Method for fabricating three-dimensional porous adsorbent structures

Abstract

The present invention provides a method for producing a 3D porous adsorbent structure, comprising constructing a 3D porous green body from a build material comprising a solvent, an inorganic porous adsorbent material, and an organic binder material at least partially dissolved in the solvent, depositing the build material as filaments in a plurality of layers to obtain a 3D porous green body, wherein at least a portion of the filaments in at least one of the plurality of layers are spaced apart from one another; inducing phase inversion of the 3D porous green body by exposing the 3D porous green body to a non-solvent for the organic binder material, thereby obtaining a solidified 3D porous green body; and drying the solidified 3D porous green body, thereby obtaining a 3D porous adsorbent structure; the build material comprises between 30% and 70% by weight of the inorganic porous adsorbent material and between 5% and 30% by weight of the organic binder material, based on the total weight of the build material, and the 3D porous adsorbent structure comprises at least a portion of the organic binder material, and the 3D porous adsorbent structure has an adsorbent accessibility of at least 40%, and the adsorbent accessibility is expressed by the formula (I), where S BET,構造体 is the BET surface area of ​​the 3D porous adsorbent structure, and S BET,吸着剤 is the BET surface area of ​​the initial inorganic porous adsorbent material, and X is the mass percent of the inorganic porous adsorbent material relative to the total mass of the 3D porous adsorbent structure, the BET surface area of ​​the initial inorganic porous adsorbent material and the BET surface area of ​​the 3D porous adsorbent structure being calculated according to the argon adsorption isotherm at 87 K. JPEG2025528448000011.jpg17170

Description

[Technical Field]

[0001] The present invention relates to a method for producing a three-dimensional porous adsorbent structure. The present invention further relates to a three-dimensional porous adsorbent structure, for example, a three-dimensional porous adsorbent structure obtainable by the method of the present invention. [Background technology]

[0002] Gas separation and purification, as well as catalysis, have become major parts of the chemical and petrochemical industries, and therefore extensive research is being carried out to improve the effectiveness and sustainability of existing technologies and to develop new materials that can meet these required specifications.

[0003] The development of porous materials that can specifically interact with an environment that is a liquid or gas flow has received increasing attention because these materials can be used in a variety of applications. Gas or liquid purification and separation methods based on the adsorption of specific compounds require packing of adsorbent particles or monolith designs to allow the gas or liquid flow to interact with the adsorbent particles. Also, heterogeneous catalysis in the gas or liquid phase is based on the interaction of the feed with packed materials.

[0004] The most common geometric shapes conventionally used in gas separation and catalysis applications include pellets, extrudates, and granules due to the simplicity and economic feasibility of their production methods. However, packed beds of this type of shape entail several drawbacks, such as high pressure drop when used in reactor columns and limited mass transfer due to slow diffusion into the core of the particle, which results in inefficient use of the catalyst or adsorbent material.

[0005] Porous monoliths have been found to offer a promising alternative due to their ability to reduce pressure drop, reduce mass transfer due to ordered packing and limit open channeling in the structure.

[0006] One method for producing monolithic catalyst structures is by coating a porous inert monolith support. However, coating an inert support often results in limited catalyst or adsorbent loading. Also, the surface adhesion of the coating may be limited, with the risk of leaching of valuable materials. This makes such products less useful and efficient.

[0007] Another method for producing porous adsorbent structures or monolithic catalyst structures is to form layers from a suspension or paste, for example by stacking multiple layers. There are various methods for making products in layered form, one of which is additive manufacturing or 3D printing.

[0008] 3D printing has become an interesting technology in many applications because it allows for the production of unique designs and products that cannot be produced by other methods. 3D printed structures can be used in numerous applications, such as filtration, separation, catalysis, construction, etc. Various 3D printing methods are currently known, allowing for the creation of 3D printed products with a wide range of possible compositions and properties. The designs of 3D printed structures can also vary greatly in recent years.

[0009] Certain 3D printing techniques, which produce 3D printed articles in layered form from build materials, often pastes or (viscous) suspensions, involve layer-upon-layer (micro)extrusion of the pastes or suspensions in the form of filaments, fibers, or strands. These techniques are known as robocasting, microextrusion, or direct ink writing (DIW). Typical build materials used in these techniques include an active compound, a binder material, and a solvent.

[0010] 3D printing of inorganic materials has been achieved through the use of build materials that are combinations of (typically inorganic) active compounds and one or more organic and / or inorganic binders to ensure the required mechanical strength of the 3D-printed structure. Examples of inorganic active compounds include ceramic materials, inorganic oxides, and mineral materials, such as various types of clay, zeolites, silica, or alumina. However, such 3D-printed inorganic structures are often too brittle. Furthermore, they typically require multiple post-processing steps, including heat treatment (calcination) and / or sintering of the 3D-printed structure. Because heat treatment causes decomposition of the organic binder, carbon residues from such decomposition can remain in the structure and blockages of the porous structure or deactivate the active compound. Furthermore, heat treatment is often time- and / or energy-consuming.

[0011] Another promising option is the incorporation of inorganic materials into organic matrices to develop hybrid composites.

[0012] "Robocasting of porous alumina hollow fiber monoliths by non-solvent induced phase inversion," Michielsen, B., Mertens, M., et al., Open Ceramics 6, (2021), discloses the development of 3D-printed porous hollow alumina (Al2O3) filaments. The 3D structures are constructed by extrusion (robocasting) of a paste containing porous Al2O3 and Amperit powders, polyetherimide as a polymer binder, and N-methyl-2-pyrrolidone as a solvent in a humid atmosphere. The humid atmosphere induces phase inversion, providing sufficient strength for the extruded hollow fiber to be self-supporting. The extruded filament, in the shape of the 3D structure, is then immersed in a non-solvent to complete the phase inversion and thereby fully solidify the filament. The solidified green body is then dried, calcined, and sintered to obtain the alumina hollow fiber structure. Calcination removes the polymer binder and organic additives, and sintering is used to obtain the final properties of the porous Al2O3 fiber.

[0013] WO 2009 / 027525 discloses a method for producing three-dimensional microporous filamentary structures. The structures are obtained by 3D printing a suspension containing particles of an inorganic material (especially titanium), a solvent, and one or more (organic) binders onto a filament-based green body and solidifying the filaments by phase inversion with a non-solvent. The solidified green body is then dried, calcined, and sintered. Calcination in an inert atmosphere pyrolyzes the organic material, resulting in carbon-containing pyrolysis products. These carbon-containing products may be adsorbed in the porous structure, reducing the accessibility or blocking of active sites in the structure. Furthermore, sintering shrinks the pores of the solidified green body, i.e., sintering increases the density of the solidified green body, thereby reducing the specific surface area of ​​the final three-dimensional porous structure. Furthermore, sintering may result in the loss of functional groups, which may cause embrittlement of the inorganic material, especially titanium.

[0014] "Development of 3D-printed polymer-zeolite composite monoliths for gas separation," Thakkar, H., Lawson, S., et al., Chemical Engineering Journal, 348, pp. 109-116 (2018), discloses the development of a 3D porous adsorbent structure containing approximately 30% by weight of zeolite 13X or zeolite 5A embedded in approximately 40% by weight of Torlon (a polyamide-imide polymer) binder, and further containing additives for CO2 removal from fuel gases. Such monoliths are obtained by extrusion of a paste containing Torlon, zeolite, a polymer binder (polyvinylpyrrolidone), and N-methyl-2-pyrrolidone (NMP), with water as the solvent. After extrusion of a single layer of the structure, DI water was dripped onto the last extruded layer to induce phase inversion of that layer. This provides freestanding properties to the partially finished structure (and the final structure).

[0015] One of the drawbacks of the aforementioned method is the requirement of a humid environment during extrusion or repeated extrusion-phase inversion cycles to ensure that the porous structure (i.e., the green body) remains self-supporting during extrusion. In other words, complex and expensive measures are required to avoid collapse or deformation of the 3D monolith during the building process. This makes the method time-consuming, complicated, and expensive.

[0016] A further drawback of the aforementioned method is that the resulting three-dimensional porous adsorbent structure exhibits a significantly reduced specific surface area of ​​the active material (e.g., zeolite material) compared to the initial surface area of ​​the active material prior to incorporation of the active material in the build material or paste composition. In other words, the accessibility of the active material in the three-dimensional porous structure is greatly reduced. Another drawback is that the pore volume is significantly reduced when compared to the initial pore volume of the active material prior to incorporation of the active material in the build material or paste composition. Furthermore, the amount of active material incorporated into the three-dimensional porous adsorbent structure is low, resulting in an adsorbent structure with low adsorbent capacity.

[0017] "Chemically active, porous 3D-printed thermoplastic composites," Evans KA, Kennedy ZC, et al., ACS Applied Materials & Interfaces, 10, pp. 15112-15121 (2018), describes the fabrication of three-dimensional metal-organic framework (MOF)-thermoplastic polymer composites with complex internal structural features using a standard 3D printer. Polylactic acid (PLA) pellets as the thermoplastic polymer are dissolved in trichloromethane. The zeolite-imidazolate framework ZIF-8 as the MOF is dispersed in ethyl acetate, and the PLA solution is subsequently added to the ZIF-8 dispersion. The resulting mixture is then formed into a thin film by casting, heating, and drying, thereby removing most of the solvent. The thin film is then formed into a filament by extrusion. The filament is then printed by 3D printing.

[0018] U.S. Patent Application Publication No. 2022 / 0250029 discloses a method for producing 3D-printed zeolite monoliths containing zeolite material and a binder. The monoliths are produced by mixing the zeolite and binder and adding distilled water to obtain a paste. The paste is extruded in a Robocast 3D printer, subsequently dried at room temperature to partially remove the water, and then heated in an oven to remove the remaining water, which can increase strength and prevent skin cracking. Subsequent sintering can be performed to decompose and remove the binder and increase the mechanical strength of the monolith. [Prior art documents] [Patent documents]

[0019] [Patent Document 1] International Publication No. 2009 / 027525 [Patent Document 2] US Patent Application Publication No. 2022 / 0250029 [Non-patent literature]

[0020] [Non-Patent Document 1] “Robocasting of porous alumina hollow fiber monoliths by non-solvent induced phase inversion”, Michielsen, B., Mertens, M., et al., Open Ceramics 6, (2021) [Non-patent document 2] "Development of 3D-printed polymer-zeolite composite monoliths for gas separation", Thakkar, H., Lawson, S., et al., Chemical Engineering Journal, 348, pp. 109-116 (2018) [Non-patent document 3] "Chemically active, porous 3D-printed thermoplastic composites", Evans KA., Kennedy ZC, et al., ACS Applied Materials & Interfaces, 10, pp. 15112~15121 (2018) Summary of the Invention [Problem to be solved by the invention]

[0021] The present invention aims to overcome one or more of the above-mentioned drawbacks. It is an object of the present invention to provide a three-dimensional (3D) porous adsorbent structure or adsorbent product and a method for producing the 3D porous adsorbent structure or adsorbent product, which has reduced energy consumption, requires a reduced number of process steps to obtain the 3D porous adsorbent structure, and is less time-consuming, less complex, and less expensive. One object is to provide a method that can produce a 3D porous adsorbent structure with high adsorbent accessibility, in which the access to the adsorbent material (pores) in the adsorbent structure is significantly maintained compared to the initial or raw adsorbent material, and therefore the activity of the adsorbent is significantly maintained or preserved. Another object is to provide a method for producing a 3D porous adsorbent structure in which much of the structure of the adsorbent material is preserved. [Means for solving the problem]

[0022] Thus, according to a first aspect of the present invention, there is provided a method of fabricating a 3D porous adsorbent structure, as set out in the appended claims. The method of fabricating a three-dimensional porous adsorbent structure described herein comprises the steps of constructing a 3D porous green body, inducing phase inversion in the 3D porous green body, and drying the porous green body, thereby obtaining a three-dimensional porous adsorbent structure.

[0023] The porous green body is obtained in a layered form from a build material comprising an inorganic porous adsorbent material and an organic binder material. At least a portion of the organic binder material is dissolved in a solvent. In other words, the build material also comprises a solvent. Advantageously, at least 10% by weight, for example, at least 25% by weight, preferably at least 50% by weight, for example, at least 60% by weight, at least 70% by weight, at least 80% by weight, more preferably at least 90% by weight, for example, at least 95% by weight, or 100% by weight, of the organic binder material is dissolved in the solvent, based on the total weight of the organic binder material.

[0024] The term "build material" is used in this disclosure to refer to a composition used to fabricate or produce a three-dimensional porous adsorbent structure. In particular, the build material of the present disclosure is constructed into a 3D porous green body, which is then converted into a 3D porous adsorbent structure. Synonyms for "build material" as used in this disclosure include "building material" and "3D printing composition," and when the porous green body is obtained by a 3D printing method, "3D printing composition" is used.

[0025] The porous green body is obtained in layered form by depositing the build material in multiple layers, advantageously with at least some of the filaments in at least one of the multiple layers spaced apart from one another, e.g., deposited apart from one another.

[0026] Accordingly, the present invention provides a method for producing a three-dimensional porous adsorbent structure, comprising the steps of: Constructing a three-dimensional (3D) porous green body from a build material comprising an inorganic porous adsorbent material and an organic binder material, wherein at least a portion of the organic binder material is dissolved in a solvent and the build material is deposited as filaments in a plurality of layers to obtain the three-dimensional porous green body, wherein at least a portion of the filaments in at least one of the plurality of layers are spaced apart from one another; inducing phase inversion of the three-dimensional porous green body by exposing the three-dimensional porous green body to a non-solvent for the organic binder material, thereby obtaining a solidified three-dimensional porous green body; drying the solidified three-dimensional porous green body, thereby obtaining a three-dimensional porous adsorbent structure; Including, The build material comprises between 30% and 70% by weight of an inorganic porous adsorbent material and between 5% and 30% by weight of an organic binder material, based on the total weight of the build material, wherein the organic binder material is at least partially retained in a three-dimensional porous adsorbent structure, and the three-dimensional porous adsorbent structure has an adsorbent accessibility of at least 40%, wherein the adsorbent accessibility satisfies the following formula (I):

[0027]

number

[0028] (In the formula, S BET,構造体 is the BET surface area of ​​the three-dimensional porous adsorbent structure, S BET,吸着剤 is the BET surface area of ​​the initial inorganic porous adsorbent material, X is the mass percent of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure; The BET surface area of ​​the initial inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure are determined from the argon adsorption isotherm at 87 K. The method is related to the calculation according to

[0029] Advantageously, the three-dimensional green body is constructed by 3D printing technology. In other words, the 3D porous adsorbent structure is advantageously a porous 3D-printed adsorbent structure. The 3D porous green body can be obtained by any 3D printing technology that allows obtaining a 3D porous structure in a layered form. Examples of suitable 3D printing technologies include microextrusion of a build material, such as a viscous paste or solution (also known as robocasting or direct ink writing (DIW)), filament melt fabrication (FFF; also known as extrusion of molten polymer material through a nozzle or orifice), and binder jetting.

[0030] Advantageously, the inorganic porous adsorbent material comprises one or more of zeolitic adsorbent materials, metal-organic framework (MOF) adsorbent materials, metal oxides, carbon-based materials, clays, molecular sieves, resins, and MXenes (i.e., layers of transition metal carbides, nitrides, or carbonitrides that are a few atoms thick). The term "layers a few atoms thick" is used in the present disclosure for layers having a thickness of between 1 and 20 atoms, preferably between 1 and 10 atoms.

[0031] The inorganic porous adsorbent material can further comprise a catalytically active material. Advantageously, the catalytically active material is active at temperatures to which the porous green bodies and three-dimensional porous adsorbent structures are exposed during manufacture and use. Advantageously, the catalytically active material is active at temperatures below the maximum continuous use temperature of the organic binder material, preferably below 180°C, as determined by the Underwriters Laboratories (UL746B) Relative Temperature Index (RTI).

[0032] The catalytically active material is advantageously applied to the surface of the inorganic porous adsorbent material. Advantageously, the catalytically active material is immobilized, e.g., adsorbed, on the surface of the inorganic porous adsorbent material. The catalytically active material may be applied to the surface of the inorganic porous adsorbent material before the inorganic porous adsorbent material is added to the build paste. Alternatively, or additionally, the catalytically active material may be applied to the surface of the inorganic porous adsorbent material after the 3D porous adsorbent structure has been obtained.

[0033] Advantageously, the catalytically active material comprises or consists essentially of one or more of an enzyme and a microorganism, such as yeast or bacteria. In other words, the catalytically active material is advantageously a biological catalytically active material, i.e., for use in biocatalysis. Non-limiting examples of enzymes include amylases, such as starch, glucose, fructose, and dextrose, lipases, ketoreductases, halogenases, methyltransferases, and aldolases.

[0034] The build material comprises at least 30% by weight of inorganic porous adsorbent material, preferably between 30% and 70% by weight, for example between 40% and 60% by weight, more preferably between 45% and 55% by weight, based on the total weight of the build material.

[0035] The organic binder material advantageously comprises or consists essentially of a phase inversion polymer. Advantageously, the organic binder (phase inversion polymer) material advantageously comprises one or more of polysulfone, polyethersulfone, cellulose acetate, polyvinylidene fluoride, polyacrylonitrile, polyethylene-co-vinyl alcohol, polycarbonate, polyimide, polyetherimide, polyamide, or polyamide-imide.

[0036] The build material comprises up to 30% by weight of organic binder material, preferably between 5% and 30% by weight, for example between 5% and 20% by weight, more preferably between 10% and 15% by weight, based on the total weight of the build material.

[0037] The solvent advantageously comprises a polar aprotic solvent. Advantageously, at least a portion of the organic binder material is dissolved in the solvent. Advantageously, the phase inversion polymer is dissolved in the solvent in the build material. Advantageously, the solvent comprises or essentially consists of N-methyl-pyrrolidone (NMP), acetone, dimethyl-acetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), dioxane, acetic acid, formylpiperidine, morpholine, s-caprolactam, gamma-butyrolactone, methyl ethyl ketone, chloroform, or a combination of two or more thereof. Advantageously, the build material comprises between 5% and 65% by weight, preferably between 20% and 55% by weight, of the solvent, based on the total weight of the build material.

[0038] Phase inversion of the 3D porous green body is induced by exposing the 3D porous green body to a non-solvent for the organic binder material, thereby inducing a demixing process of the solution into binder-rich and binder-poor phases. Further separation occurs, decreasing the solubility of the binder in the solvent and forming a solid phase with a unique morphology, thereby obtaining a solidified 3D porous green body.

[0039] Advantageously, the non-solvent comprises or consists essentially of a polar protic solvent, such as water, an alcohol, an acid, or a combination thereof.

[0040] Advantageously, phase inversion is induced by exposing the three-dimensional porous green body to a non-solvent for the phase inversion polymer.

[0041] Advantageously, phase inversion is induced by immersing the three-dimensional porous green body in a non-solvent and / or by spraying the non-solvent onto the three-dimensional porous green body.

[0042] Advantageously, the solidified three-dimensional porous green body obtained after phase inversion of the three-dimensional porous green body is dried at a temperature below the maximum continuous use temperature of the organic binder material. As used herein, the term "maximum continuous use temperature" refers to the highest allowable temperature above which the mechanical or electrical properties of a part made from a material (here, the organic binder material) significantly degrade over the reasonable lifetime of the product (here, the 3D porous adsorbent structure). The maximum continuous use temperature can be determined by the Underwriters Laboratories (UL746B) Relative Temperature Index (RTI).

[0043] Advantageously, the solidified three-dimensional porous green body obtained after phase inversion of the three-dimensional porous green body is dried at a temperature between 20°C and 180°C, preferably between 20°C and 150°C, for example between 20°C and 130°C.

[0044] Advantageously, the three-dimensional porous green bodies and the three-dimensional porous adsorbent structure are not exposed to temperatures exceeding the maximum continuous use temperature of the organic binder material, which maximum continuous use temperature being as previously described herein. Advantageously, any heat treatment to which the three-dimensional porous green bodies and the three-dimensional porous adsorbent structure are subjected is carried out at a maximum temperature of 180°C. Consequently, and advantageously, the three-dimensional porous adsorbent structure is not subjected to either calcination or sintering operations, as these are typically carried out at temperatures above at least 200°C, and more often above 300°C.

[0045] After drying, the resulting three-dimensional porous adsorbent structure contains at least a portion of the organic binder material contained in the build material, in other words, the organic binder material is at least partially retained in the three-dimensional porous adsorbent structure.

[0046] The 3D porous adsorbent structure obtained by the method of the present disclosure has an adsorbent accessibility of at least 40%, for example at least 50%, or at least 60%. The adsorbent accessibility is advantageously determined by the following formula (I):

[0047]

number

[0048] (In the formula, S BET,構造体 is the BET surface area of ​​the three-dimensional porous adsorbent structure, S BET,吸着剤 is the BET surface area of ​​the original (or raw) inorganic porous adsorbent material; X is the mass percent of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure; The BET surface area is determined from the argon adsorption isotherm at 87 K of the initial inorganic porous adsorbent material and the argon adsorption isotherm at 87 K of the three-dimensional porous adsorbent structure. is calculated according to

[0049] "Initial porous adsorbent material" in the context of the present invention means an inorganic porous adsorbent material prior to its incorporation in a build material, i.e., raw porous adsorbent material.

[0050] According to a second aspect of the present invention there is provided a three-dimensional porous adsorbent structure as set out in the accompanying claims. Advantageously, the structure is obtainable by the method of the first aspect.

[0051] The three-dimensional porous adsorbent structures described herein include filaments in multiple layers, with at least some of the filaments within the same layer being spaced apart from one another.

[0052] The three-dimensional porous adsorbent structure described herein comprises at least 50% by weight, preferably between 70% and 98% by weight, more preferably between 80% and 95% by weight, of inorganic porous adsorbent material, based on the total weight of the three-dimensional porous adsorbent structure. Advantageously, the inorganic porous adsorbent material is as described above.

[0053] The three-dimensional porous adsorbent structure described herein comprises up to 50% by weight of an organic binder material, preferably between 2% and 30% by weight, more preferably between 5% and 20% by weight, based on the total weight of the three-dimensional porous adsorbent structure. Advantageously, the organic binder material is as described above. In particular, the organic binder material advantageously comprises or consists essentially of a phase inversion polymer.

[0054] Advantageously, the three-dimensional porous adsorbent structure has an adsorbent accessibility of at least 40%, such as at least 50%, or at least 60%. Advantageously, the adsorbent accessibility is calculated according to formula (I) previously described herein.

[0055] Advantageously, the three-dimensional porous adsorbent structure has a micropore volume that is at least 30% of the micropore volume of the initial (or raw) inorganic porous adsorbent material, where "micropore volume" refers to the total volume of micropores in the structure. The micropore volume is advantageously preferably determined by t-plot method using an argon adsorption isotherm at 87 K of the initial inorganic porous adsorbent material and an argon adsorption isotherm at 87 K of the three-dimensional porous adsorbent structure.

[0056] A further aspect of the present invention relates to the use of the 3D porous adsorbent structure of the second aspect for gas adsorption applications and / or liquid adsorption applications. Advantageously, gas adsorption and liquid adsorption involve the separation of one or more compounds or components from a gas or liquid stream, respectively, and / or the purification of a gas or liquid stream, respectively. Advantageously, adsorption, advantageously gas adsorption, is carried out for the separation of compounds or components from a gas or liquid stream, respectively, such as CO2, HO, volatile organic compounds (VOCs), sulfur oxides (SO4), and the like. x ), and nitrogen oxides (NO x ) adsorption of one or more of the following.

[0057] Advantageously, the three-dimensional porous adsorbent structure, during its use, is not exposed to temperatures that exceed the maximum continuous use temperature of the organic binder material as determined by the Underwriters Laboratories (UL746B) Relative Thermal Index (RTI). Advantageously, the three-dimensional porous adsorbent structure, during its use, is not exposed to temperatures that exceed 180°C.

[0058] Advantages of the method of the present invention include the ability to fabricate mechanically strong 3D porous adsorbent structures that contain or maintain the high accessibility of the adsorbent material provided in the adsorbent structure. Furthermore, the method allows the micropore volume of the original inorganic porous adsorbent material to be maintained to a large extent, i.e., the method does not significantly fill or cover the (micro)pores of the inorganic adsorbent material.

[0059] Furthermore, the method of the present invention is suitable for producing 3D porous adsorbent materials and structures with low temperature stability or structures that are sensitive to oxidation or thermal decomposition.

[0060] Aspects of the present invention will now be described in more detail with reference to the accompanying drawings, in which like reference numerals refer to like features. [Brief explanation of the drawings]

[0061] [Figure 1] 1 is a graph showing argon adsorption isotherms at 87 K for three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 2]1 is a graph showing the pore size distribution of three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 3A] FIG. 1 shows a scanning electron microscope (SEM) image of the surface of a first 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 3B] FIG. 1 shows a scanning electron microscope (SEM) image of a cross section of a first 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 4A] FIG. 1 shows a scanning electron microscope (SEM) image of the surface of a second 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 4B] FIG. 1 shows a scanning electron microscope (SEM) image of a cross section of a second 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 5A] FIG. 1 shows a scanning electron microscope (SEM) image of the surface of a third 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 5B] FIG. 1 shows a scanning electron microscope (SEM) image of a cross section of a third 3D porous adsorbent structure obtained by the method of the present invention, measured on a single extruded fiber. [Figure 6] 1 is a graph showing the pore size distribution of mesopores and macropores of three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 7] 1 is a graph showing the cumulative pore volume of mesopores and macropores of three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 8] 1 is a graph showing CO2 adsorption capacity as a function of pressure for a reference 3D porous adsorbent structure. [Figure 9] 1 is a graph showing CO2 adsorption capacity as a function of pressure for a first 3D porous adsorbent structure obtained by the method of the present invention. [Figure 10]1 is a graph showing CO2 adsorption capacity as a function of pressure for a second 3D porous adsorbent structure obtained by the method of the present invention. [Figure 11] 10 is a graph showing CO2 adsorption capacity as a function of pressure for a third 3D porous adsorbent structure obtained by the method of the present invention. [Figure 12] 1 is a graph showing water adsorption capacity as a function of pressure for a reference 3D porous adsorbent structure. [Figure 13] 1 is a graph showing water adsorption capacity as a function of pressure for a first 3D porous adsorbent structure obtained by the method of the present invention. [Figure 14] 1 is a graph showing water adsorption capacity as a function of pressure for a second 3D porous adsorbent structure obtained by the method of the present invention. [Figure 15] 10 is a graph showing water adsorption capacity as a function of pressure for a third 3D porous adsorbent structure obtained by the method of the present invention. [Figure 16] 1 is a graph showing the water absorption amount for humidity steps from 5% RH to 10% RH as a function of time for a reference 3D porous adsorbent structure and three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 17] 1 is a graph showing the water absorption amount for humidity steps from 5% RH to 10% RH as a function of time for a reference 3D porous adsorbent structure and three 3D porous adsorbent structures obtained by the method of the present invention. [Figure 18] 1 is a graph showing CO2 breakthrough curves at 10% partial pressure at relative times up to 1250 seconds for a reference 3D porous adsorbent structure and three 3D porous adsorbent structures obtained by the method of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0062] In the first step of the method according to the present disclosure, a 3D porous green body is constructed in a layered form from a build material. The build material refers to a viscous paste, emulsion, or solution. The build material comprises an inorganic porous adsorbent material and an organic binder material at least partially, preferably completely, dissolved in a solvent. In other words, the build material comprises a solvent, an inorganic porous adsorbent material, and an organic binder material.

[0063] Advantageously, the method does not include the step of removing at least a portion of the solvent from the build material prior to constructing the 3D porous green body.

[0064] Porous green bodies can be obtained by any additive manufacturing technique that allows obtaining a porous structure. A particularly suitable technique is (micro)extrusion, which comprises extruding a build material in the form of filaments or strands through a nozzle or orifice. Advantageously, the nozzle or orifice has a diameter between 20 μm and 5 mm, preferably between 30 μm and 4 mm, more preferably between 50 μm and 3 mm, for example between 100 μm and 2 mm. Advantageously, the strands or filaments are deposited in layers on a printing surface, resulting in a green body built up as multiple laminates. Either the nozzle or the printing surface is arranged on a positioning table, for example an XY table, for extruding the filaments or strands in a predetermined pattern. Advantageously, the strands or filaments within one layer are deposited apart from each other, thereby forming (macro)pores between the strands or filaments. Advantageously, the strands or filaments are deposited such that the filaments or strands of adjacent layers cross each other or are at least partially located on top of each other. Thus, the filaments or strands of adjacent layers are in contact, resulting in interlocking between adjacent / consecutive layers. Advantageously, the porous green body is constructed by depositing the build material as filaments or strands to construct a three-dimensional structure, for example by (micro)extrusion. Immediately after deposition, the organic binder in the filaments or strands is advantageously (at least partially) dissolved in a solvent. As further described below, the solvent is removed in a subsequent step by phase inversion.

[0065] Advantageously, the filaments or strands have a diameter between 20 μm and 5 mm, preferably between 30 μm and 4 mm, more preferably between 50 μm and 3 mm, for example between 100 μm and 2 mm.

[0066] The (macro)porosity of the porous green body can be varied depending on the final application or use of the porous (3D printed) structure. Porosity can be varied by adjusting the parameters of the 3D printing process, which methods are known in the art. Advantageously, the pores between adjacent filaments or strands have an average size between 1 μm and 5 mm, preferably between 20 μm and 4 mm, more preferably between 50 μm and 3 mm, for example between 100 μm and 2 mm.

[0067] The porous green bodies, and the 3D porous adsorbent structures obtained by the methods of the present disclosure, can have a variety of geometries. The green bodies are advantageously monolithic. The green bodies may be monolithic having a cubic or cylindrical shape.

[0068] Advantageously, the (initial or raw) inorganic porous adsorbent material, i.e., the inorganic porous adsorbent material itself, is subjected to at least 20 minutes of heating before it is applied to the build material. 2 / g, preferably at least 25m 2 / g, more preferably at least 50m 2 / g, e.g., at least 75m 2 / g, or at least 100m 2 / g, the BET surface area being advantageously determined from the nitrogen adsorption isotherm at 77K or from the argon adsorption isotherm at 87K.

[0069] Advantageously, the inorganic porous adsorbent material is a particulate material, for example a powder. Advantageously, the inorganic porous adsorbent material particles have a diameter between 1 / 5 and 1 / 20 of the diameter of the filament or strand, preferably between 1 / 7 and 1 / 15, for example substantially 1 / 10 of the filament diameter. 50 It has a particle size distribution with a value.

[0070] Non-limiting examples of metal oxides suitable for inorganic porous adsorbent materials include silica, titania, alumina, and zirconia. Non-limiting examples of carbon-based materials include activated carbon, carbon molecular sieves, and carbon nanotubes (CNTs). Non-limiting examples of clays include natural clay minerals and synthetic clays, such as bentonite clay, attapulgite, fuller's earth, kaolin clay, laponite, and wollastonite. Non-limiting examples of molecular sieves include aluminosilicates and titanosilicates. MXenes contain layers of transition metal carbides, nitrides, or carbonitrides several atoms thick. Preferred inorganic porous adsorbent materials include zeolites and metal-organic frameworks. One suitable zeolite is 13X.

[0071] Optionally, the inorganic porous adsorbent material may be functionalized, including silanization, treatment with phosphonic acid, impregnation, or grafting of functional groups onto at least a portion of the surface of the inorganic porous adsorbent material. Advantageously, functionalization provides the inorganic porous adsorbent material with an increased ability to interact with the environment.

[0072] Advantageously, the disclosed method makes it possible to obtain 3D porous adsorbent structures comprising functionalized inorganic porous adsorbent materials. An advantage of the present invention, as explained above and below, is that the temperatures to which the porous green bodies and porous adsorbent structures are exposed remain relatively low, preferably below 180° C. This allows the functionality of the functional groups to be maintained, as these are often temperature sensitive and tend to decompose when exposed to high temperatures.

[0073] The inorganic porous adsorbent material can be dried before adding it to the build material. This reduces the risk of phase inversion starting during the process of constructing the 3D porous green body or before using it, even during the process of storing the adsorbent material before adding it to the build material. This also allows for improved control of pore formation (amount, size).

[0074] Advantageously, the build material comprises at least 30% by weight, preferably between 30% and 70% by weight, such as between 40% and 60% by weight, more preferably between 45% and 55% by weight, such as between 45% and 50% by weight, of inorganic porous adsorbent material relative to the total weight of the build material.

[0075] Advantageously, the build material comprises up to 30% by weight of organic binder material, preferably between 5% and 30% by weight, for example between 5% and 25% by weight, between 5% and 20% by weight, between 5% and 15% by weight, more preferably between 10% and 15% by weight, relative to the total weight of the build material.

[0076] The build material may further include one or more additives. The additives may be selected to act as, but are not limited to, plasticizers, dispersants, and / or pore formers. Examples of such additives are calcium carbonate, 1,4-dioxane, and diethylene glycol dimethyl ether.

[0077] Advantageously, the build material comprises at least 35% by weight, preferably more than 40% by weight, for example more than 45% by weight, more preferably more than 50% by weight, and most preferably more than 55% by weight, of solids, based on the total weight of the build material. The solids include inorganic porous adsorbent materials, organic binder materials, and further optional compounds such as plasticizers and dispersants.

[0078] The solvent advantageously comprises a polar aprotic solvent. Advantageously, at least a portion of the organic binder material is dissolved in the solvent. The solvent may be a non-volatile liquid, a volatile liquid, or a mixture thereof. Preferred solvents include NMP (a non-volatile solvent) and acetone (a volatile solvent).

[0079] Advantageously, the build material comprises at least 5% by weight, preferably at least 10% by weight, such as at least 20% by weight, at least 30% by weight, more preferably at least 35% by weight of solvent, based on the total weight of the build material.

[0080] Advantageously, the build material comprises between 5% and 65% by weight of solvent, preferably between 20% and 55% by weight, for example between 30% and 50% by weight, more preferably between 35% and 45% by weight, relative to the total weight of the build material.

[0081] Advantageously, the amount of solvent is selected based on the type and amount of adsorbent material and binder material to obtain a build material with the viscosity required for the method or technique used to build the 3D porous green body. Depending on the technique or method used to build the 3D porous green body, the optimal viscosity will vary. For example, when an extrusion-based 3D printing technique is applied, the build material is advantageously heated at a shear rate of about 0.01 s -1 and at a temperature of 25°C, 10 Pa.sec to 10 6 mPa.sec, preferably 10 2 mPa.sec ~ 10 6 It has a printing viscosity (so-called printable (shear-thinning) viscosity) of between 1000 and 10000 mPa.sec.

[0082] The build material can be prepared according to any one of a variety of routes and can be used in the methods of the present disclosure. In some instances, an inorganic porous adsorbent material and an organic binder material are mixed together in a solvent, thereby obtaining the build material.

[0083] Alternatively, two or more separate solutions are prepared, each containing at least one different component of the build material. These separate solutions are then mixed to obtain the build material. As an example, a first solution and a second solution are prepared. The first solution can be prepared by mixing an inorganic porous adsorbent material in (a portion of) a solvent, preferably without adding an organic binder material. The second solution can be prepared by mixing an organic binder material in (a portion of) a solvent, preferably without adding an inorganic porous adsorbent material, thereby at least partially dissolving the organic binder material in the solvent. The first solution and the second solution are then mixed to obtain the modulator.

[0084] Advantageously, build materials having the compositions described hereinabove provide porous green bodies with sufficient mechanical strength during the deposition of filaments of the build material in multiple stacked layers to obtain the porous green body. The inventors believe that this mechanical strength is due to the organic binder material. As a result, stabilization does not need to be performed during the construction of the porous green body, such as during water spraying or during construction in a humid environment, to initiate (i.e., induce) phase inversion during construction. The inventors have found that even small amounts of organic binder material, for example, as little as 5% by weight or up to 10% by weight relative to the weight of the build material, can provide sufficient mechanical strength during construction. Such small amounts also have the advantage of providing high accessibility to the inorganic adsorbent material in the resulting 3D porous adsorbent structure and significantly preserving the (micro)porosity of the inorganic adsorbent material. Furthermore, the resulting 3D porous structure is also sufficiently mechanically strong for its intended use.

[0085] Optionally, the 3D porous green body can be exposed to a non-solvent during construction of the 3D porous green body. This can be achieved by spraying or spraying water or another non-solvent onto one or more layers of the green body as the filaments form a particular deposited layer. Alternatively, the construction process can be carried out in a humid atmosphere, i.e., an atmosphere having a relative humidity of at least 50% RH, preferably at least 75% RH, more preferably at least 80% RH, or at least 90% RH.

[0086] In the second step of the disclosed method, the porous green body is subjected to phase inversion. During phase inversion, the porous green body is exposed to a non-solvent for the organic binder material. Advantageously, the solvent contained in the porous green body is compatible or soluble in the non-solvent.

[0087] Upon exposure to a non-solvent, the binder solution demixes into a binder (polymer)-rich phase and a binder (polymer)-poor phase. Upon further separation, the solubility of the binder (polymer) is reduced and a solid phase with a unique morphology is formed. This leads to the solidification of the porous green body.

[0088] Advantageously, the structure of the porous green body is not significantly altered during phase inversion. In other words, the structure of the plurality of laminations, where the laminations are constructed from filaments and where at least some of the filaments in at least one of the plurality of laminations are spaced apart from one another, is substantially maintained during phase inversion. In other words, the solidified porous green body advantageously comprises filaments in the plurality of laminations and where at least some of the filaments in at least one of the plurality of laminations are spaced apart from one another.

[0089] Phase inversion also results in the formation of pores, particularly micropores, in the solidified porous green body. According to the IUPAC definition, micropores are pores with a diameter of less than 2 nm. Porosity is highly dependent on the type of solvent / non-solvent system, which affects the kinetics of the demixing process. For example, immediate demixing, which occurs very quickly after immersion, typically results in a relatively porous matrix. For example, delayed demixing typically results in reduced porosity and more spongy pores. In other words, the degree of porosity can be controlled by selecting the solvent and non-solvent.

[0090] Advantageously, the non-solvent comprises or consists essentially of a polar protic solvent. Advantageously, the non-solvent is a liquid or vapor. Non-limiting examples of liquid non-solvents include water, alcohols (e.g., methanol, ethanol, n-propanol, or isopropanol), acids (e.g., acetic acid), or combinations of two or more thereof. Preferably, the non-solvent comprises or consists essentially of water, e.g., demineralized water.

[0091] Phase inversion can be induced by techniques known in the art, non-limiting examples of which include one or more of immersing the 3D porous green body in a non-solvent, spraying, spraying, or misting a non-solvent onto the 3D porous green body, or exposing the 3D porous green body to an atmosphere comprising or consisting essentially of a non-solvent.

[0092] In the third step of the disclosed method, the solidified porous green body is dried, which allows residual solvent and / or non-solvent to be removed from the solidified porous green body, thereby obtaining a three-dimensional porous adsorbent structure.

[0093] Advantageously, the structure of the solidified porous green body is not significantly altered during the drying process. In other words, the structure of the plurality of layers, where the layers are constructed from filaments and where at least a portion of the filaments in at least one of the plurality of layers are spaced apart from one another, is substantially maintained during the drying process. In other words, the three-dimensional porous adsorbent structure advantageously comprises filaments in a plurality of layers, where at least a portion of the filaments in at least one of the plurality of layers are spaced apart from one another.

[0094] When the organic binder material comprises a polymer, the drying step is advantageously carried out at a temperature below the melting point or glass transition temperature of the organic binder material. By drying at such temperatures, damage to and / or any removal of the organic binder material can be avoided. As a result, advantageously, the three-dimensional porous adsorbent structure obtained after the drying step comprises at least a portion of the organic binder material. Furthermore, by avoiding damage to or removal of at least a portion of the organic binder material, the mechanical strength of the 3D porous adsorbent structure can be maintained.

[0095] Furthermore, because the organic binder material does not melt, it does not flow into the pores of the 3D porous adsorbent structure and / or the pores of the inorganic adsorbent material itself, thereby maintaining accessibility to and porosity of the inorganic porous adsorbent material.

[0096] The drying temperature is advantageously selected based on the organic binder material. Advantageously, the drying step is carried out at a temperature below the maximum continuous use temperature of the organic binder material, for example at least 5°C lower, at least 10°C lower, at least 20°C lower, or at least 30°C lower than the maximum continuous use temperature, for example at a temperature between 5°C and 50°C lower than the maximum continuous use temperature. The maximum continuous use temperature is as described above. Advantageously, the drying step is carried out at a temperature between 20°C and 180°C, preferably between 20°C and 150°C, for example between 20°C and 130°C, for example between 20°C and 100°C, between 20°C and 75°C, for example at room temperature. For example, polysulfone has a maximum continuous use temperature of 180°C, and the drying step is advantageously carried out at a temperature between 20°C and 150°C. For example, polyvinylidene fluoride has a maximum continuous use temperature of 150°C, and the drying step is advantageously carried out at a temperature between 20°C and 130°C.

[0097] Advantageously, the three-dimensional porous green body and the three-dimensional porous adsorbent structure are not exposed to temperatures exceeding the maximum continuous use temperature of the organic binder material. Advantageously, the three-dimensional porous green body and the three-dimensional porous adsorbent structure are not exposed to temperatures exceeding 180°C. As a result, advantageously, at least a portion of the organic binder material is retained in the three-dimensional porous adsorbent structure. Advantageously, the three-dimensional porous adsorbent structure is not subjected to any heat treatment exceeding the maximum continuous use temperature of the organic binder material. Advantageously, the three-dimensional porous adsorbent structure is not subjected to any heat treatment exceeding 180°C. The heat treatment may be either a calcination operation or a sintering operation.

[0098] A second aspect of the present invention is a three-dimensional porous adsorbent structure comprising at least 50% by weight of an inorganic porous adsorbent material and no more than 50% by weight of an organic binder material, based on the total weight of the three-dimensional porous adsorbent structure, wherein the three-dimensional porous adsorbent structure has an adsorbent accessibility of at least 40%, and the adsorbent accessibility satisfies the following formula (I):

[0099]

number

[0100] (In the formula, S BET,構造体 is the BET surface area of ​​the three-dimensional porous adsorbent structure, S BET,吸着剤 is the BET surface area of ​​the initial inorganic porous adsorbent material, X is the mass percent of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure; The BET surface area of ​​the initial inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure are determined from the argon adsorption isotherm at 87 K. The present invention relates to a three-dimensional porous adsorbent structure characterized in that the adsorbent is calculated according to the following formula:

[0101] The three-dimensional porous adsorbent structure of the present invention comprises an inorganic porous adsorbent material and an organic binder material. Advantageously, the inorganic porous adsorbent material and the organic binder material are as previously described herein. Accordingly, the 3D porous adsorbent structure may be considered a hybrid organic / inorganic structure or a hybrid organic / inorganic composite. When the organic binder material comprises a polymer as described above and the inorganic adsorbent material comprises a zeolite, the structure may be considered a hybrid polymer / zeolite structure or a hybrid polymer / zeolite composite. Advantageously, the three-dimensional porous adsorbent structure is obtained by the method of the present invention.

[0102] The 3D porous adsorbent structure advantageously comprises at least 50% by weight, preferably between 60% and 98% by weight, more preferably between 70% and 98% by weight, such as between 75% and 95% by weight, most preferably between 80% and 95% by weight, of inorganic porous adsorbent material relative to the total weight of the three-dimensional porous adsorbent structure.

[0103] The 3D porous adsorbent structure advantageously comprises at least 50% by volume of inorganic porous adsorbent material, preferably between 60% and 98% by volume, more preferably between 70% and 98% by volume, such as between 70% and 95% by volume, most preferably between 75% and 95% by volume.

[0104] The 3D porous adsorbent structure advantageously comprises up to 50% by weight of organic binder material, preferably between 2% and 40% by weight, more preferably between 2% and 30% by weight, such as between 5% and 25% by weight, most preferably between 5% and 20% by weight, relative to the total weight of the three-dimensional porous adsorbent structure.

[0105] The 3D porous adsorbent structure advantageously comprises up to 50% by volume of organic binder material, preferably between 2% and 40% by volume, more preferably between 2% and 30% by volume, for example between 5% and 30% by volume, most preferably between 5% and 25% by volume.

[0106] Advantageously, the three-dimensional adsorbent structure, and in particular the three-dimensional adsorbent structure obtained by the method of the present invention, has an adsorbent accessibility of at least 40%, for example at least 50%, at least 60%, or at least 70%. The adsorbent accessibility is advantageously represented by the following formula (I):

[0107]

number

[0108] (In the formula, S BET,構造体 is the BET surface area of ​​the three-dimensional porous adsorbent structure, SBET,吸着剤 is the BET surface area of ​​the initial (or raw) inorganic porous adsorbent material, the initial inorganic porous adsorbent material being as defined above; X is the mass percent of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure. is calculated according to

[0109] Advantageously, the BET surface area of ​​the initial (or raw) inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure are preferably determined from argon adsorption isotherms at 87 K. Alternatively, the BET surface area of ​​the initial inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure can be determined from nitrogen adsorption isotherms at 77 K. According to IUPAC, the determination of the BET surface area from an argon adsorption isotherm at 87 K is considered more accurate than that from a nitrogen adsorption isotherm at 77 K, particularly with regard to the detection and measurement of micropores. In the context of the present invention, the BET surface area refers to the specific surface area calculated by the Brunauer-Emmett-Teller (BET) method.

[0110] "X*S" in formula (I) BET,吸着剤 " is the so-called theoretical maximum, which is the BET surface area of ​​the initial inorganic porous adsorbent material multiplied by its mass percentage in the 3D porous adsorbent structure. Consequently, the closer the adsorbent accessibility is to 100%, the closer the BET surface area of ​​the adsorbent structure is to the theoretical maximum, and the less the organic binder influences the surface area (e.g., by filling the pores or forming a layer on the adsorbent material). A high adsorbent accessibility of at least 40% can be considered a criterion for a high-performance adsorbent structure.

[0111] Advantageously, the three-dimensional porous adsorbent structure of the present invention, and in particular the three-dimensional porous adsorbent structure obtainable by the method of the present invention, has a micropore volume that is at least 30% of the micropore volume of the initial (or raw) inorganic porous adsorbent material. Micropore volume herein advantageously refers to the total volume of micropores in the structure. Advantageously, the micropore volume of the initial inorganic porous adsorbent material and the micropore volume of the three-dimensional porous adsorbent structure are preferably determined by t-plot method using argon adsorption isotherms at 87 K. Alternatively, the micropore volume of the initial inorganic porous adsorbent material and the micropore volume of the three-dimensional porous adsorbent structure can be determined by t-plot method using nitrogen adsorption isotherms at 77 K. Because argon has no quadrupole moment and is less reactive than diatomic nitrogen molecules, argon measurements at 87 K are actually recommended by IUPAC over nitrogen measurements at 77 K for the determination of surface area and pore size distribution.

[0112] Examples of suitable applications of the three-dimensional porous adsorbent structures according to embodiments of the present invention include: - purification of gaseous or liquid streams by adsorption of one or more compounds; - separation of certain compounds or components from gaseous or liquid streams by adsorption of compounds of such components; - selective adsorption of metal ions from process (liquid) streams; Biocatalysis to realize certain reactions in liquid streams at relatively low temperatures, for example by immobilizing enzymes or microorganisms by adsorption of such enzymes or microorganisms onto adsorbent structures; is.

[0113] Advantageously, the three-dimensional porous adsorbent structures of the present invention, and in particular the three-dimensional porous adsorbent structures obtainable by the methods of the present invention, are particularly suitable for the adsorption of CO2 from gaseous or liquid streams. Advantageously, they are also particularly suitable for the adsorption of water from gaseous or liquid streams.

[0114] Advantageously, the rate at which a compound is adsorbed is represented by the overall mass transfer coefficient k for the adsorbed compound during its adsorption and / or desorption. Advantageously, the overall mass transfer coefficient is calculated using the linear driving force model (LDF) described by Glueckauf and Coates. [Example]

[0115] Three build materials were prepared, each containing zeolite 13X (Sylosiv A10H, Grace) as the inorganic porous adsorbent material. Three different polymers were used as organic binder materials: polysulfone (PSF, Amoco), polyvinylidene fluoride (PVDF Kynarflex 2801, Arkema), and polyamide-imide (Torlon 4000TF, Solvay).

[0116] A concentrated polymer solution containing 22.9 wt. % PSF, 22.6 wt. % PVDF, and 22.2 wt. % Torlon was prepared by dissolving the polymer in N-methyl-2-pyrrolidone (NMP, Brenntag) by stirring the solution for 15 min using an IKA400 overhead stirrer. The resulting polymer solution was then kept overnight on a roller bench to ensure complete dissolution of the polymer.

[0117] Before adding Zeolite 13X to the polymer solution, the zeolite was dried overnight at 473 K to remove adsorbed water. After drying, a certain mass of heated zeolite powder was mixed with each of the three polymer solutions to achieve build materials containing 80% / 20% zeolite / polymer by weight, respectively. This resulted in build materials with total solids contents of 59.7%, 59.4%, and 58.8% for the Zeolite / PSF, Zeolite / PVDF, and Zeolite / Torlon build materials, respectively.

[0118] A reference build material containing a typical ceramic binder combination was similarly prepared. Zeolite 13X, an inorganic porous adsorbent material, was mixed with a compound containing 50% by weight of bentonite (VWR) and 50% by weight of colloidal silica solution (Ludox AS-40, Grace) based on the total weight of the compound. A build material with a zeolite / binder mass ratio of 80% / 20% by weight was obtained. Methylcellulose (Merck) was then added as a rheology modifier to achieve the required viscosity. This resulted in a reference build material with a solids content of 57%.

[0119] The build materials were each loaded (separately) into a syringe and extruded through a thin nozzle using a mechanically driven piston mounted on a computer numerically controlled (CNC) machine. A constant volume flow was thus ensured, and the porous green body was constructed layer by layer. Two nozzle sizes, ranging from 600 μm to 1200 μm, were used to fabricate rectangular monolithic structures 3 cm high and 3 cm in diameter. The distance between adjacent filaments was kept equal to the filament diameter, while each successive layer was rotated 90°, resulting in straight channels of macropore size throughout the porous green body.

[0120] After printing, the porous green bodies obtained from the build material according to the present invention were immersed in demineralized (DI) water, a non-solvent, for 16 hours to initiate the exchange of NMP (solvent) with DI water (non-solvent) and the precipitation (solidification) of the polymer. The solidified porous green bodies were then dried at room temperature to remove any residue or residual water, resulting in a 3D porous adsorbent structure.

[0121] The green bodies obtained from the reference build material were not subjected to the phase inversion process but were dried at room temperature for 2 days and calcined at 823 K to pyrolyze the organic binder material.

[0122] Characterization of 3D porous adsorbent structures (monoliths) Prior to characterization of the 3D porous adsorbent structures obtained according to the present invention, the 3D porous adsorbent structures were activated (degassed) by heating them under vacuum overnight. Structures containing PSF and polyamide-imide were degassed at 423 K. Structures containing PVDF were degassed at 383 K due to the thermal instability of PVDF at 423 K.

[0123] The porosity of the 3D porous adsorbent structure according to the present invention obtained with a 600 μm nozzle size was evaluated by comparing the specific surface area, total pore volume, and pore size distribution with the respective values ​​of the initial zeolite 13X, i.e., zeolite 13X before the 3D porous adsorbent structure was added to the build material. The results are presented in Table 1.

[0124] For this purpose, the argon isotherm of each sample was measured on the degassed structure on a Quantachrome Autosorb AS-1 at 87 K, and the nitrogen isotherm of each sample was measured on the degassed structure on a Quantachrome Autosorb-iQ-MP (volumetric) at liquid nitrogen temperature (77 K).

[0125] The specific surface area was calculated by the Brunauer-Emmett-Teller (BET) method (the so-called BET surface area, S in Table 1). BET Argon has no quadrupole moment and is less reactive than the diatomic nitrogen molecule, therefore argon measurements at 87 K are actually recommended by IUPAC over nitrogen measurements at 77 K for the determination of surface area and pore size distribution, both results of which are listed in Table 1.

[0126] The argon isotherm and degassing results at 423 K show that the initial zeolite 13X has a BET surface area of ​​787 m 2 / g, while the zeolite / PSF adsorbent structure has a BET surface area of ​​572 m 2 / g, and the zeolite / polyamide-imide (Zeolite / Torlon in Table 1) has a BET surface area of ​​427 m 2 / g, which are 72.7% and 54.3% of the BET surface area of ​​the initial zeolite 13X, respectively. The argon isotherm and degassing results at 383 K show that the initial zeolite 13X has a BET surface area of ​​586 m 2 / g, while the zeolite / PVDF adsorbent structure has a BET surface area of ​​432 m 2 / g, which is 73.7% of the BET surface area of ​​the initial zeolite 13X.

[0127] Figure 1 shows argon adsorption isotherms at 80% of the value (theoretical maximum) for pristine zeolite 1 degassed at 423 K and pristine zeolite 2 degassed at 383 K, pristine zeolite 3 degassed at 423 K, and pristine zeolite 4 degassed at 383 K, as well as zeolite / PSF adsorbent structure 5, zeolite / PVDF adsorbent structure 6, and zeolite / Torlon adsorbent structure 7. The BET surface area values ​​corresponded well to the predicted values ​​for structures containing PSF and PVDF. Indeed, since the zeolite can be considered "diluted" to 80% due to the presence of the organic binder material, the "theoretical maximum" can be considered to be 80% of the value for pristine zeolite 13X. This suggests that PSF and PVDF have sufficient porosity, thereby allowing excellent access to the zeolite. However, a significant decrease in specific surface area was observed for the adsorbent structure containing polyamide-imide (Torlon). Furthermore, the large amount of argon adsorption at the lower pressure range suggests the presence of microporosity, which is characteristic of the microporous nature of zeolite powders.

[0128] The total pore volume of the 3D porous adsorbent structure (V in Table 1) tot ) was calculated by the Barrett-Joyner-Halenda (BJH) method using the argon adsorption isotherm at 87 K.

[0129] The volume of the micropores (V in Table 1) mic) was calculated by the t-plot method using the argon adsorption isotherm at 87 K. The initial zeolite 13X had a micropore volume of 0.291 cm after degassing at 423 K. 3 / g, while the zeolite / PSF adsorbent structure has a micropore volume of 0.207 cm 3 / g, and the zeolite / polyamide-imide (Zeolite / Torlon in Table 1) has a micropore volume of 0.154 cm 3 / g, which are 71.1% and 52.9% of the micropore volume of the initial zeolite 13X, respectively. The initial zeolite 13X, after degassing at 383 K, has a micropore volume of 0.286 cm 3 / g, while the zeolite / PVDF adsorbent structure has a micropore volume of 0.214 cm 3 / g, which is 74.8% of the micropore volume of the initial zeolite 13X.

[0130] The micropore volume values ​​correspond well to those predicted for structures containing PSF and PVDF, suggesting that PSF and PVDF do not appear to fill or block the (micro)pores of zeolite 13X to any significant extent. Indeed, since the zeolite can be considered "diluted" to 80% due to the presence of the organic binder material, the "theoretical maximum" can be considered to be 80% of the initial zeolite 13X value. However, a significant reduction in micropore volume was observed for the adsorbent structures containing polyamide-imide (Torlon).

[0131] [Table 1]

[0132] Pore ​​size distributions were determined by using nonlocal density functional theory (NLDFT) on argon adsorption isotherms at 87 K. Figure 2 shows the results for pristine zeolite 10, degassed at 423 K, and pristine zeolite 11, degassed at 383 K, as well as for zeolite / PSF adsorbent structures 12, zeolite / PVDF adsorbent structures 13, and zeolite / Torlon adsorbent structures 14. Comparing the pore size distributions of the zeolite powders to the porous adsorbent structures, no significant differences were observed for the zeolite / PVDF adsorbent structures, and a small shift to smaller pore sizes was observed for the zerolite / PSF adsorbent structure, suggesting the preservation of much of the zeolite structure.

[0133] This is further confirmed by scanning electron microscope (SEM) images of the surface morphology of both adsorbent structures obtained using a FEGFEI Nova NanoSEM450 at an accelerating voltage of 5 kV. Figure 3A shows the surface of a single filament of the zeolite / PSF adsorbent structure, and Figure 3B shows a cross-section of a single filament of the zeolite / PSF adsorbent structure. Figure 4A shows the surface of a single filament of the zeolite / PVDF adsorbent structure, and Figure 4B shows a cross-section of a single filament of the zeolite / PVDF adsorbent structure. A transparent outer polymer layer, obtained by phase inversion, was present on the surface. The solvent / nonsolvent exchange is believed to have created a porous network on the outside of the fiber, ensuring easy accessibility of the zeolite particles and preventing their diffusion out of the polymer composite.

[0134] In contrast to PVDF and PSF, the addition of Torlon polymer to zeolite powder significantly reduces the total volume adsorbed compared to the theoretical maximum. Furthermore, a hysteresis curve forms, which may be a first indication of typical pore / ink bottle blockage or diffusion of the polyamide-imide polymer into the zeolite pores. This is also observed in a shift from the derived pore size distribution, with a significant increase in the peak intensity at a pore width of 0.75 nm. This is also confirmed by scanning electron microscope (SEM) images of the surface morphology. Figure 5A shows the surface of a single filament of a zeolite / Torlon adsorbent structure, from which multiple portions of the polymer appear to melt together, thereby blocking access to the zeolite. Figure 5B shows a cross-section of a single filament of a zeolite / Torlon adsorbent structure.

[0135] When calculating zeolite accessibility according to equation (I) expressed above, a significant decrease, possibly caused by polymer pore blockage as explained above, is observed for the zeolite / Torlon adsorbent structures. However, in the zeolite / PSF and zeolite / PVDF adsorbent structures, more than 90% of the zeolite material remains accessible.

[0136] The mesoporosity and macroporosity of three porous adsorbent structures of the present invention were measured by mercury intrusion porosimetry using a Thermo Electron Corporation Pascal 140-240 series instrument. Figure 6 shows the pore size distributions (meso- and macro-) for zeolite / PVDF adsorbent structure 20, zeolite / PSF adsorbent structure 21, and zeolite / Torlon adsorbent structure 22. Figure 7 shows the cumulative pore volume for zeolite / PVDF adsorbent structure 30, zeolite / PSF adsorbent structure 31, and zeolite / Torlon adsorbent structure 32. High degrees of mesoporosity and macroporosity were observed. The polymer used as the organic binder material has a significant effect on the pore size distribution and overall porosity of the structure. The highest pore volume was observed in the PVDF composite, with a major pore width of approximately 0.35 μm and a total pore volume of 528 m.3 The PSF and Torlon composites exhibited a unimodal pore distribution with a cumulative volume of 335 m for the PSF and Torlon composites, respectively. 3 / g and 345mm 3 / g. The PSF composite also exhibits a unimodal pore distribution with a predominant pore width of about 0.25 μm, whereas a trimodal pore distribution is observed for the Torlon composite with predominant pore diameters of 0.03 μm, 0.09 μm, and 0.20 μm.

[0137] Adsorption performance The CO2 adsorption performance of the degassed adsorbent structures obtained using a 600 μm nozzle was evaluated based on isotherm measurements performed at 273 K on a Chemstar TPx chemisorption analyzer (Quantachrome Instruments). Helium was used as the carrier gas at a flow rate of 200 mL / min. The same measurements were also performed on pristine zeolite 13X, which was degassed at the same temperature as the compared adsorbent structures. In addition, a ceramic zeolite / clay reference sample was also measured after degassing at 383 K to evaluate the influence of the polymer binder compared to the clay binder. The measured static CO2 adsorption capacities are presented in Table 2.

[0138] From the static adsorption capacities of the zeolite and adsorbent structure, the relative capacity is calculated as the CO2 adsorption capacity of the adsorbent divided by 80% of the value for pure initial zeolite, since the adsorbent structure contains 80% zeolite by weight. The closer this value is to 100%, the less the binder material reduces CO2 adsorption. While high values ​​(greater than 90%) are obtained for all adsorbent structures, it is clear that the zeolite / Torlon adsorbent structure has a relative capacity higher than 100%. The latter may suggest that the Torlon polymer itself adsorbs CO2 to some extent.

[0139] Water isotherm measurements were performed on the degassed adsorbent structures using an IGAsorp standard dynamic vapor sorption (DVS) analyzer under isothermal conditions at 298 K, with simultaneous measurement of both kinetic information and equilibrium uptake. The carrier gas used throughout the measurements was industrial grade nitrogen (Air Products) at a flow of 250 mL / min. Distilled water was used in the IGAsorp reservoir to humidify the gas as needed. The measured static water adsorption capacities are presented in Table 2.

[0140] Comparing the total HO uptake of the polymer composites with that of pure zeolite powder, the adsorption capacity approaches the theoretical maximum. The relative mass change, defined as the water adsorption capacity of the adsorbent (or its mass increase), divided by 80% of the value of the pure initial zeolite, was calculated to be 93.3%, 86.8%, and 103.1% for the PSF-based, PVDF-based, and Torlon-based porous adsorbent structures, respectively. These high values ​​suggest the consistent accessibility of the zeolite pores. The relative mass change of the zeolite / clay adsorbent structure was calculated to be 122.6%. This extremely high value can be explained by the presence of plate-like clay particles, which resulted in slit-shaped pores.

[0141] [Table 2]

[0142] FIG. 8 shows the CO adsorption capacity as a function of pressure for pristine zeolite 40, degassed at 423 K, the theoretical maximum 41, which is 80% of the value of the pristine zeolite, and for zeolite / clay adsorbent structures 42 and 43 with filament thicknesses of 1200 μm and 600 μm, respectively (also degassed at 423 K). A rapid increase in CO adsorption was observed in the lower pressure range, suggesting the microporous nature of zeolite 13X. Furthermore, the total adsorption capacity was very close to the theoretical maximum, regardless of filament thickness. This suggests that the presence of the clay binder does not affect the adsorption properties of the zeolite.

[0143] FIG. 9 shows the CO adsorption capacity as a function of pressure for pristine zeolite 40, degassed at 423 K, the theoretical maximum 41, which is 80% of the value of the pristine zeolite, and for zeolite / PSF adsorbent structures 52 and 53 with filament thicknesses of 1200 μm and 600 μm, respectively (also degassed at 423 K). A rapid increase in CO adsorption was observed in the lower pressure range, suggesting the microporous nature of zeolite 13X. Furthermore, the total adsorption capacity was very close to the theoretical maximum, regardless of filament thickness. This suggests that the presence of the PSF binder does not significantly affect the adsorption properties of the zeolite.

[0144] FIG. 10 shows the CO adsorption capacity as a function of pressure for pristine zeolite 60, degassed at 383 K, the theoretical maximum 61, which is 80% of the value of the pristine zeolite, and for zeolite / PVDF adsorbent structures 62 and 600 μm filament thicknesses (also degassed at 423 K). A rapid increase in CO adsorption was observed in the lower pressure range, suggesting the microporous nature of zeolite 13X. Furthermore, the total adsorption capacity was very close to the theoretical maximum, regardless of filament thickness. This suggests that the presence of the PVDF binder does not significantly affect the adsorption properties of the zeolite.

[0145] Figure 11 shows CO2 adsorption capacity as a function of pressure for initial zeolite 40, degassed at 423 K, the theoretical maximum 41, which is 80% of the initial zeolite value, and for zeolite / Torlon adsorbent structures 72 and 73 with 1200 μm and 600 μm filaments, respectively (also degassed at 383 K). Inconsistent adsorption capacity was found as a function of filament thickness. A significantly reduced CO2 uptake was observed for the 1200 μm filament, corresponding to the reduced total pore volume observed in N2 and Ar porosity measurements. In contrast to the 1200 μm filaments, the 600 μm filament-based adsorbent structure showed an uptake slightly above the theoretical maximum. This difference in adsorption capacity may suggest a different internal structure when comparing the two filament thicknesses and, for the 1200 μm filaments, polymer accumulation in the internal core during the phase inversion process. Furthermore, a possible explanation for the high adsorption capacity of the 600 μm filaments could be a combination of the interaction of CO2 with the Torlon polymer and additional pore volume in the ultrafine pore range that is undetectable by argon measurements but accessible by CO2 molecules.

[0146] 12 shows the water adsorption capacity as a function of pressure for pristine zeolite 80 degassed at 423 K, the theoretical maximum 81, which is 80% of the value of the pristine zeolite, and for zeolite / clay adsorbent structures 82 with a filament thickness of 1200 μm and 83 with a filament thickness of 600 μm (also degassed at 423 K). The shape of the isotherm for the zeolite / clay adsorbent structures showed H3-type hysteresis, regardless of filament thickness. This may be due to the plate-like structure of the bentonite clay particles and their expansion and contraction.

[0147] Figure 13 shows the water adsorption capacity as a function of pressure for pristine zeolite 80, the theoretical maximum 81, which is 80% of the value of the pristine zeolite, degassed at 423 K, as well as for zeolite / PSF adsorbent structures 92 with filament thicknesses of 1200 μm and 93 with filament thicknesses of 600 μm (also degassed at 423 K). The water adsorption isotherms of the adsorbent structures exhibited Type I isotherms, regardless of filament thickness, which is believed to be characteristic of the microporous nature of the zeolite powder.

[0148] 14 shows the water adsorption capacity as a function of pressure for pristine zeolite 100 degassed at 383 K, the theoretical maximum 101, which is 80% of the value of the pristine zeolite, and for zeolite / PVDF adsorbent structures 102 with filament thicknesses of 1200 μm and 103 with filament thicknesses of 600 μm (also degassed at 423 K). The water adsorption isotherms of the adsorbent structures exhibited Type I isotherms, regardless of filament thickness, which is believed to be characteristic of the microporous nature of the zeolite powder.

[0149] Figure 15 shows the water adsorption capacity as a function of pressure for the initial zeolite 80, the theoretical maximum 81, which is 80% of the initial zeolite value, degassed at 423 K, as well as for the 1200 μm filament-thick zeolite / Torlon adsorbent structure 112 and the 600 μm filament-thick zeolite / Torlon adsorbent structure 113 (also degassed at 383 K). The water adsorption isotherms of the adsorbent structures exhibited hysteresis, similar to that observed in the argon adsorption isotherm measurements. This is believed to be caused by a combination of pore blockage by the polymer and chemical interactions between water molecules and the amine functional groups of the polyamide-imide, resulting in delayed desorption. Furthermore, significantly reduced water uptake was observed for the 1200 μm filament thickness compared to the 600 μm filament thickness, which corresponds to the reduced total pore volume observed in the N and Ar porosity measurements.

[0150] Adsorption kinetics The adsorption kinetics of an adsorbent structure is a measure of the adsorption and desorption rates of the adsorbent structure. Higher adsorption kinetics indicates faster adsorption and desorption, and therefore the ability to perform more adsorption / desorption cycles within a given time frame, resulting in a more commercially interesting adsorbent structure.

[0151] The adsorption rates were expressed as the overall mass transfer coefficient k, calculated using the linear driving force model (LDF) described by Glueckauf and Coates. Table 3 shows the overall mass transfer coefficients for water adsorption rates calculated based on the water isotherms described above for the reference zeolite / clay adsorbent structure, the zeolite / PSF adsorbent structure, the zeolite / PVDF adsorbent structure, and the zeolite / Torlon adsorbent structure. All four adsorbent structures, with 600 μm and 1200 μm filaments, were tested and degassed at the temperatures described above.

[0152] [Table 3]

[0153] FIG. 16 shows the water absorption curves for humidity steps from 5% RH to 10% RH as a function of time measured on a single filament with a filament diameter of 1200 μm for the zeolite / clay reference adsorbent structure 120, the zeolite / PSF adsorbent structure 121, the zeolite / PVDF adsorbent structure 122, and the zeolite / Torlon adsorbent structure 123.

[0154] FIG. 17 shows the water absorption curves for humidity steps from 5% RH to 10% RH as a function of time measured on a single filament with a filament diameter of 600 μm for the zeolite / clay reference adsorbent structure 130, the zeolite / PSF adsorbent structure 131, the zeolite / PVDF adsorbent structure 132, and the zeolite / Torlon adsorbent structure 133.

[0155] In Figures 16 and 17, the slope of the linear portion of the initial water adsorption provides an indication of the absorption rate. A steeper curve, i.e., a higher absorption rate, implies a shorter overall time to saturation. Comparing Figures 16 and 17, a significantly increased diffusion coefficient was observed for the adsorbent with a filament diameter of 600 μm, suggesting that reducing the filament diameter reduces the material diffusion limitation.

[0156] Furthermore, as is evident from Table 3, the zeolite / PSF and zeolite / PVDF adsorbent structures exhibited adsorption coefficients comparable to the zeolite / clay reference adsorbent structure. Unlike PSF and PVDF, the addition of the Torlon polymer appears to slightly decrease the rate constant. However, this is closely related to the reduced total pore volume and pore size distribution discussed earlier in this specification, which may therefore be the primary reason for the decreased absorption rate.

[0157] The CO2 breakthrough curve was measured at an applied CO2 partial pressure of 10%. The CO2 breakthrough curve was obtained by measuring the CO2 concentration at the end of a column filled with adsorbent material, where a certain partial pressure of CO2 was passed through the column. The slope of the CO2 breakthrough curve is known to give an idea of ​​the kinetics of CO2 adsorption.

[0158] FIG. 18 shows CO2 breakthrough curves at 10% CO2 partial pressure for zeolite / clay reference adsorbent structure 140, zeolite / PSF adsorbent structure 141, zeolite / PVDF adsorbent structure 142, and zeolite / Torlon adsorbent structure 143 at elapsed times up to 1250 seconds.

[0159] From Figure 18, it is clear that the zeolite / PSF and zeolite / PVDF adsorbent structures exhibited very similar adsorption coefficients compared to the zeolite / clay reference adsorbent structure. Unlike PSF and PVDF, the addition of Torlon polymer appears to slightly lower the rate constant at low CO2 partial pressures. As previously discussed herein, this lower rate constant is believed to be closely related to the reduced total pore volume and pore size distribution of the zeolite / Torlon adsorbent structure. In conclusion, the presence of PSF and PVDF polymers to develop hybrid zeolite composites does not adversely affect the kinetic absorption of CO2 and HO, exhibiting behavior very similar to that of the frequently used reference clay binder. [Explanation of symbols]

[0160] 1. Argon adsorption isotherms of pristine zeolites degassed at 423K 2. Argon adsorption isotherms of pristine zeolites degassed at 383K 3 Argon adsorption isotherm of 80% of the value of the initial zeolite degassed at 423K 4. Argon adsorption isotherm of 80% of the value of the initial zeolite degassed at 383K 5 Zeolite / PSF adsorbent structure 6 Zeolite / PVDF adsorbent structure 7 Zeolite / Torlon adsorbent structure 10. Initial zeolite degassed at 423K 11. Primitive zeolite degassed at 383K 12 Zeolite / PSF adsorbent structure 13 Zeolite / PVDF adsorbent structure 14 Zeolite / Torlon adsorbent structure 20 Zeolite / PVDF adsorbent structure 21 Zeolite / PSF adsorbent structure 22 Zeolite / Torlon adsorbent structure 30 Zeolite / PVDF adsorbent structure 31 Zeolite / PSF adsorbent structure 32 Zeolite / Torlon adsorbent structure 40. Initial zeolite degassed at 423K 41 Theoretical maximum, which is 80% of the initial zeolite value 42 Zeolite / clay adsorbent structure with filament thickness of 1200 μm 43 Zeolite / clay adsorbent structure with filament thickness of 600 μm 52 Zeolite / PSF adsorbent structure with filament thickness of 1200 μm 53 Zeolite / PSF adsorbent structure with filament thickness of 600 μm 60. Initial zeolite degassed at 383K 61 Theoretical maximum value, which is 80% of the initial zeolite value 62 Zeolite / PVDF adsorbent structure with filament thickness of 1200 μm 63 Zeolite / PVDF adsorbent structure with filament thickness of 600 μm 72 Zeolite / Torlon adsorbent structure with filament thickness of 1200 μm 73 Zeolite / Torlon adsorbent structure with filament thickness of 600 μm 80. Initial zeolite degassed at 423K 81 Theoretical maximum, which is 80% of the initial zeolite value 82 Zeolite / clay adsorbent structure with filament thickness of 1200 μm 83 Zeolite / clay adsorbent structure with filament thickness of 600 μm 92 Zeolite / PSF adsorbent structure with filament thickness of 1200 μm 93 Zeolite / PSF adsorbent structure with filament thickness of 600 μm 100 Initial zeolite degassed at 383K 101 Theoretical maximum, which is 80% of the value of the initial zeolite 102 Zeolite / PVDF adsorbent structure with filament thickness of 1200 μm 103 Zeolite / PVDF adsorbent structure with filament thickness of 600 μm 112 Zeolite / Torlon adsorbent structure with filament thickness of 1200 μm 113 Zeolite / Torlon adsorbent structure with filament thickness of 600 μm 120 Zeolite / clay reference adsorbent structure 121 Zeolite / PSF adsorbent structure 122 Zeolite / PVDF adsorbent structure 123 Zeolite / Torlon adsorbent structure 130 Zeolite / clay reference adsorbent structure 131 Zeolite / PSF adsorbent structure 132 Zeolite / PVDF adsorbent structure 133 Zeolite / Torlon adsorbent structure 140 Zeolite / clay reference adsorbent structure 141 Zeolite / PSF adsorbent structure 142 Zeolite / PVDF adsorbent structure 143 Zeolite / Torlon adsorbent structure

Claims

1. A method for manufacturing a three-dimensional porous adsorbent structure, A process for constructing a three-dimensional porous green body from a build material comprising a solvent, an inorganic porous adsorbent material, and an organic binder material, comprising: dissolving at least a portion of the organic binder material in the solvent; depositing the build material as filaments in multiple layers to obtain a three-dimensional porous green body; and separating at least a portion of the filaments within at least one of the multiple layers from each other. A process to induce a phase inversion of a three-dimensional porous green body by exposing it to a non-solvent for an organic binder material, thereby obtaining a solidified three-dimensional porous green body, The process involves drying the solidified three-dimensional porous green material to obtain a three-dimensional porous adsorbent structure. Includes, The build material contains an inorganic porous adsorbent material in an amount between 30% and 70% by mass, and an organic binder material in an amount between 5% and 30% by mass, relative to the total mass of the build material. The three-dimensional porous adsorbent structure comprises at least a portion of an organic binder material, and the three-dimensional porous adsorbent structure has an adsorbent accessibility of at least 40%, and the adsorbent accessibility is given by the following formula (I): [Math 1] (In the formula, S ＢＥＴ，構造体 This is the BET surface area of ​​the three-dimensional porous adsorbent structure. S ＢＥＴ，吸着剤 This is the BET surface area of ​​the initial inorganic porous adsorbent material. X is the mass percentage of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure, and The initial BET surface area of ​​the inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure are determined from the argon adsorption isotherm at 87K. It is characterized by being calculated according to method.

2. The method according to claim 1, wherein the organic binder material comprises a phase inversion polymer, the phase inversion polymer is dissolved in a solvent in the build material, and the phase inversion is induced by exposing a three-dimensional porous green body to a non-solvent for the phase inversion polymer.

3. The method according to claim 1, wherein the phase inversion is induced by immersing a three-dimensional porous green body in its non-solvent and / or by spraying the non-solvent onto the three-dimensional porous green body.

4. The method according to claim 1, wherein the drying process is carried out at a temperature between 20°C and the maximum continuous use temperature of the organic binder material as defined by the Insurers Laboratories for Safety and Testing (UL) Relative Temperature Index (RTI).

5. The method according to claim 1, wherein the three-dimensional porous green body and the three-dimensional porous adsorbent structure are not exposed to temperatures higher than the maximum continuous use temperature of the organic binder material as defined by the Insurers Laboratories for Safety and Testing (UL) Relative Temperature Index (RTI).

6. The method according to claim 1, wherein the three-dimensional porous adsorbent structure is not subjected to either a calcination operation or a sintering operation.

7. The method according to claim 1, wherein the inorganic porous adsorbent material comprises one or more of the following: zeolite adsorbent material, metal-organic frame (MOF) adsorbent material, metal oxide, carbon-based material, clay, molecular sieve, or a layer of several atomic thickness of carbides, nitrides, or carbonitrides of transition metals.

8. The method according to claim 7, wherein the inorganic porous adsorbent material further comprises a catalytically active material applied to the surface of the inorganic porous adsorbent material, and the catalytically active material comprises an enzyme and / or a microorganism.

9. The method according to claim 1, wherein the organic binder material comprises one or more of the following: polysulfone, polyethersulfone, cellulose acetate, polyvinylidene fluoride, polyacrylonitrile, polyethylene-co-vinyl alcohol, or polycarbonate.

10. The method according to claim 1, wherein the build material contains a solvent in an amount of 5% to 65% by mass relative to the total mass of the build material.

11. The method according to claim 1, wherein the solvent includes a polar aprotic solvent.

12. The method according to claim 11, wherein the polar aprotic solvent is N-methyl-2-pyrrolidone (NMP), acetone, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), or a combination of two or more of these.

13. The method according to claim 1, wherein the non-solvent includes a polar protic solvent.

14. The method according to claim 13, wherein the polar protic solvent is water, alcohol, acid, or a combination thereof.

15. The method according to claim 1, wherein the builder is a viscous paste, emulsion, or solution.

16. A three-dimensional porous adsorbent structure that can be obtained by the method according to any one of claims 1 to 15, comprising filaments in a plurality of layers, wherein at least a portion of the filaments within the same layer of the plurality of layers are spaced apart from each other, and the three-dimensional porous adsorbent structure comprises at least 50% by mass of an inorganic porous adsorbent material and 50% by mass or less of an organic binder material, based on the total mass of the three-dimensional porous adsorbent structure. The three-dimensional porous adsorbent structure has at least 40% adsorbent accessibility, and the adsorbent accessibility is given by the following formula (I): [Math 2] (In the formula, S ＢＥＴ，構造体 This is the BET surface area of ​​the three-dimensional porous adsorbent structure. S ＢＥＴ，吸着剤 This is the BET surface area of ​​the initial inorganic porous adsorbent material. X is the mass percentage of the inorganic porous adsorbent material relative to the total mass of the three-dimensional porous adsorbent structure, and The initial BET surface area of ​​the inorganic porous adsorbent material and the BET surface area of ​​the three-dimensional porous adsorbent structure are determined from the argon adsorption isotherm at 87K. It is characterized by being calculated according to Three-dimensional porous adsorbent structure.

17. The three-dimensional porous adsorbent structure according to claim 16, comprising 70% to 98% by mass of an inorganic porous adsorbent material and 2% to 30% by mass of an organic binder material.

18. The three-dimensional porous adsorbent structure according to claim 16, having a micropore volume of at least 30% of the micropore volume of the initial inorganic porous adsorbent material, wherein the micropore volume is determined by a t-plot method on the argon adsorption isotherm at 87 K of the initial inorganic porous adsorbent material and the argon adsorption isotherm at 87 K of the three-dimensional porous adsorbent structure.

19. The three-dimensional porous adsorbent structure according to claim 16, wherein the organic binder material is selected from one or more of polysulfone, polyethersulfone, cellulose acetate, polyvinylidene fluoride, polyacrylonitrile, polyethylene-co-vinyl alcohol, and polycarbonate.

20. For gas adsorption applications and / or liquid adsorption applications, in particular, CO ２ Use of the three-dimensional porous adsorbent structure according to claim 16 for the adsorption of one or more of volatile organic compounds, sulfur oxides, and nitrogen oxides.

21. The use according to claim 20, wherein the three-dimensional porous adsorbent structure is not exposed to temperatures exceeding the maximum continuous use temperature of the organic binder material as defined by the Insurers Laboratories for Safety and Testing (UL) Relative Temperature Index (RTI).

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