangular shape and arranging the hollow fiber bundles in a suitable aspect ratio or rectangular shape, modules with a suitable aspect ratio or rectangular hollow fiber bundle shape can be obtained.

[0130] Furthermore, in the above process, a core rod may be placed inside or outside the hollow fiber bundle and simultaneously fixed to the adhesive fixing layer.

[0131] The process of opening the hollow fibers at the end of the adhesive fixing layer involves cutting the adhesive fixing layer together with the hollow fiber bundle, thereby opening the hollow portion of the hollow fiber bundle.

[0132] While there are no particular limitations on the cutting method, it can be done using gas cutting, mechanical cutting with saw blades, electric cutting with plasma, laser cutting, or water jet cutting.

[0133] To visualize the arrangement of embedded hollow fibers, the chamber and binding material can be made transparent. The arrangement of embedded hollow fibers can be sealed within the chamber, and the sealing surface can be provided at the end of the chamber. During operation, or in the process of attaching the chamber to the hollow fiber module, the chamber can be attached to the TSA or RCTSA hollow fiber module in a manner that prevents fluid communication between the separation medium and the heat exchange medium.

[0134] In another aspect of the present disclosure, a system for removing CO2 and water from combustion flue gas can be provided, comprising a plurality of hollow fiber modules. In the system according to the present disclosure, the combustion flue gas flow may pass through a first hollow fiber module to remove a first component of the medium and through a second hollow fiber module to remove a second component of the medium. For example, when removing multiple components from a medium (e.g., combustion flue gas) using separate operating units (e.g., hollow fiber modules) for each component of the medium, one hollow fiber module can be optimized for the removal of one specific component.

[0135] The system relating to this disclosure comprises a first hollow fiber module for removing water, and SO Ｘ NO Ｘ , and CO ２ A second hollow fiber module may be included for removing one or more of the above. One or more hollow fiber modules can be regenerated by the regeneration method after the completion of the adsorption process as described above.

[0136] In yet another aspect of this disclosure, a system for removing CO2 and water from combustion flue gas can be provided, comprising a hollow fiber module containing multiple adsorbents. In this system, the adsorbents can independently adsorb water and / or CO2. Typically, a water-selective adsorbent can be placed near the feed flow inlet, and a CO2-selective adsorbent can be placed downstream of the water-selective adsorbent. Such an arrangement is intended to remove water first from the combustion flue gas, followed by CO2, so that the combustion flue gas comes into contact with the water-selective adsorbent before the CO2-selective adsorbent. In some embodiments, the same adsorbents used for CO2 removal are used to adsorb, for example, SO2 in the combustion flue gas. X NO X It can also remove other components such as water. X NO X Adsorbent materials capable of adsorbing water include, but are not limited to, zeolites, cationic zeolites, mesoporous materials, carbon, polymers, mixed matrix materials, and combinations thereof.

[0137] In removing CO2 and water from combustion flue gas, a dehydration step can be performed, and this dehydration step may include glycol dehydration. The combustion flue gas can be dehydrated in a separate process or in a unit operation before introducing the combustion flue gas into the hollow fiber module. To efficiently remove water by glycol dehydration, the temperature of the combustion flue gas can be lowered to below 110°C or below 75°C.

[0138] The dehydration step may include the physical knockout of condensed water (e.g., water droplets or mist) before the combustion flue gas comes into contact with the hollow fiber module, thereby allowing the hollow fiber module to contain an adsorbent that selectively removes water from the combustion flue gas. Adsorbents capable of selectively removing water from the combustion flue gas include, but are not limited to, cationic zeolites, functional micropores and mesopores, carbon, mixed matrix materials, polymers, or combinations thereof.

[0139] The treated combustion exhaust gas present in the hollow fiber module can be dehydrated to a water content of approximately 400 ppm or less, approximately 50 ppm or less, or approximately 20 ppm or less at at least one point during the adsorption cycle.

[0140] If the hollow fiber module removes a significant proportion (e.g., greater than 75%) of CO2 and water from the combustion exhaust gas, a regeneration process can be performed to remove both of these components. The regeneration process can be carried out so that a separated water-rich flow and a separated CO2-rich flow are generated between the thermal regeneration process.

[0141] While the foregoing description relates to typical embodiments, numerous improvements or alternatives can be made without departing from the concept and scope of the invention as described herein.

[0142] Typical embodiments relating to this disclosure are described in detail by examples, but these examples should not be construed as limiting the scope of this disclosure. This disclosure may include embodiments other than those described by examples, improvements, and equivalents or equivalent processes thereof.

[0143] <Acquisition of basic data for simulation> - Experimental conditions: One silica-containing hollow fiber impregnated with polyethyleneimine is placed in a cell, and 400 ppm CO2 is introduced at an arbitrary flow rate. ２ The CO2 is applied perpendicularly to the hollow fiber, and CO2 is applied to the medium inlet and outlet sides of the cell. ２ Measure the concentration, CO ２ Adsorption breakthrough curve (CO ２ A service life curve and an integrated adsorption curve were obtained. At this time, the length of the hollow fiber was 45 mm, the outer diameter was 0.80 mm, the inner diameter was 0.38 mm, the silica content was 35% by weight, and the polyethyleneimine content was 37%. The cross-sectional area of ​​the cell channel was 1 mm × 45 mm.

[0144] Under the experimental conditions described above, CO ２ Five basic experiments were conducted by varying the gas wind speed. CO2 obtained from the basic experiments ２ The adsorption breakthrough curve and the cumulative adsorption curve are shown in Figures 6 and 7, respectively.

[0145] The obtained CO ２Based on the adsorption breakthrough curve and the cumulative adsorption curve, the following relationship (I): y = -32.3x + 191.09 (I) was derived from the linear velocity and the time to reach 0.5 mmol / g. A graph of the linear velocity versus the time to reach 0.5 mmol / g is shown in Figure 8. The basic data obtained as described above is shown in Table 1.

[0146]

[0147] <Module Shape Simulation> The shape of the hollow fiber module was varied, and the internal fiber velocity of the module was simulated as follows.

[0148] As shown in Figure 9 (where all dimensions are in "mm"), modules (hereinafter sometimes abbreviated as "Mo"), velocity inlets, pressure outlets, and planes of symmetry were set for both wall surfaces. To shorten the calculation time, only half of the modules (Mo) divided by the planes of symmetry drawn in Figure 9 were included in the calculation (*1 in Table 2).

[0149] In accordance with the yarn arrangement method shown in Figure 10 (all dimensions in the figure are in "mm"), the yarn spacing was set to 1.42 mm so that the area of ​​the circle within the triangle (the black area) would be 45% of the area of ​​the triangle (i.e., the yarn filling rate would be 45%).

[0150] - Calculation conditions: Assuming air supply by a fan, the inlet air velocity for each Mo shape is determined so that the pressure loss in all Mo shapes is approximately constant. The calculation conditions are shown in Table 2 below.

[0151] *1: As mentioned above regarding Figure 9, in order to reduce calculation time, only half of the module divided by the symmetry plane drawn in Figure 9 was used for calculation. *2: The analysis is performed in a two-dimensional plane. *3: See the section "How to determine the inlet wind speed" below. *4: Inlet wind speed × velocity inlet area

[0152] The graph in Figure 11 shows the effect of each module shape, as shown in Table 2, on the distance from the inlet and the pressure.

[0153] - How to determine the inlet wind speed: When the pressure loss is kept constant, using a rectangular 50 model, which is considered to have the greatest wind speed inside Mo as shown in Figure 11, the CO shown in Figure 6 is used. ２ Based on the adsorption breakthrough curve, the inlet wind speed is determined so that the wind speed inside the Mo chamber is 2.39 m / s or less. The pressure loss at that time is also calculated (pressure loss = approximately 13 Pa), and the inlet wind speed is adjusted so that the pressure loss is 13 Pa under conditions other than the rectangular 50 chamber.

[0154] • Analysis Results: As mentioned above, the analysis was performed assuming a constant pressure loss (i.e., the fan capacity = cost was kept constant). If a powerful fan is used regardless of cost, the air velocity inside the module will be increased regardless of the module shape, thus reducing CO2 emissions. ２ While it is possible to increase the adsorption capacity, it is not practical for real-world use. ２ In the industrial practical application of CO2 recovery, efficiently and at low cost ２ Since recovery is crucial, calculations were performed under constant pressure to fairly compare performance under identical cost conditions.

[0155] Figures 12 to 14 show the wind speed distribution map obtained from the analysis, the wind speed distribution within Mo obtained by acquiring the wind speed between hollow fibers, and the wind speed histogram within Mo, respectively. From Figure 14, it is confirmed that rectangle 50 is the most effective shape among the comparison subjects because it has the highest wind speed within Mo and also a large airflow.

[0156] The time to reach the target adsorption amount was derived from the average linear velocity using the above relational equation (I). If the time to reach the target adsorption amount was within 120 seconds, the evaluation was S (best); if it was within 150 seconds, the evaluation was A (good); if it was within 175 seconds, the evaluation was B (acceptable); and if it was greater than 175 seconds, the evaluation was C (poor). The results obtained as described above are shown in Table 3. From these results, modules with a suitable aspect ratio are CO ２ The adsorption rate is fast, meaning CO is efficiently adsorbed. ２ It can be said that this is a module that can be recovered.

[0157]

[0158] 1. Hollow fiber module 2. Hollow fiber 3. Hollow fiber bundle 4. Adhesive fixing layer 5. Adsorbent material 6. Barrier layer 7. Core rod

Claims

1. A hollow fiber module comprising a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, and the length of the line A is greater than the length of the line B when the line A is the line with the maximum distance between the hollow fibers in the cross-section of the adhesive fixing layer, and the line B is the line perpendicular to line A with the maximum distance.

2. The hollow fiber module according to claim 1, wherein the aspect ratio of the straight line A and the straight line B (ratio of the length of straight line A to the length of straight line B) is greater than 1.0 and less than 1,000.

3. The hollow fiber module according to claim 1 or 2, wherein the adsorbent is silica particles impregnated with an amine.

4. The hollow fiber module according to claim 1 or 2, wherein one or more core rods are provided at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer, to support the adhesive fixing layer at both ends of the hollow fiber module.

5. The hollow fiber module according to claim 1 or 2, wherein the outer shape of the hollow fiber bundle present in the cross-section of the adhesive fixing layer is rectangular or has an R portion.

6. The hollow fiber module according to claim 1 or 2, wherein the hollow fiber module is a bare module that does not have an outer covering body that covers the module.

7. A hollow fiber module comprising a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers comprise an adsorbent substance and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, and the outer shape of the bundle of hollow fibers in the cross-section of the adhesive fixing layer is rectangular or substantially rectangular.

8. The hollow fiber module according to claim 7, wherein the adsorbent is silica particles impregnated with an amine.

9. The hollow fiber module according to claim 7 or 8, further comprising one or more core rods at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer, which support the adhesive fixing layer at both ends of the hollow fiber module.

10. The hollow fiber module according to claim 7 or 8, wherein the hollow fibers are randomly arranged in the substantially rectangular shape, and the outer periphery of the substantially rectangular shape has bumps and irregularities.

11. The hollow fiber module according to claim 7 or 8, wherein the hollow fiber bundle present in the cross-section of the adhesive fixing layer includes, in addition to the rectangular or substantially rectangular region, a region of hollow fiber present spaced apart from the rectangular or substantially rectangular region.

12. The hollow fiber module according to claim 7 or 8, wherein in the substantially rectangular shape, there are multiple regions where the hollow fiber bundle exists, and there are gaps between them.

13. The hollow fiber module according to claim 7 or 8, wherein the substantially rectangular shape has a rounded (R) portion.

14. The hollow fiber module according to claim 7 or 8, wherein the rectangle or substantially rectangular shape is hollow in the middle.

15. The hollow fiber module according to claim 7 or 8, wherein the hollow fiber module is a bare module that does not have an outer covering body that covers the module.

16. A method for flowing gas through a hollow fiber module, which includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, and the aspect ratio (ratio of length of line A / length of line B) of the bundle of hollow fibers present in the cross-section of the adhesive fixing layer is greater than 1.0 and less than 1,000 when line A is the line where the distance between the hollow fibers is maximum and line B is the line perpendicular to line A with the maximum distance, and the gas is directed toward the longer side of the outer shape of the cross-section of the bundle of hollow fibers, or the gas is flowed perpendicular to the longer side of the outer shape.

17. A method for flowing gas through a hollow fiber module, which includes a bundle of hollow fibers made up of a plurality of hollow fibers and an adhesive fixing layer that adhesively fixes the bundle of hollow fibers at both ends, wherein the hollow fibers include an adsorbent and a barrier layer covering the hollow fiber cavity, the hollow portion of the bundle of hollow fibers is open at the end of the adhesive fixing layer, the outer shape of the bundle of hollow fibers in the cross-section of the adhesive fixing layer is rectangular or substantially rectangular, and the gas is directed toward the longer side of the rectangle or substantially rectangular shape, or the gas is flowed perpendicular to the longer side of the outer shape of the cross-section of the bundle of hollow fibers.

18. The method according to claim 16 or 17, wherein the adsorbent is silica particles impregnated with an amine.

19. The method according to claim 16 or 17, wherein one or more core rods are provided at the center of the cross-section of the adhesive fixing layer, inside the adhesive fixing layer, or on the outer periphery of the adhesive fixing layer, supporting the adhesive fixing layer at both ends of the hollow fiber module.

20. The method according to claim 16 or 17, wherein gas is flowed through the hollow fiber module and the adsorbed component is adsorbed at the same time.

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