Novel monolithic compositions of metal-organic structures

Abstract

This disclosure relates to a composition for use in a gas storage container, the composition comprising at least two MOF monoliths, each comprising at least about 50% by weight of a first MOF monolith and a second MOF monolith. The MOF monoliths contain an MOF and a binder. The first MOF monolith has a macropore volume of about 15% or less of the envelope volume of the first MOF monolith, a particle aspect ratio of about 2 or more, and a minimum particle diameter of about 1 mm or more. The second MOF monolith has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first MOF monolith.

Description

[Technical Field]

[0001] The present invention relates to metal-organic structure (MOF) monolithic compositions, processes for preparing such compositions, gas storage containers containing the compositions, and the use of such compositions in gas storage containers for gas intake, storage, and release.

[0002] There has been, and continues to be, significant interest in the use of improved sorbents for gas storage applications. Gas separation and purification processes are crucial in gas production and storage, as well as in applications requiring high-purity gases, such as air purification, electronics, fine chemicals, fuel cells, and power plants (Metal-Organic Frameworks: Applications from Catalysis to Gas Storage, Part II: Gas Storage and Separation Applications, Wiley, July 2011, Ed.D. Farrusseng). Solubilizing materials are materials that can adsorb and desorb specific chemical species, such as gases, under specific conditions. Solid sorbents are highly porous, and their pores provide a mechanism for adsorbing target chemical species.

[0003] MOF Metal-organic structures (known as MOFs) are a class of sorbent materials that can be used to adsorb, store, and desorb gases. MOFs can offer many performance advantages over current sorbent materials (such as zeolites and activated carbon) and are candidates for improved gas storage systems required for practical transport systems, as well as applications such as gas separation, purification, and carbon capture. A particular characteristic of MOFs is their high selectivity for specific species. Certain MOFs can be modified by altering the organolinker and metal ions to fine-tune and modify their properties, thereby increasing their selectivity when adsorbing specific species.

[0004] MOFs are widely studied for a variety of gas storage and purification applications, such as carbon capture from air and flue gases, methane storage, hydrogen storage, gas separation and purification, and noble gas purification. MOFs are typically highly porous, have a large surface area, and are regenerative for continuous use, making them suitable for these applications and potentially offering an effective and environmentally friendly solution for gas storage and purification. However, so far, handling issues have often limited their industrial applications.

[0005] MOFs can have advantages due to their ability to be functionalized and fine-tuned for the adsorption of specific materials. For example, the unique properties of MOFs allow for fine-tuning of pore shape, size, and chemical properties, making them ideal for gas separation, storage, and purification processes (Eddaoudi et al., Science 2002, 295(5554), pp. 469-472).

[0006] Challenges related to the synthesis and manufacturing of MOF materials and objects. MOF materials are typically synthesized almost universally as fine particles or microcrystals by sol-gel or mechanosynthesis techniques. Forming MOF material fine particle powders into larger MOF monolithic bodies is crucial when using MOF materials in bulk industrial processes involving gas flow or low-pressure drops, and when material handling is a concern, in order to avoid issues such as compression and channeling.

[0007] These MOF monoliths need to be mechanically robust and wear-resistant for industrial use, while also possessing high sorption performance. Ideally, these large objects have high envelope density and bulk density to increase the volumetric capacity of any storage container containing the MOF monoliths. Volumetric capacity represents the adsorption capacity of the container per unit volume. A higher volumetric capacity means that a smaller, and therefore cheaper or more space-efficient, container can be used for a given application. Satisfying the simultaneous requirements of high monolith density and high sorption performance (i.e., high porosity) seems contradictory.

[0008] A key challenge is to properly mold less robust MOF materials into mechanically stable, robust monolithic bodies that still retain high accessibility, porosity, and surface area. Therefore, there is considerable interest in preparing high-density MOF monolithic bodies from fine, low-density powders that retain the beneficial properties of the original MOF material and are suitable for industrial gas storage and purification applications.

[0009] The use of compression techniques, such as tableting, to form MOF monolithic bodies can be problematic for many MOFs, as it can lead to the collapse and disappearance of smaller porosities within the MOF microcrystals that form the molded body. For example, very high pressures typically result in the collapse of some or all of the micropores in the MOF material, which contribute significantly to the material's surface area and gas storage capacity (compared to macropores). This pressure-induced collapse of micropores needs to be reduced or avoided.

[0010] Any process for fabricating high-density MOF monolithic bodies must be able to operate at high speed. Processes that cannot be scaled up in an efficient and cost-effective manner have little commercial viability. Industrial-scale gas storage and separation processes, such as carbon capture and hydrogen storage, require large quantities of sorbent materials, which must be prepared in an efficient and cost-effective manner.

[0011] Therefore, the successful large-scale use of MOF monolithic materials for gas storage, as well as for purification and carbon capture purposes, requires that MOF monolithic materials simultaneously meet multiple quality parameters and processing requirements.

[0012] MOF monolithic materials must simultaneously possess good sorbent capacity and high bulk density to obtain gas storage containers with high volumetric capacity suitable for use in gas separation, storage, and purification processes. However, the development of MOF monolithic materials of suitable quality that can be manufactured by industrially relevant methods, efficiently filled into gas storage containers, and thereby result in high volumetric capacity has received little attention. Many processes, when scaled up from small-scale laboratory production to industrial-scale production, inherently become less efficient and produce products with reduced homogeneity.

[0013] Various methods for producing MOF-containing sorbents, such as granulation (WO2014118054), tableting (US7524444), and extrusion (WO2017089344), are described. However, these methods may have various drawbacks, resulting in a variety of problems including low density, high macroporosity levels, low surface area, high excipient or binder content, damaged MOF structure leading to internal pore collapse, and MOF monoliths with pore blockage due to additives.

[0014] Several known processing routes for preparing MOF monolithic materials, such as tableting, face various problems. Known MOF monolithic materials, such as tablets, can have high envelope density. However, even if they retain porosity during compression and can be manufactured at a rapid rate, their bulk filling efficiency is typically low, leading to low bulk density and reduced gas container volume efficiency.

[0015] In addition, most MOF powders typically have low bulk density and therefore poor flowability. Flowability is usually further worsened when MOF materials are solvated to reduce porosity loss during compression. Therefore, it can be difficult to supply MOF at the required rate into the small individual molds used to form tablets. Such powders may also crosslink with such molds, failing to flow into them and thus failing to fill them. Consequently, additives are often used in tablets to aid in processing. However, this results in tablets with a low content of active material (i.e., MOF), thereby resulting in MOF monolithic tablets with lower performance.

[0016] Many of the tableting problems described herein also apply to roller compression.

[0017] Other processing routes for preparing MOF monolithic materials, such as granulation, also face drawbacks. For example, it is difficult to prepare MOF monolithic materials with high bulk density and / or envelope density through granulation. Adsorbent powders such as MOFs are typically difficult to handle and have low bulk density. Because granulation processes tend to lack a strong compression step during processing, the resulting granules typically have a high level of macroporosity and a lower envelope density. Furthermore, in granulation processes, most or all of the adsorbent material needs to be dried and processed into a powder, for example by spray drying. This can result in undesirable macroporosity and extra processing complexity.

[0018] Use of extrusion for monolithic fabrication Extrusion can be used to prepare MOF monolithic bodies and is widely reported in the art for producing MOF bodies (e.g., WO2014 / 118074). However, extrusion typically results in extruded bodies with lower filling efficiency and bulk density. This is inherent to the shape of the extruded body, particularly the high aspect ratio typical of extruded bodies. The aspect ratio is the ratio of the length of an extruded body to its width / diameter. This is a measure that is actually applicable only to extruded bodies and other shaped bodies. For example, if a monolithic body has a length of 10 mm and a width of 2 mm, it will have a particle aspect ratio of 5. The aspect ratio of most granules is typically close to 1, and the aspect ratio of a sphere is 1. Some granules can be described as "ellipsoids," but ellipsoids are essentially deformed spheres and will typically have a small aspect ratio, for example, less than 2.

[0019] The porosity of extruded body filling in a container typically increases linearly with the aspect ratio of the extruded body. Porosity is the percentage of container volume left unfilled by randomly packed extruded bodies due to the voids between them. The porosity of randomly packed extruded bodies increases linearly with aspect ratio, from 0.32 at an aspect ratio of 1 to 0.46 at an aspect ratio of 5 (Rolland et al., Ind.Eng.Chem.Res.2019,58(9),p.3902-3911). Higher porosity is clearly detrimental to the volumetric capacity of a gas container. However, for various reasons, mass production of extruded bodies with aspect ratios close to 1 is typically difficult and often requires specific processing equipment where the rheology of the extruded mixture is typically within certain parameters that can limit the composition.

[0020] Unlike other more spherical particle forms, extruded products typically have a variety of particle dimensions and aspect ratios, especially when manufactured on an industrial scale. This often results in lower bulk density or higher porosity.

[0021] Therefore, the volumetric performance of gas storage containers containing sorbent monolithic MOF extruded bodies may be limited. In practice, due to processing variability and material rheology, it is difficult and constrained to rapidly manufacture extruded bodies with aspect ratios close to 1. It is easier to produce extruded bodies with higher aspect ratios. This is problematic because extrusion has many processing advantages. Therefore, there is interest in developing compositions that have properties that allow extrusion to be used as the primary manufacturing process, but that offset some of the disadvantages associated with the use of extruded bodies.

[0022] These limitations include both bulk density and adsorption kinetics. The initial adsorption kinetics are partially limited by the outer surface of the MOF body. The gas diffuses into the MOF body from contact with the outer surface. Adsorption kinetics can be important in separation processes where process cycle times can be very short. The rate at which a substance can be adsorbed and released by the sorbent can be as important as the total volume of the sorbent. One example is the Rapid Cycle Pressure Swing Adsorption process, which can be used in processes such as carbon dioxide adsorption and capture.

[0023] Simultaneously, extrusion may be a promising method for preparing MOF monolithic bodies, provided that the limitations described herein can be overcome. Extrusion is a practical process due to the ease of mixing powders and liquids, as well as the formation of the extruder by passing the material through an orifice in the die plate at the end of the extruder. The extruder may be either a single-screw extruder or a twin-screw extruder, which are commonly used in plastics processing. A twin-screw extruder (either co-rotating or reversing) is preferred for this application as it allows for strong mixing of materials such as MOF powder and binders.

[0024] The inventors found that MOF monolithic compositions, combining beneficial chemical and physical attributes with the shape and distribution of the monolithic body size, can result in optimized sorbent products that can be more easily manufactured on an industrial scale.

[0025] The present invention relates to MOF monolithic compositions, methods for preparing such compositions, gas storage containers containing such compositions, and uses of such gas storage containers. The inventors have found that the compositions are practical to prepare and can be used to provide gas storage containers having advantageous gas absorption, storage, separation, and / or release properties, and having improved volumetric performance and efficient gaskinetic performance.

[0026] MOFs may vary depending on the gas storage or purification application and the type of gas or adsorbed species involved. For example, in carbon capture applications, it may be preferable to select an MOF with high uptake and selectivity for carbon dioxide.

[0027] The selection of an MOF may also be based on the environment and conditions to which the MOF monolithic is exposed, as well as the stability of the MOF, such as its thermal stability, chemical stability, and / or mechanical stability. For example, in gas purification and / or storage applications involving high temperatures and / or the presence of certain types of water or steam, it may be preferable to select an MOF with high thermal and chemical stability. For example, for carbon capture from flue gas, the gas stream may contain water, and therefore it may be preferable to select an MOF with high stability against water.

[0028] It is important that MOFs maintain their porosity during processing. MOFs are often not very robust due to the nature of the ligand-metal ion bonds that form the pore structure. These bonds depend more on metal coordination chemistry than on stronger covalent or ionic bonds. By applying external pressure, it is possible to deform and crush the pores of MOFs, thus reducing the surface area of ​​the MOF available for gas sorption. Different MOFs have different stability and strength depending on properties such as the MOF composition and crystal structure.

[0029] It is also advantageous that the MOF monolithic body possesses suitable properties that provide fast gas uptake and release kinetics. One aspect of this is that the distance between the interior and exterior surface of the MOF monolithic body should not be too large; otherwise, the diffusion rate will be limited. It is advantageous to have a maximum distance of 2.5 mm or less than 2 mm, or less than 1 mm. In this way, the gas can rapidly diffuse into the interior of the MOF monolithic body. Furthermore, the gas must be able to flow easily into and around the monolithic body within the gas storage container. Therefore, efficient filling of the MOF monolithic body in the gas storage container must also enable fast gas kinetics.

[0030] Extruded bodies with reduced diameter may seem potentially advantageous due to the increased external surface area of ​​the extruded body, which would improve the kinetics of sorption in high-speed cycle pressure swing adsorption processes, for example. For instance, an extruded body with a cross-sectional diameter of 2 mm and an aspect ratio of 3 has a surface area / volume ratio 3.2 times greater than an extruded body with a diameter of 4 mm and an aspect ratio of 3. An extruded body with a cross-sectional diameter of 1 mm and an aspect ratio of 3 has a surface area / volume ratio 11.2 times greater than an extruded body with an aspect ratio of 3 and a diameter of 4 mm. However, extruded bodies with reduced diameter present numerous problems, as described herein.

[0031] MOF monolithic bodies must also be robust enough to withstand agitation in general use and avoid excessive dust generation. Typically, MOF bodies contain a binder to improve the robustness and resistance to the MOF and mechanical abrasion. Such binders can be inorganic, such as alumina hydrate, or organic polymers, such as PVA. However, including a binder in MOF monolithic bodies can lead to problems such as pore blockage and / or dilution of the active sorbent material. Therefore, the development of MOF monolithic bodies with good mechanical stability, high surface area, porosity, and volumetric capacity is of significant interest.

[0032] The MOF monolithic material itself also needs to have good properties, particularly low macroporosity. Larger macropores do not contribute significantly to the adsorption capacity of adsorbents and only reduce density. There is little point in efficiently filling highly macroporous adsorbents in an efficient manner. The overall porosity in a gas storage container is a combination of bulk porosity and the macroporosity of the MOF monolithic material itself. Both must be addressed to minimize bulk porosity.

[0033] The problems addressed by this composition are widely applicable to most MOFs and binders, as well as a wide range of processes.

[0034] According to one aspect of the present invention A composition comprising at least two MOF monolithic bodies, The composition comprises at least about 50% by weight of a first MOF monolithic body, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids), The first MOF monolithic body is Organic binders and, Based on the total weight of the first solid MOF monolithic body (i.e., the object excluding gases, liquids, and / or fluids), it includes at least about 80% by weight of MOF, The first MOF monolithic body has a macropore volume of approximately 15% or less of the envelope volume of the first MOF monolithic body, a particle aspect ratio of approximately 2 or more, and a minimum particle diameter of approximately 1 mm or more. The second MOF monolithic body is A binder and MOF and, A composition is provided in which the second MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first MOF monolithic body.

[0035] Manufacturing of the composition A further aspect of the present invention provides a method for preparing a composition comprising at least two MOF monolithic bodies.

[0036] One example method is: a. A step of providing a wetting binder MOF mass, wherein the wetting binder MOF mass is i.MOF and, ii. Based on the total weight of the MOF mass, a first solvent is added in an amount of approximately 50% to approximately 95% by weight, iii. A step comprising providing an organic binder, wherein the binder may be added as a solution, dispersion, powder, or mixture thereof. b. Optionally, the step of reducing the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass, c. The step of extruding and cutting a wet binder MOF mass or an undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, d. The step of removing at least some of the remaining first solvent from the first undried MOF monolithic to provide the first dried MOF monolithic, e. Optionally, the step of adding a second solvent to the first dried MOF monolithic to remove at least some of any residual first solvent, at least some of any unreacted reactants, and at least some of the organic binder from the first dried MOF monolithic to provide an optional first binder-reduced MOF monolithic, f. Optionally, the step of removing at least some second solvent from an optional first binder-reduced MOF monolith to provide an optional first inactivated MOF monolith, g. The step of activating the first dried MOF monolith or an optional first inactivated MOF monolith by exposing it to a temperature of approximately 100°C or higher to provide the first MOF monolith; h. Providing a composition by combining a first MOF monolithic body with a second MOF monolithic body, wherein the second MOF monolithic body is as described herein and has a minimum particle diameter of the first MOF monolithic body and a maximum particle diameter of approximately the same or less.

[0037] Alternative methods are described later in this specification.

[0038] The method of the present invention may further include one of a plurality of steps for providing a second MOF monolithic body for use in step (h), the step being: A step of grinding several first dried MOF monolithic bodies to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the dried first MOF monolithic body, and / or The step of providing an optional second binder-reduced MOF monolithic body by grinding several optional first binder-reduced MOF monolithic bodies, wherein the optional second binder-reduced MOF monolithic body has a minimum particle diameter and a maximum particle diameter approximately less than or equal to that of the optional first binder-reduced MOF monolithic body.

[0039] The second MOF monolithic can be produced by other processes, provided that the size and composition requirements are met. For example, if the first MOF monolithic includes an activated extruded body with a particle width of approximately 2 mm, the second MOF monolithic may include aggregates or granules with a particle size of approximately 2 mm or less.

[0040] A preferred method for producing a second MOF monolithic is to mill a portion of the first MOF monolithic and sift it to the appropriate size. The second MOF monolithic can then be blended with the first MOF monolithic.

[0041] A gas storage container comprising the composition is provided according to a further aspect of the present invention.

[0042] A further aspect of this disclosure provides the use of a gas storage container comprising the composition for gas intake, storage and / or release.

[0043] Further aspects of this disclosure provide the use of the composition for gas intake, storage and / or release.

[0044] MOF monolithic bodies and compositions The inventors have unexpectedly discovered a composition that overcomes one or more drawbacks associated with prior art compositions.

[0045] Specifically, the compositions of the present invention have a high bulk density and can provide rapid kinetics for adsorption and desorption, while also being suitable for use in industrial production and gas sorption applications.

[0046] The inventors have found that large-scale production of reduced-diameter or thinner extruded products is difficult because thinner extruded products typically stick together to form lumps after extrusion. Therefore, there is an advantage to having MOF compositions that can be manufactured more easily on an industrial scale and still possess adsorption kinetics and capacity suitable for many adsorption processes, particularly carbon capture and hydrogen storage.

[0047] While we do not wish to be bound by theory, the aggregation of thin extruded bodies is thought to be due to the weight reduction of the reduced-diameter extruded bodies. According to aggregation theory, the tendency of two objects to stick together after a collision is strongly influenced by the size and mass of the objects. The larger the object, the more momentum and kinetic energy it needs to dissipate in order for the objects to stay together. In practice, this means that larger objects tend to repel and separate after a collision, while smaller objects, such as reduced-diameter extruded bodies, tend to stick together. Numerous extruded body-extruded body interactions are unavoidable in any large-scale process, typically resulting in a large portion of the reduced-diameter extruded bodies sticking together in clumps, making separation difficult. Limiting the number of holes in the die plate so that the extruded bodies are far enough apart to avoid contact reduces the production rate to an impractical level. Making the extrusion mixture sufficiently "dry" and non-stick so that the reduced-diameter extruded bodies do not stick together typically results in extremely high extrusion pressures (which can cause MOF or material damage) and die plate clogging.

[0048] The inventors have surprisingly found that MOF extruded articles must have a minimum particle width / diameter in order to be manufactured on a large scale and practically.

[0049] Furthermore, the inventors have found that the presence of a second MOF monolithic body can increase the gas sorption capacity of the MOF composition while simultaneously increasing the rate of gas sorption / desorption, particularly as a result of the efficient packing arrangement of the first and second MOF monolithic bodies.

[0050] Limiting the proportion of the second MOF monolithic body in the composition also helps to avoid excessive pressure drops when using the composition in the gas sorption process.

[0051] Furthermore, the production of a second, smaller MOF monolithic body may be more difficult than the production of the first MOF monolithic body. The production of a second MOF monolithic body with reduced particle size, such as through granulation or extrusion, is typically carried out by processes involving milling and / or sieving. Such production processes often result in high levels of fine particles (which need to be recycled back into the process) and low yields. Therefore, it is advantageous to avoid high levels of the second MOF monolithic body in the composition.

[0052] As a result, a balance is struck between ease of production suitable for large-scale production and the dynamic and volumetric performance of MOF monolithic bodies.

[0053] Furthermore, the MOF monolithic material of the present invention contains an organic binder sufficient to ensure adequate robustness, in contrast to other MOF materials that contain an inorganic binder or contain no binder at all. For example, extruded MOF materials that do not contain a binder are typically too brittle to be useful for industrial-scale applications.

[0054] The inclusion of a second MOF monolithic in the composition promotes heat transfer throughout the composition as a result of an increased number of contact points between MOF monolithic particles, and in addition, provides a favorable gas sorption profile, particularly during desorption. For example, the gas in the second MOF monolithic is released faster than the gas in the first MOF monolithic, providing a more stable gas flow.

[0055] The term "MOF monolithic body" refers to a solid, uniform, and continuous external and internal structure containing a high proportion of MOF material and having a high envelope density. These materials are distinct from MOF bodies in which the MOF material is deposited on the surface of a substrate or incorporated into a thin film of another material. MOF monolithic bodies do not contain individual MOF particles or MOF microcrystals.

[0056] The MOF monolithic compositions of the present invention comprise an MOF and a binder. These MOF monolithic compositions are combined to provide an MOF monolithic composition that is more efficiently filled in gas storage containers. MOF monolithic compositions are typically in a form that is easy to manufacture on a large scale.

[0057] The first MOF monolithic body comprises an organic binder and at least 80% by weight of MOF, based on the total weight of the first solid MOF monolithic body (i.e., the substance excluding gases, liquids, and / or fluids).

[0058] The first MOF monolithic body may contain, based on the total weight of the first solid MOF monolithic body (i.e., the substance excluding gases, liquids, and / or fluids), at least about 80 wt% of MOF and up to about 20 wt% of organic binders, e.g., about 80 to about 98 wt% of MOF and about 2 to about 20 wt% of organic binders, e.g., about 80 to about 96 wt% of MOF and about 4 to about 20 wt% of organic binders, e.g., about 90 to about 95 wt% of MOF and about 5 to about 10 wt% of organic binders, e.g., about 94 to about 95 wt% of MOF and about 5 to about 6 wt% of organic binders.

[0059] The second MOF monolithic material contains a binder and an MOF.

[0060] The second MOF monolithic body may include, based on the total weight of the solid second MOF monolithic body (i.e., the substance excluding gases, liquids, and / or fluids), a binder and at least about 50 wt% of MOF, e.g., a binder and at least about 70 wt% of MOF, e.g., a binder and at least about 80 wt% of MOF, e.g., at least about 80 wt% of MOF and up to about 20 wt% of binder, e.g., about 80 to about 98 wt% of MOF and about 2 to about 20 wt% of binder, e.g., about 85 to about 96 wt% of MOF and about 4 to about 15 wt% of binder, e.g., about 90 to about 95 wt% of MOF and about 5 to about 10 wt% of binder, e.g., about 94 to about 95 wt% of MOF and about 5 to about 6 wt% of binder, and so on.

[0061] A first MOF monolithic can consist essentially of (or comprise) an MOF and an organic binder, and / or a second MOF monolithic can consist essentially of (or comprise) an MOF and a binder.

[0062] A first MOF monolithic can essentially consist of (or comprise) about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of organic binder, based on the total weight of the first MOF monolithic, and / or a second MOF monolithic can essentially consist of (or comprise) about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of binder, based on the total weight of the second MOF monolithic in solid form (i.e., the substance excluding gases, liquids and / or fluids).

[0063] The first MOF monolithic and the second MOF monolithic may contain the same binder and / or the same MOF, or they may contain different binders and / or different MOFs.

[0064] Preferably, the MOFs of the first and second MOF monolithic bodies are the same. Preferably, the binders of the first and second MOF monolithic bodies are the same. More preferably, the MOFs of the first and second MOF monolithic bodies are the same and present in the same amount, and the binders of the first and second MOF monolithic bodies are the same and present in the same amount.

[0065] The composition contains at least two MOF monolithic bodies. The composition may contain more than two MOF monolithic bodies.

[0066] The composition may essentially consist of first and second MOF monoliths. The composition may essentially consist of first and second MOF monoliths and optionally a gas.

[0067] The composition may consist of first and second MOF monoliths. The composition may consist of first and second MOF monoliths and optionally a gas.

[0068] The composition contains at least about 50% by weight of a first MOF monolithic body, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids). The composition may contain up to about 50% by weight of a second MOF monolithic body, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids).

[0069] The composition may contain, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids and / or fluids), at least about 55% by weight of the first MOF monolithic body, for example, at least about 60% by weight, for example, at least about 70% by weight, or about 50 to about 99.9% by weight, for example, about 55 to about 99.9% by weight, for example, about 60 to about 99.9% by weight, for example, about 80 to about 99.9% by weight, for example, about 82 to about 99.5% by weight, about 85 to about 99% by weight, for example, about 88 to about 98% by weight, for example, about 92 to about 97% by weight, for example, about 94 to about 96% by weight of the first MOF monolithic body.

[0070] The composition may contain, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids and / or fluids), up to about 45% by weight of the second MOF monolithic body, for example, up to about 40% by weight, for example, up to about 30% by weight, or about 0.1 to about 50% by weight, for example, about 0.1 to about 45% by weight, for example, about 0.1 to about 40% by weight, for example, about 0.1 to about 20% by weight, for example, about 0.5 to about 18% by weight, for example, about 1 to about 15% by weight, for example, about 2 to about 12% by weight, for example, about 3 to about 8% by weight, for example, about 4 to about 6% by weight of the second MOF monolithic body.

[0071] For example, the composition may consist of at least about 55% by weight of a first MOF monolithic and up to about 45% by weight of a second MOF monolithic, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids), for example, at least about 60% by weight of a first MOF monolithic and up to about 40% by weight of a second MOF monolithic, for example, at least about 70% by weight of a first MOF monolithic and up to about 30% by weight of a second MOF monolithic, or about 50 to about 99.9% by weight of a first MOF monolithic and about 0.1 to about 50% by weight of a second MOF monolithic, for example, about 55 to about 99.9% by weight of a first MOF monolithic and about 0.1 to about 45% by weight of a second MOF monolithic, for example, about 60 to about 99.9% by weight of a first MOF monolithic and about 0.1 to approximately 40% by weight of a second MOF monolithic, e.g., approximately 80 to approximately 99.9% by weight of a first MOF monolithic and approximately 0.1 to approximately 20% by weight of a second MOF monolithic, e.g., approximately 82 to approximately 99.5% by weight of a first MOF monolithic and approximately 0.5 to approximately 18% by weight of a second MOF monolithic, e.g., approximately 85 to approximately 99% by weight of a first MOF monolithic and approximately 1 to approximately 15% by weight The first MOF monolithic may include, for example, about 88 to about 98% by weight of the first MOF monolithic and about 2 to about 12% by weight of the second MOF monolithic, for example, about 92 to about 97% by weight of the first MOF monolithic and about 3 to about 8% by weight of the second MOF monolithic, for example, about 94 to about 96% by weight of the first MOF monolithic and about 4 to about 6% by weight of the second MOF monolithic.

[0072] Preferably, the composition comprises, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids), about 50 to about 99% by weight of a first MOF monolithic and about 1 to about 50% by weight of a second MOF monolithic, for example, about 55 to about 98% by weight of a first MOF monolithic and about 2 to about 45% by weight of a second MOF monolithic, or about 70 to about 97% by weight of a first MOF monolithic and about 3 to about 30% by weight of a second MOF monolithic.

[0073] The composition may contain a low content of the second MOF monolithic. For example, the composition may contain, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids), about 80 to about 99% by weight of the first MOF monolithic and about 1 to about 20% by weight of the second MOF monolithic, e.g., about 90 to about 98% by weight of the first MOF monolithic and about 2 to about 10% by weight of the second MOF monolithic, e.g., about 94 to about 97% by weight of the first MOF monolithic and about 3 to about 6% by weight of the second MOF monolithic.

[0074] The first and second MOF monolithic materials may have the same, similar, or different properties. For example, the following properties of the two MOF monolithic materials may have some of the same features and properties (e.g., type of sorbent, surface area, porosity such as microporosity and / or mesoporosity, envelope density, relative density, etc.).

[0075] The first and second MOF monolithic bodies may have different features and / or properties (e.g., amount of MOF and / or binder, type of MOF and / or binder, surface area, porosity, microporosity, mesoporosity, macroporosity, envelope density, relative density, etc.).

[0076] In some embodiments, the first MOF monolithic and the second MOF monolithic may comprise different MOFs. The second MOF monolithic may have complementary functions to the first MOF monolithic, which are beneficial for gas storage and separation applications. For example, the second MOF monolithic may function as a scavenger for cleaning gases and / or compounds when the composition is used for gas intake, storage, and / or release.

[0077] In particular, the second MOF monolithic may include an MOF that can function as a water scavenger (e.g., the MOF prefers to adsorb water rather than other gases such as CO2) or a sulfur scavenger (e.g., the MOF prefers to adsorb sulfur compounds rather than other gases such as methane). Thus, the second MOF monolithic may improve volumetric capacity and remove specific gases or compounds from the gas stream.

[0078] In such embodiments, the composition preferably contains a low content of a second MOF monolithic. For example, the composition may contain, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids, and / or fluids), about 90 to about 99.9% by weight of a first MOF monolithic and about 0.1 to about 10% by weight of a second MOF monolithic, for example, about 95 to about 99% by weight of a first MOF monolithic and about 1 to about 5% by weight of a second MOF monolithic, for example, about 97 to about 98.5% by weight of a first MOF monolithic and about 3 to about 1.5% by weight of a second MOF monolithic.

[0079] The composition may include two or more MOF monoliths having the same or different characteristics and properties as the first and / or second MOF monolith.

[0080] Problems related to the use of optimized monolithic materials and binders While not wishing to be constrained by theory, it is proposed that a binder is necessary to provide robustness and resistance to mechanical wear to MOF monolithic bodies. Furthermore, a binder applied partially or completely as a solution or paste can facilitate extrusion. With this binder, MOF monolithic bodies, such as extruded articles, have high strength and wear resistance. Advantageously, the binder allows the MOF monolithic body to be appropriately molded into an object having a specific particle shape and particle size distribution as well as a particle aspect ratio.

[0081] The inventors have found that the combination of process selection, binder, and MOF in this disclosure can result in MOF monolithic bodies having optimal properties such as porosity, particularly macroporosity, surface area, pore accessibility, and mechanical robustness. Preferably, such MOF monolithic bodies can be used in the compositions of the present invention. Surprisingly, when processed by a preferred process, relatively low levels of binder can impart good mechanical robustness to the MOF monolithic body.

[0082] The use of binders and extrusion processes to obtain MOF monolithic bodies can provide compositions that are robust enough to avoid fracture of the MOF monolithic bodies while simultaneously offering adapted and controlled multimodal particle size distributions, such as multimodal shape and / or size distributions, and high filling efficiency. Thus, the multimodal distribution is achieved in a controlled manner, for example, by controlled preparation and / or processing. This can provide a controlled multimodal shape and / or size distribution that is not a result of material fragility.

[0083] The first and / or second MOF monolithic body may have an elastic modulus (e.g., Young's modulus, E) of about 0.5 to about 100 GPa, for example, about 1 to about 50 GPa, for example, about 2 to about 20 GPa.

[0084] The first and / or second MOF monolithic bodies may have a hardness H of about 100 to about 5000 MPa, for example, about 200 to about 2500 MPa, for example, about 400 to about 1500 MPa.

[0085] Young's modulus and hardness values ​​can be determined using standard characterization methods, such as nanoindentation.

[0086] Low levels of binder may be achieved by using an organic polymer binder on the MOF body and contacting the dried MOF body with a second solvent before activation to remove a portion of the initially added organic polymer binder. The amount of organic polymer binder removed may be less than 20% or more than 20%, based on the total amount of organic polymer binder added.

[0087] While we do not wish to be constrained by theory, it is conceivable that partial removal of organic polymer binders from a dried MOF monolithic material would remove at least a portion of the organic polymer binders that are most readily accessible to the solvent. These are thought to be organic polymer binders coated on the surface of the MOF microcrystals, which can clog pores but are least involved in the bonding of the MOF microcrystals to each other. We believe that the organic binders in closest contact with the MOF microcrystals are least accessible to the solvent and therefore dissolve the slowest. Consequently, the remaining organic polymer binders are thought to be most effective in bonding the MOF particles to each other.

[0088] Furthermore, this process allows for limiting the macroporosity of MOF monoliths by controlling the amount of organic polymer binders removed from the dried MOF monoliths.

[0089] While we do not wish to be bound by theory, it is believed that partial removal of organic polymer binders from dry MOF monoliths results in MOF monoliths with a desirable porosity profile that has high levels of micropores and mesopores but not high levels of macropores, and therefore they become particularly suitable for gas storage due to their high density and high, useful combination of porosity and BET surface area. Other processes typically result in the formation of high levels of macropores along with high levels of micropores and mesopores, resulting in a decrease in monolithic density.

[0090] Throughout this application, we define three pore size regimes using the standard IUPAC definition of pore size. Micropores refer to pores with a size of less than approximately 2 nm. Mesopores refer to pores with a size of approximately 2 nm to approximately 50 nm. Macropores refer to pores with a size greater than approximately 50 nm. Macropores have very little adsorption capacity and do not contribute to the sorption capacity of the material. Pore size is an important factor because it can determine the reachability of species to the pores. Pores are also beneficial for species movement throughout the MOF monolithic body.

[0091] MOF monolithic materials may be microporous, or in other words, they may have micropores. The micropores of the MOF monolithic material may be provided by the MOF, i.e., the MOF may have micropores. Having micropores is advantageous for MOF monolithic materials because it may result in desirable properties for gas sorption, storage, separation, and purification.

[0092] In some embodiments, the MOF monolithic material has mesopores (i.e., pores larger than micropores but smaller than macropores). Mesopores can be beneficial for the movement of species and / or fluids throughout the MOF monolithic material. In particular, mesopores can provide high-speed gas kinetic transport throughout the MOF monolithic material. Preferably, the MOF monolithic material contains mesopores.

[0093] The first and / or second MOF monolithic material may have a high level of microporosity based on the total pore volume measured by N2 adsorption. The first and / or second MOF monolithic material may have a microporosity of about 40% or more, for example, about 40% to about 75%, based on the total pore volume measured by N2 adsorption.

[0094] The macroporosity of an object can be defined as the macropore volume of the object relative to its envelope volume.

[0095] Macroporosity can be measured by mercury porosimetry. Mercury porosimetry does not measure microporosity or mesoporosity. The pressure required to push mercury into very small micropores and mesopores exceeds the capabilities of available instruments. Conversely, nitrogen adsorption methods do not detect large pores.

[0096] The first MOF monolithic body has a macropore volume of about 15% or less of the envelope volume of the first MOF monolithic body, and the macropore volume may be about 13% or less of the envelope volume of the first MOF monolithic body, for example, about 12% or less, for example, about 10% or less, for example, about 7% or less, for example, about 5% or less, or about 0.1 to about 15%, for example, about 0.2 to about 13%, for example, about 0.5 to about 10%.

[0097] The second MOF monolithic body may have a macropore volume of approximately 15% or less of the envelope volume of the second MOF monolithic body, for example, approximately 13% or less, for example, approximately 12% or less, for example, approximately 10% or less, for example, approximately 7% or less, for example, approximately 5% or less, or approximately 0.1 to approximately 15%, for example, approximately 0.2 to approximately 13%, for example, approximately 0.5 to approximately 10%.

[0098] The macropore volume of the second MOF monolithic may be lower than the envelope volume of the second MOF monolithic.

[0099] The second MOF monolithic body may have a macropore volume of about 15% or less of the envelope volume of the second MOF monolithic body, and the macropore volume may be about 12% or less of the envelope volume of the second MOF monolithic body, for example, about 10% or less, for example, about 7% or less, for example, about 5% or less.

[0100] The macroporosity of the first and second MOF monolithic bodies may be different or the same. Preferably, the first and second MOF monolithic bodies have the same macroporosity (i.e., the macropore volume with respect to the envelope volume of the first and second MOF monolithic bodies).

[0101] The available surface area / unit mass for gas sorption is the BET surface area as described below, which is measured by nitrogen adsorption at 77K. Ideally, the MOF monolithic body has a high surface area and porosity. The surface area of the MOF monolithic body contributes to the volume capacity of the MOF monolithic body, and thus it is preferred that the MOF monolithic body has a high surface area such that when the MOF monolithic body is filled in a gas storage container, it has a high surface area / unit volume within the gas storage container.

[0102] The first and / or second MOF monolithic body has a BET surface area measured by N2 sorption of about 0 m 2 / g or more, for example about 10 m 2 / g or more, for example about 100 m 2 / g or more, for example about 200 m 2 / g or more, for example about 300 m 2 / g or more, for example about 400 m 2 / g or more, for example about 700 m 2 / g or more, for example about 1000 m 2 / g or more, for example about 1500 m 2 / g or more, or about 0 to about 4,000 m 2 / g, for example about 0 to about 2,500 m 2 / g, for example about 100 to about 2,000 m 2 / g and may have a BET surface area measured by N2 sorption.

[0103] Certain MOF materials may have a low BET surface area but still exhibit high uptake of other gases such as hydrogen, methane, carbon dioxide, krypton, and / or water, for example hydrogen, methane, carbon dioxide and / or krypton.

[0104] These characteristics can provide MOF monolithic bodies with desirable performance for gas separation, purification, and storage applications, and therefore there are particular advantages to providing MOF monolithic bodies with high microporosity, low macroporosity, high BET surface area, and a high percentage (by weight) of MOF. Extruded MOF monolithic bodies may have these characteristics and are therefore particularly suitable for use in these applications.

[0105] The use of MOF monolithic bodies prepared using extrusion molding is advantageous due to the industrial feasibility of this process. The use of MOF monolithic extruded bodies having the properties defined above, combined with the bulk properties of the entire extruded body assembly, offers further advantages, as it is further optimized to further improve the performance of MOF-containing gas storage vessels.

[0106] The need to store as much gas as possible in a given volume of gas storage container means that the bulk density of the MOF monolithic body is extremely important, as is the composition and surface area of ​​individual MOF bodies.

[0107] There are further advantages to using MOF monolithic materials having the properties defined above, as the bulk properties of the composition have been further optimized to further improve the performance of the MOF monolithic material when supplied as a composition in gas storage containers.

[0108] When MOF monolithic bodies are filled into gas storage containers, their bulk density is a critical parameter. A high bulk density of the MOF composition within a gas storage container is beneficial to the container's volumetric capacity and performance. This allows for higher levels of gas adsorption and / or storage within a given volume. Maximizing the filling efficiency of MOF monolithic bodies to increase bulk density can improve the volumetric performance of gas storage containers for use in gas separation, purification, and storage applications. As mentioned earlier, the filling efficiency of extruded bodies is typically low.

[0109] The present invention further defines the shape and size distribution of MOF monolithic bodies having the properties described herein, which are particularly suitable for use in gas storage containers. MOF monolithic bodies may be multimodal in terms of shape and / or size distribution. Multimodal means that the composition comprises at least two MOF monolithic bodies, and at least two MOF monolithic bodies may have different shape and size characteristics.

[0110] The non-uniform shapes of some MOF monolithic materials, such as extruded bodies, can make it difficult to define them using simple measures such as particle diameter and / or particle shape. Instead, parameters such as particle aspect ratio, elongation, and / or particle roundness ratio can be used to define the particles of MOF monolithic materials.

[0111] The inventors determined that higher packing density and bulk density can be best achieved by using a combination of at least two MOF monolithic bodies having different size and shape distributions.

[0112] The first MOF monolith has a particle aspect ratio of about 2 or more, for example, the particle aspect ratio may be about 3 or more, for example, about 2 to about 7, for example, about 3 to about 7. Further particle aspect ratios of the first MOF monolith include about 2.4 or more, about 2.5 or more, about 2.6 or more, or about 2 to about 6, for example, about 2 to about 5, for example, about 2 to about 4, and about 2.4 to about 5.1, or even about 3 to about 5. For the aforementioned process reasons, the production of monoliths with an aspect ratio of less than 2 by large-scale extrusion is undesirable. Furthermore, larger aspect ratios are undesirable due to very poor packing. For example, particle aspect ratios greater than 20, greater than 10, greater than 7, or in some cases greater than 5 may have low packing density.

[0113] The first MOF monolithic body may not be in the form of a sphere, flake, and / or ellipsoid. For example, in some embodiments, the first MOF monolithic body may not have a particle aspect ratio of less than 3, e.g., less than 2.5. In particular, if the first MOF monolithic body is an extruded body, it may not have a spherical, flake, or ellipsoidal shape.

[0114] The first MOF monolith has low packing efficiency and therefore low bulk density. The second MOF monolith particles can fit into the voids between the first MOF monolith particles. Importantly for the second MOF monolith, its particle diameter is less than or equal to the width of the first MOF monolith extrusion. The aspect ratio of the second MOF monolith is close to approximately 1 (typical for most granules or particles), but this is not a critical parameter for efficient packing; rather, it is the particle size required to fit into the available voids. The improved bulk density of the resulting composition results in higher volumetric performance when packed into a gas storage container. The packing arrangement may depend on the particle diameter, particle shape, particle aspect ratio, and / or relative volume of the first and / or second MOF monoliths.

[0115] Monolithic bodies with a high particle aspect ratio, i.e., extruded bodies, are typically easy to manufacture on a large scale, and therefore, having a high level of such monolithism in the composition is typically advantageous. Accordingly, the composition preferably contains a larger amount of the first MOF monolithic body having a higher particle aspect ratio compared to the second MOF monolithic body.

[0116] The first MOF monolithic material has a higher particle aspect ratio than the second MOF monolithic material. The first MOF monolithic material may have a larger particle diameter than the second MOF monolithic material.

[0117] In particular, the second MOF monolithic material has a minimum particle diameter and a maximum particle diameter that is approximately the same as or less than that of the first MOF monolithic material.

[0118] In some embodiments, the ratio of the maximum particle diameter of the second MOF monolithic to the minimum particle diameter of the first MOF monolithic may be about 1 or less, for example, about 0.05 to about 0.95, for example, about 0.1 to about 0.75, for example, about 0.15 to about 0.5.

[0119] The maximum and / or minimum particle size of the first and / or second MOF monolithic may refer to particle diameter, particle length, and / or particle width.

[0120] If the first MOF monolithic body has a high aspect ratio, for example, a particle aspect ratio of about 2 or more, and in particular a form having the particle aspect ratio disclosed herein for the first MOF monolithic body (e.g., a typical extruded body), such as a rod form, the minimum particle diameter of the first MOF monolithic body may refer to the particle width.

[0121] When the first MOF monolithic body is prepared using an extrusion method, the minimum particle size, in this specification width / thickness, of the first MOF monolithic body may be based on measurements of the extruded body. Since the extruded body may shrink during drying, the orifice diameter is not necessarily a reliable indicator of the extruded body's thickness. For example, particle dimensions may shrink by about 10% during drying, and as a result, the particle dimensions of the dried extruded body may be about 10% smaller than those of the current body. For clarity, references to particle dimensions of the MOF monolithic body refer to the particle dimensions of the final dried monolithic body. Nevertheless, extruded bodies prepared using a particular orifice will be consistent in their thickness.

[0122] Using the extrusion method, the particle width of the first MOF monolithic body may be about 500 μm or more, for example, about 750 μm or more, for example, about 900 μm or more, for example, about 1 mm or more, for example, about 1 to about 5 mm, for example, about 1 to about 3 mm, or any value disclosed herein with respect to the minimum particle diameter of the first MOF monolithic body.

[0123] The first MOF monolithic body may have a minimum particle diameter, e.g., particle width, of approximately 1 mm or more, approximately 1.5 mm or more, or approximately 2 mm or more, or approximately 0.5 mm to approximately 10 mm, for example, approximately 0.75 mm to approximately 5 mm, for example, approximately 1 to approximately 5 mm, for example, approximately 1 to approximately 3 mm, or approximately 1.5 to approximately 5 mm, for example, approximately 2 to approximately 5 mm, for example, approximately 2 to approximately 4 mm.

[0124] Preferably, the first MOF monolithic body may have a minimum particle diameter of about 1 mm or more.

[0125] More preferably, the first MOF monolithic body may have a minimum particle diameter of about 2 to about 5 mm.

[0126] The first MOF monolithic body may have a maximum particle diameter, e.g., particle length, of about 2 mm or more, for example, about 2 mm to about 100 mm, for example, about 2 mm to about 50 mm, for example, about 2 mm to about 35 mm, for example, about 2 mm to about 30 mm, for example, about 2.25 mm to about 25 mm, for example, about 2.5 mm to about 15 mm, for example, about 2.75 mm to about 10 mm, for example, about 3 mm to about 10 mm.

[0127] Specifically, if the minimum particle size of the first MOF monolithic body is about 1 to about 5 mm, the maximum particle size may be about 2 to about 35 mm, for example, about 3 to about 25 mm, preferably about 3 to about 15 mm. If the minimum particle size of the first MOF monolithic body is about 1.5 to about 5 mm, the maximum particle size may be about 3 to about 35 mm, for example, about 4 to about 25 mm, preferably about 4.5 to about 20 mm. If the minimum particle size of the first MOF monolithic body is about 2 to about 5 mm, the maximum particle size may be about 4 to about 35 mm, for example, about 6 to about 25 mm.

[0128] The second MOF monolithic can typically have a particle aspect ratio close to 1. If the second MOF monolithic has an aspect ratio close to 1 (e.g., about 1 to about 2, e.g., about 1 to about 1.5, e.g., about 1 to about 1.2, e.g., about 1 to about 1.1), the maximum and / or minimum particle diameters of the second MOF monolithic can be essentially the same or close to 1. If the second MOF monolithic has an aspect ratio close to 1, the maximum and / or minimum particle diameters of the second MOF monolithic can refer to the particle diameter.

[0129] The second MOF monolithic body may have a maximum particle diameter less than the minimum particle diameter of the first MOF monolithic body.

[0130] The maximum particle size of the second MOF monolithic body may be approximately 5 mm or less, for example approximately 3 mm or less, for example approximately 1 mm or less, for example approximately 20 μm to approximately 1 mm, 3 mm or 5 mm, or approximately 50 μm to approximately 5 mm, for example approximately 50 μm to approximately 3 mm, for example approximately 100 μm to approximately 2 mm, for example approximately 50 μm to approximately 1 mm, for example approximately 150 μm to approximately 1 mm.

[0131] The minimum particle size of the second MOF monolithic body may be 20 μm or more, for example 50 μm or more, for example approximately 20 μm to approximately 5 mm, for example approximately 50 μm to approximately 5 mm, for example approximately 50 μm to approximately 3 mm, for example approximately 100 μm to approximately 2 mm, for example approximately 50 μm to approximately 1 mm, for example approximately 150 μm to approximately 1 mm.

[0132] In the context of this disclosure, particle diameter may refer to the average particle diameter. Similarly, particle aspect ratio may refer to the average particle aspect ratio.

[0133] In the context of this disclosure, maximum particle diameter may refer to the average maximum particle diameter, i.e., the average of the maximum diameters of the first and / or second MOF monolithic particles.

[0134] In the context of this disclosure, minimum diameter may refer to the average minimum particle diameter, i.e., the average of the minimum diameters of the first and / or second MOF monolithic particles.

[0135] The average particle size(s) and average particle aspect ratio may be determined using methodologies and apparatus well known to those skilled in the art. Further details are provided in the following Methods section.

[0136] Bulk density is not the only parameter important for the gas storage and purification performance of a gas storage container. The gas must be able to flow through the packed bed without excessive pressure drop, thus achieving fast gas kinetics during gas sorption and separation. Therefore, it is important to leave some gaps between the MOF monoliths. This means that the composition should not contain an excessive amount of small particles that could clog all the gaps between the first MOF monoliths. Thus, limiting the proportion of the second MOF monolith in the composition helps to avoid the problem of high pressure drop.

[0137] Since the first monolithic sorbates have shapes and particle aspect ratios that are easy to manufacture on an industrial scale, for example by using extrusion, the composition preferably contains a higher proportion of the first MOF monoliths compared to the second MOF monoliths.

[0138] Furthermore, it is preferable that the composition does not contain MOF monoliths and / or MOF materials with particle sizes that are too small, because very small particles, known as fine particles or microparticles, can clog all the gaps between MOF monoliths. If the composition contains too many MOFs and / or excessively small MOF monolithic particles, it may result in excessive pressure drop and slow gas kinetics during use of the MOF monoliths when filled into gas storage containers. In addition, too many microparticles can generate excessive dust when handling MOF monoliths.

[0139] In the context of this disclosure, MOF materials are understood as MOF monoliths or MOF particles having a particle size of less than approximately 20 μm (i.e., individual fragments of MOF, or MOF in which the majority does not form part of a MOF monolith). For example, MOF particles may consist essentially of MOF (where only small amounts of other substances, e.g., binders, are present).

[0140] The composition may contain MOF material having a particle size of less than about 20 μm, in amounts of about 10% by weight or less, for example, about 5% by weight or less, for example, about 2% by weight or less, for example, about 1% by weight or less, for example, about 0.1% by weight or less, or about 0.01 to about 10% by weight, for example, about 0.05 to about 5% by weight, for example, about 0.1 to about 2% by weight, based on the total weight of the solid composition (i.e., the composition excluding gases, liquids and / or fluids).

[0141] The need to store as much gas as possible in a given volume of gas storage container means that the bulk density of a composition is extremely important. The higher the bulk density, the more material can be packed into the usable working volume. The bulk density of an aggregate of materials is determined by the density of the individual materials (generally defined as envelope density) and how the materials are packed in bulk. Having MOF monolithic bodies with high individual envelope densities is of little significance if they are shaped in such a way that they are packed together inefficiently. Therefore, compositions with high bulk density can provide gas storage containers with high volumetric performance for use in gas storage applications. This may also be related to the surface area of ​​the MOF monolithic body, and for this reason, compositions with high surface area and high bulk density may also have a high surface area / unit volume, thereby resulting in compositions with desirable volumetric performance when used in gas storage containers.

[0142] Bulk density may be defined as the mass of the MOF monolithic bodies divided by the total volume occupied by those MOF monolithic bodies, or in other words, the mass of the composition divided by the total volume occupied by the composition.

[0143] The composition is approximately 0.3 g / cm³. 3 For example, approximately 0.5 g / cm³ 3 For example, approximately 0.6 g / cm³ 3 For example, approximately 0.7 g / cm³ 3 For example, approximately 0.8 g / cm³ 3 For example, approximately 0.9 g / cm³ 3 For example, approximately 0.3 to 3 g / cm³ 3 For example, approximately 0.3 to 1.5 g / cm³ 3 It may have a bulk density.

[0144] To avoid misunderstanding, "bulk density" may refer to either "untapped density" (i.e., the density of a freely settled material or powder) or "tapped density" (i.e., the maximum density achieved when the material is tapped under specific conditions). Preferably, bulk density is tapped density.

[0145] The untapped density and tapped density may be similar. For example, extruded articles typically have a high aspect ratio and a low fill density, and therefore tapping may have little effect on the bulk density.

[0146] To minimize the volume of the MOF monolithic body required for a given gas sorption process, it is preferable that the MOF monolithic body has a high envelope density.

[0147] The envelope density may depend on the crystalline structure of the sorbent and MOF, which may vary depending on the gas storage and separation application; therefore, the envelope density of MOF monoliths may be application-dependent.

[0148] The first and / or second MOF monolithic body contains approximately 0.3 g / cm³. 3 For example, approximately 0.4 g / cm³ 3 For example, approximately 0.6 g / cm³ 3 For example, approximately 0.7 g / cm³ 3 For example, approximately 0.8 g / cm³ 3 For example, approximately 1 g / cm³ 3 For example, approximately 0.3 to 3 g / cm³ 3 For example, approximately 0.4 to 2 g / cm³ 3 It may have an envelope density of [value].

[0149] Furthermore, the relative density of an MOF monolithic is an important parameter for defining the porosity of the MOF monolithic and the accessibility of the pores of the MOF monolithic, which is related to the porosity of the MOF. Relative density may also be defined as the ratio of the envelope density of the MOF monolithic to the crystalline density of the MOF. The crystalline density of an MOF is the theoretical density of a single MOF crystal. The crystalline densities of many MOFs have been calculated and are available in the Cambridge Structural Database (CSD).

[0150] Whether the internal pores of a MOF monolithic material have collapsed during processing is typically indicated by the relative density of the resulting MOF monolithic material. Different MOFs can have different crystal densities depending on their structure. If the envelope density of the MOF monolithic material is greater than the crystal density (i.e., the relative density is >1), this is likely due to the collapse of internal pores. The greater the relative density exceeds 1, the more the internal pores collapse and the lower the sorption capacity. A relative density greater than 1 means a wasteful loss of porosity, as such a high value can only be achieved by destroying some of the useful pores. Therefore, to avoid inefficient internal pore collapse in MOFs, it is preferable that the relative density of the MOF monolithic material not be too high.

[0151] However, the relative density of MOF monolithic materials should not typically be far below 1 because it is volumetrically inefficient. Very low relative densities typically indicate an excess level of undesirable, larger macropores. Relative densities significantly less than 1, e.g., below 0.3, mean the presence of excess porosity, primarily in the form of larger (and therefore unhelpful) pores (i.e., macropores) within the material.

[0152] The first and / or second MOF monolithic may have a relative density of about 0.3 or more, for example, about 0.3 to about 1.7, for example, about 0.5 to about 1.5, or about 0.3 to about 1.3, preferably about 0.7 to about 1.2.

[0153] MOF and binder The MOF of the second MOF monolithic may be the same as or different from the MOF of the first MOF monolithic. Preferably, the MOF of the second MOF monolithic is the same as the MOF of the first MOF monolithic.

[0154] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic may be independently selected from MOFs, and the metal ions of the MOF are selected from elements of groups la, lla, IIIa, IVa-VIIIa, Ib-VIIIb of the periodic table, and mixtures thereof. The metal ions may be selected from Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Ti, Si, Ge, Sn, Pb, As, Sb, Bi, and mixtures thereof. The metal ions may be selected from transition metals, Si, Mg, Al, and mixtures thereof. Preferably, the metal ion is Zr, Zn, Al, Fe, Ti, Nb, Ni, Cu, Mg, Co, Cr, Mn, Si, or mixtures thereof. More preferably, the metal ion is Zr, Zn, Nb, Ni, Cu, Nb, Si, Ti, or mixtures thereof. For example, the metal ion may be selected from the group consisting of: Zn2+ , Zr 2+ Cu 2+ , Al 3+ Mn 2+ Mg 2+ Nb 2+ Fe 2+ Fe 3+ Ti 2+ Ti 3+ Ti 4+ Co 2+ , Cr 2+ Nb 2+ Ni 2+ Ca 2+ , and mixtures and combinations thereof. The metal ions may be provided by salts of metal ions such as ZrCl4.

[0155] In this specification, transition metals can be understood as chemical elements in the d block of the periodic table (i.e., groups 3-12, i.e., Zn, Pd and Pt, as well as Sc and Y).

[0156] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic may be independently selected from zeolite-like imidazolate structures (i.e., ZIFs), mixed metal MOFs, such as Si, Ni, Fe, Ti and / or Zn mixed metal MOFs, and mixtures thereof.

[0157] The organic linker of the MOF may be at least a monodentate organic linker or a derivative thereof. Preferably, the organic linker of the MOF is a monodentate and / or bidentate organic linker, for example, in which the organic linker exists in the MOF in a partially deprotonated or fully deprotonated form. Alternatively, the organic ligand may be a polydentate organic ligand capable of donating two or more electron pairs in a complex formation reaction to form two or more coordinate bonds. One or more organic ligands may contain two or more oxygen and / or nitrogen atoms suitable for donating electron pairs to form two or more coordinate bonds. Preferably, the oxygen atoms may exist as a carboxylate group or a nitro group. Preferably, the nitrogen atoms may exist as an amine group. Typically, the multiple organic ligands may be aromatic carboxylates, aromatic amines, and / or aromatic nitros.

[0158] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic may be independently selected from MOFs comprising organic linkers including carboxylic acids such as dicarboxylic acids, tricarboxylic acids and / or tetracarboxylic acids, azines such as diazines, azoles such as imidazoles and / or triazoles, and mixtures thereof.

[0159] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic are independently fumaric acid, oxalic acid, citric acid, succinic acid, benzenedicarboxylic acid (e.g., terephthalic acid, 1,3-benzenedicarboxylic acid), naphthalenedicarboxylic acid, biphenyldicarboxylic acid (e.g., 4,4'-biphenyldicarboxylic acid (BPDC)), terphenyldicarboxylic acid (e.g., p-terphenyl-4,4''-dicarboxylic acid), azine (e.g., pyrazine), bipyridinedicarboxylic acid (e.g., 2,2'-bipyridine-5,5'-dicarboxylic acid), benzenetricarboxylic acid (e.g., 1,2,3-,1, The MOF may be selected from those comprising organic linkers selected from 2,4- and 1,3,5-benzenetricarboxylic acid (BTC), benzenetetracarboxylic acid, dihydroxyterephthalic acid (e.g., 2,5-dihydroxytephthalic acid (DHBDC)), azoles (e.g., imidazoles (2-methylimidazole, 4,5-dichloroimidazole, 2-imidazole carboxaldehyde, etc.), triazoles (1,2,4-triazole, etc.)), pyrene (e.g., tetrakis(p-benzoic acid)pyrene), porphyrins (e.g., tetrakis(4-carboxyphenyl)porphyrin), and mixtures thereof.

[0160] Preferably, the organic linker of the MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic is independently selected from terephthalic acid, aminoterephthalic acid, 1,3,5-benzenetricarboxylic acid, 2-methylimidazole, oxalic acid, citric acid, 1,2,4-triazole, pyrazine, 2,5-dihydroxyterephthalic acid, and mixtures thereof.

[0161] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic are independently UiO-66, UiO-66-NH2, UiO-67, UiO-68, NU-1000, PCN-222, MOF-808, ZU-301, Zr fumarate, ZIF-8, ZIF-67, ZIF-71 and ZIF-90, Al fumarate, MIL-53, CAU-10, MIL-160(Al) and may be selected from soc-MOF-1, MIL-101 and MIL-100, SIFSIX-3-Ni, TIFSIX-3-Ni, NbOFFIVE-1-Ni, SIFSIX, SIFSIX-2-Cu-i, HKUST-1, ROS-17, UTSA-16, CALF-16, MOF-74 / CPO-27, and mixtures thereof.

[0162] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic may be independently selected from, for example, HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UiO-66-NH2, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, NbOFFIVE-1-Ni, MOF-74 / CPO-27, SIFSIX, and mixtures thereof.

[0163] MOFs may vary depending on the gas storage or purification application and the type of gas or adsorbed species involved. For example, in carbon capture applications, it may be preferable to select an MOF with high uptake and selectivity for carbon dioxide.

[0164] The MOF of the first MOF monolithic and / or the MOF of the second MOF monolithic can be independently selected from MOFs suitable for the type of gas or adsorbed species involved.

[0165] The selection of an MOF may also be based on the environment and conditions to which the MOF monolithic is exposed, as well as the stability of the MOF, such as its thermal stability, chemical stability, and / or mechanical stability. For example, in gas purification and / or storage applications involving high temperatures and / or the presence of certain types of water or steam, it may be preferable to select an MOF with high thermal and chemical stability. For example, for carbon capture from flue gas, the gas stream may contain water, and therefore it may be preferable to select an MOF with high stability against water.

[0166] It is important that MOFs maintain their porosity during processing. MOFs are often not very robust due to the nature of the ligand-metal ion bonds that form the pore structure. These bonds depend more on metal coordination chemistry than on stronger covalent or ionic bonds. By applying external pressure, it is possible to deform and crush the pores of MOFs, thus reducing the surface area of ​​the MOF available for gas sorption. Different MOFs have different stability and strength depending on properties such as the MOF composition and crystal structure.

[0167] For clarity, references to MOFs include derivatives of that MOF, including derivatives of the organolinker and changes in the metal ions and / or metal clusters used, as well as combinations and mixtures thereof. For example, a reference to CPO-27 may include CPO-27-Ni, CPO-27-Mg, CPO-27-Co or other variants (i.e., different metal ions in the MOF), and a reference to UiO-66 may include UiO-66-NH2, UiO-66-Br, UiO-66-OH, or other variants (i.e., different organolinkers in the MOF).

[0168] Furthermore, references to MOFs may include MOFs that are part of the same isoticular series having the same secondary structural units (SBUs) and topology, but with variations in organic linkers, functionalization, and / or pore size. For example, a reference to IRMOF-1 may include IRMOF-8, IRMOF-11, and IRMOF-18 (i.e., those with different organic linker lengths, functionalization, and / or catenation in the MOFs).

[0169] The binder may be any binder capable of providing cohesiveness to the MOF monolithic body, for example, to provide mechanical and chemical stability and robustness.

[0170] The binder for the second MOF monolithic material may be an organic binder, an inorganic binder, or a combination thereof. Preferably, the binder is an organic binder. More preferably, the binder is an organic polymer binder.

[0171] The binder for the first MOF monolithic is an organic binder. Preferably, the organic binder for the first MOF monolithic is an organic polymer binder.

[0172] Preferably, the binder for the first and / or second MOF monolithic is an organic polymer binder.

[0173] More preferably, the binder for the second MOF monolithic is the same as the organic binder (preferably an organic polymer binder) for the first MOF monolithic.

[0174] The binder may not be highly soluble in water, or may be insoluble in water. For example, a hydrophobic binder may advantageously provide hydrophobic properties to the first and / or second MOF monolithic. In this way, when the first and / or second MOF monolithic is used in gas separation and storage applications where the gas stream contains water, the first and / or second MOF monolithic, for example, may preferentially adsorb other gases in the gas stream (e.g., carbon dioxide) over water.

[0175] The binder may be soluble in an aqueous mixture of water and a solvent, or it may be soluble in a non-aqueous solvent.

[0176] The first and / or second MOF monolithic may be modified after synthesis, for example by modifying the binder, to provide the first and / or second MOF monolithic with hydrophobic properties.

[0177] Preferably, when the first and / or second MOF monolithic is prepared with an organic binder using the method of the present disclosure, the solubility of the organic binder in the first solvent is equal to or greater than the solubility of the organic binder in the second solvent. When using this method, the second solvent is added to the first and / or second dry MOF monolithic to remove some of the organic binder from the first and / or second dry MOF monolithic, providing the first and / or second binder-reduced MOF monolithic. Typically, the dissolved organic binder material may diffuse from the first and / or second dry MOF monolithic to the second solvent. Therefore, it is preferable that the solubility of the organic binder is lower in the second solvent than in the first solvent.

[0178] While we do not wish to be bound by theory, the removal of organic binders from the first and / or second dry MOF monolithic is thought to remove the organic binder that is most easily accessible, the one least involved in binding the sorbent particles together, and instead the one most likely to clog the pores of the sorbent within the first and / or second dry MOF monolithic. In this way, first and / or second binder-reduced MOF monolithic can be prepared with a more easily accessible pore system, e.g., a higher BET surface area and higher porosity. Thus, MOF monolithic prepared using this process may have better volumetric performance and, in particular, a more easily accessible pore system that allows for faster gas flow and gas kinetics throughout the MOF monolithic.

[0179] Preferably, the polymeric organic binder is selected from biopolymer materials such as polyvinyl alcohol (PVA), polyethyleneimine, polyvinylpyrrolidone (PVP), polyimide (PI), polyvinyl formal, polyacrylate (including polyacrylic acid), polycarboxylate, polylactic acid, polyethylene glycol, polypropylene glycol, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, polysaccharide rubber including xanthan gum and guar gum, alginates, and chitosan; cellulosic polymers such as cellulose, cellulose acetate, hydroxypropyl methylcellulose (HPMC), methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, and hydroxypropyl methylcellulose (HPMCP); and mixtures thereof. Preferably, the binder is selected from PVA and cellulosic polymers (especially methylcellulose), and mixtures thereof.

[0180] The polymeric organic binder may also be a hydrophobic polymeric organic binder.

[0181] Preparation of MOF monolithic bodies and compositions The composition may be prepared using any suitable preparation process.

[0182] Furthermore, the MOFs in the compositions of the present invention may be manufactured using any process and / or purchased from any commercial source.

[0183] The inventors have developed a method for preparing the compositions of the present invention, which involves extrusion. When these compositions are prepared by these methods and loaded into a gas storage container, for example, they exhibit excellent volumetric and dynamic performance, high volumetric capacity, high gas uptake, and / or high selectivity.

[0184] Forming MOF monolithic bodies using this extrusion method is particularly beneficial because the method has excellent scalability and can be implemented on an industrial scale.

[0185] The method can provide MOF monolithic materials with high MOF content, high microporosity, and low macroporosity, thereby providing excellent volumetric performance for gas storage. Having high microporosity, low macroporosity, and a high BET surface area, there are specific advantages to using MOF monolithic materials containing high levels of MOF in gas storage containers.

[0186] However, extruded articles manufactured on an industrial scale typically have low bulk density due to inefficient filling of the extruded article as a result of the high aspect ratio of the extruded article. The method of the present invention is particularly useful because it is difficult to produce extruded articles with high filling efficiency at industrial speeds.

[0187] By using these methods to prepare MOF monoliths, the generation of fine particles can sometimes be avoided. The main constraint in preparing milled MOF monoliths is the potential for high levels of unwanted fine particles to be generated. This can be a significant problem when implemented on an industrial scale.

[0188] The first and / or second MOF monolithic body may be an extruded body (i.e., in the form of an extruded body) or may be manufactured from an extruded body. Preferably, the first and / or second MOF monolithic body is prepared by extrusion. More preferably, the first MOF monolithic body is an extruded body.

[0189] The term "extruded product" can be understood as particles produced by extrusion.

[0190] The first and / or second MOF monolithic bodies may be prepared by a process that does not involve a milling process.

[0191] While it may be possible to form a composition by combining the raw materials in any order and / or by carrying out the steps in any order, the best results for preparing MOF monolithic bodies are obtained when following the methods of this disclosure described below.

[0192] A method is provided for preparing a composition comprising at least two MOF monolithic bodies, and the method is: a. A step of providing a wetting binder MOF mass, wherein the wetting binder MOF mass is i.MOF and, ii. Based on the total weight of the MOF mass, a first solvent is added in an amount of approximately 50% to approximately 95% by weight, iii. A step of providing an organic binder, wherein the binder may be added as a solution, dispersion, powder, or mixture thereof. b. Optionally, the step of reducing the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass, c. The step of extruding and cutting a wet binder MOF mass or an undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, d. The step of removing at least some of the remaining first solvent from the first undried MOF monolithic to provide the first dried MOF monolithic, e. Optionally, the step of adding a second solvent to the first dried MOF monolithic to remove at least some residual first solvent, at least some arbitrary unreacted reactants, and at least some organic binders from the first dried MOF monolithic to provide an optional first binder-reduced MOF monolithic, f. Optionally, the step of removing at least some second solvent from an optional first binder-reduced MOF monolith to provide an optional first inactivated MOF monolith, g. The step of activating the first dried MOF monolith or an optional first inactivated MOF monolith by exposing it to a temperature of approximately 100°C or higher to provide the first MOF monolith; h. A step of providing a composition by combining a first MOF monolithic body with a second MOF monolithic body, wherein the second MOF monolithic body has a minimum particle diameter of the first MOF monolithic body and a maximum particle diameter that is approximately the same as or less than the minimum particle diameter of the first MOF monolithic body.

[0193] The first solvent may contain one or more substances, for example, one or more solvents. For example, the first solvent may be a single substance (e.g., water or methanol) or a mixture of substances (e.g., water and methanol). Similarly, the second solvent may contain one or more substances. For example, the second solvent may be a single substance (e.g., methanol) or a mixture of substances (e.g., methanol and another substance).

[0194] If the wetting binder MOF mass is too soft or too wet to form a first undried MOF monolithic body (i.e., extrude and cut), step b may be performed to reduce the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass.

[0195] Steps e and f are optional steps. For example, the composition can be prepared without adding or removing a second solvent, in which case at least a portion of the organic binder (and at least a portion of the remaining first solvent and at least a portion of any unreacted reactants) is not removed. In particular, when the first and / or second MOF monolithic is prepared from a specific MOF such as UTSA-16, MOF-808, and / or ZU-301, it may be possible to omit the optional steps e and f of this method. This can simplify the process and thereby result in a faster and / or cheaper preparation method. Preferably, steps e and f are included in this method.

[0196] The first MOF monolithic compound prepared by this method may be combined with the second MOF monolithic compound in step h to provide a composition.

[0197] The second MOF monolithic compound may be added at any step after step c of this method, and does not necessarily have to be added at step h. Preferably, the second MOF monolithic compound is added after step f in the form of a second inactivated MOF monolithic compound, and the first and second inactivated MOF monolithic compounds are activated together.

[0198] The terms “first and / or second MOF monolithic component” and “related first and / or second MOF monolithic component” are used herein to refer to the forms of the first and / or second MOF monolithic in a given method step.

[0199] A method for preparing the composition of the present invention is also provided, and the method is: i. A step of forming a wet metal-organic structure (MOF) reaction mass, wherein the wet metal-organic structure reaction mass comprises an MOF, an unreacted MOF precursor, and a reaction solvent. ii. The step of bringing a wet MOF reaction mass into contact with a binder to form a wet binder mass, iii. A step of partially drying the wet binder mass to form an undried binder MOF mass, iv. A step of forming an undried binder mass into an undried MOF monolithic body, v. The step of removing at least some residual solvent from the undried MOF monolithic to form a dried MOF monolithic, vi. The method includes the step of activating the dried adsorbent by exposing it to a temperature exceeding approximately 100°C to form an adsorbent.

[0200] Preferably, this method is I. Forming a wet MOF reaction mass, the wet MOF reaction mass is i. Based on the total weight of the wet MOF reaction mass, approximately 20% to 70% by weight, or approximately 30% to 60% by weight, or approximately 40% to 50% by weight of MOF, ii. Approximately 3% to 50%, 8% to 40%, or 10% to 30% of the weight of MOF in the wet MOF reaction mass of the unreacted MOF precursor, iii. Formation containing approximately 10% to approximately 70% by weight, preferably approximately 10% to approximately 60%, and preferably less than approximately 10% to approximately 50%, of the weight of the wet MOF reaction mass, II. To provide a wet-binder MOF mass by contacting a wet-MOF reaction mass with an organic binder, III. Optionally, reduce the proportion of reaction solvent in the wet-bonding MOF mass to provide an undried bonding MOF mass. IV. To provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more by extruding and cutting a wet-binder MOF mass or an undried-binder MOF mass, V. To provide a first dried MOF monolithic by removing at least some residual solvent from the first undried MOF monolithic, VI. To provide an optional first binder-reduced MOF monolithic by contacting the first dried MOF monolithic with a washing solvent to remove at least some residual reaction solvent, at least some any unreacted reactants, and / or at least some organic binders from the first dried MOF monolithic, VII. Optionally, to provide an optional first inactivated MOF monolith by removing at least some second solvent from an optional first binder-reduced MOF monolith, VIII. To provide a first MOF monolithic by activating a first dried MOF monolithic or an optional first inactivated MOF monolithic by exposing it to a temperature of approximately 100°C or higher, IX. Providing a composition by combining a first MOF monolithic body with a second MOF monolithic body, wherein the second MOF monolithic body has a minimum particle diameter of the first MOF monolithic body and a maximum particle diameter that is approximately the same as or less than the minimum particle diameter of the first MOF monolithic body.

[0201] The terms “unreacted precursor material” and “reaction by-product” in steps I and ii refer to unreacted material and by-products that are used to prepare the MOF and / or are present in the MOF reaction mixture after the preparation of the MOF, and which are not MOFs themselves.

[0202] The advantage of this method is that the composition and / or the first and / or second MOF monolithic can be prepared using the MOF reaction mixture without washing and / or processing the MOF reaction mixture.

[0203] This approach (i.e., providing a wet MOF mass, and / or contacting the wet MOF mass with an organic binder to provide a wet-binder MOF mass) may be used in any of the methods of the present invention.

[0204] The second MOF monolithic of the composition of the present invention may be prepared using a similar method described herein, or it may be provided by another source. For example, the second MOF monolithic can be obtained from a commercially available source.

[0205] In this way, a second MOF monolithic having a different composition and / or properties can be combined with the first MOF monolithic. This can result in a composition having excellent volumetric performance, dynamic performance, and stability.

[0206] Preferably, step (I) is carried out by bringing metal-organic structure precursor materials, preferably two or more metal-organic structure precursor materials, into contact with a reaction solvent to form a wet MOF reaction mass. Preferably, at least some of the precursor materials are in solid form. Preferably, no further reaction steps are taken after contact with each other. Preferably, the wet MOF reaction mass is not subjected to any washing or concentration steps. Preferably, the wet MOF reaction mass is not subjected to any solvent exchange process. Preferably, the wet MOF reaction mass is used immediately after preparation.

[0207] The preferred conditions for this catalytic reaction are well within the scope of the art of those skilled in the art. For example, the catalytic reaction may be carried out at a temperature below about 100°C, e.g., between about 20°C and about 100°C, or between about 50°C and about 90°C, for a period of more than about 30 minutes, or more than about 1 hour, or more than about 2 hours, or more than 4 hours, or less than about 2 days, or less than about 1 day, or less than 18 hours, and optional shearing may be performed during the reaction period to form a wet metal-organic structural reaction mass.

[0208] Suitable equipment includes sigma-type or Z-blade type high-torque mixers or helical screw type mixers. Strong shearing helps to improve the uniformity of the mixture and can reduce the resulting particle size. Alternatively, equipment such as Hosokawa Micron's cyclomixers can also be used.

[0209] The conditions of the reaction mixture forming the wet MOF reaction mass, such as the type and concentration of the solvent, temperature, and reaction time, can be varied to allow for the formation of a very wide range of different MOFs in high yield. Equipment such as twin-screw extruders are undesirable due to their short residence times, which limit the flexibility of the process and the range of MOFs that can be produced. It is preferable that steps (I) and (II), and preferably (III), can all be carried out in the same reaction vessel.

[0210] One option is to mix different precursors with a portion of the reaction solvent and then add the individual precursors together with stirring. For example, ZU-301 can be prepared by (i) preparing a dispersion / slurry of basic zinc carbonate in water by heating and stirring, (ii) dissolving oxalic acid and 3-methyl-1,2,4-triazole in a water / ethanol mixture, and (iii) adding the ligand solution to the zinc carbonate dispersion / slurry over several hours at high temperature with thorough stirring.

[0211] The wet MOF reaction mass may have a solids content of approximately 20% to 75% by weight, or approximately 25% to 60% by weight, or approximately 30% to 50% by weight. Conventional adsorbent synthesis via diluted sol-gels can only achieve a solids content of 8% by weight or less, but the process of the present invention can achieve a high solids content without requiring centrifugation. The reaction mass is kept under reaction conditions for a sufficient time to ensure that the majority of the precursor has reacted.

[0212] Step (II) involves contacting the wet MOF reaction mass with a binder, preferably a polymeric organic binder, to form a wet binder MOF mass.

[0213] The binder can be added in solution (if soluble in a suitable solvent), as a solid (preferably a fine powder), or as a slurry / dispersion in a suitable solvent. A preferred method is to add the binder as a partially solvated powder. Alternatively, the binder may be in the form of a finely dispersed dry powder. Partial pre-solvation of the binder increases the interaction and effectiveness of the binder with the wet MOF reaction mass compared to addition as a pure powder, and limits the amount of extra solvent required. Adding a soluble organic polymer binder as a solution can be very effective for the dispersion and subsequent performance of the binder (and thus limits the amount required), but significantly increases the amount of solvent that needs to be removed afterward. The binder is typically mixed with the wet MOF reaction mass and mixed for a long time to ensure homogeneity.

[0214] The binder, preferably a polymeric organic binder, can be partially solvated by pre-mixing it with one or more solvents selected from the group consisting of water, DMSO, short-chain alcohols (C1-C4) including methanol, ethanol, and propanol, short-chain (C1-C4) organic acids including formic acid and acetic acid, glycols, and mixtures thereof.

[0215] The binder may be added to the wet MOF reaction mass in an amount of about 0.5% to about 30%, or about 1% to about 25%, or about 5% to about 20%, or about 10% to about 15%, relative to the weight of the MOF in the wet MOF reaction mass.

[0216] The binder may be provided as a binder solution or dispersion of about 67% by weight; for example, 20 g of the binder is added to 30 g of the solvent. Optionally, the binder may be provided as a binder solution or dispersion of about 4% to 70% by weight, or about 10% to 50% by weight, or about 30% to 40% by weight.

[0217] The binder is brought into contact with the wet MOF reaction mass at a binder-to-MOF ratio of approximately 1:19, 1:15, 1:12, 1:7, 1:5, 1:4, or 1:3.

[0218] Preferably, step (II) follows immediately after step (I).

[0219] Step (III) partially dries the wet binder mass to form an undried binder mass. Step (III) removes at least some (but not all) of the reaction solvent from the wet binder mass to form an undried binder mass.

[0220] Step (III) can be achieved in several different ways. The wet binder mass can be further dried before cutting. This can be done, for example, with a wiped film evaporator or a heated high-torque mixer, and the resulting undried binder mass is then cut to form smaller objects. The wet binder mass can be dried on a flat surface to form an undried binder mass, which is then cut with a cutting mill or flake or other suitable cutting device. An example of such a method is to remove at least some, but not all, of the reaction solvent from the wet binder mass (e.g., by evaporation) to form an undried binder mass.

[0221] For example, step (III) can be carried out by (i) evaporation of the solvent and / or (ii) addition of an adsorbent material having a lower solvent level than the wet binder mass to the wet binder mass, the adsorbent material being selected from one or more of silica, zeolite, activated carbon, graphene, metal-organic structures, or combinations thereof.

[0222] Preferably, step (III) is carried out at a temperature of about 20°C to about 80°C, or about 40°C to about 60°C, for at least about 1 day, or at least about 2 days, or at least about 3 days.

[0223] Typically, the undried binder mass formed by the reduction of the reaction solvent level in step (III) is 10s -1 And at 25℃, approximately 3.0 × 10 5 mPa.s ~ approximately 3.0 × 10⁻¹⁰ 6 It has a viscosity of mPa·s. For example, the undried binder mass is 10s before any cutting step. -1 And at 25℃ > approximately 4.0 × 10 5 It may have a viscosity of mPa·s. The undried binder mass retains enough solvent to be deformable under pressure and impact, and can be rounded, for example, in a spheronizer. Typically, the viscosity of the undried binder mass is 10s. -1 And at 25℃, approximately 1.25 × 10 6 It is less than mPa·s.

[0224] Optionally, steps (II) and (III) may be performed simultaneously or sequentially.

[0225] Step (IV) is performed by extrusion and cutting. The undried MOF monolithic body typically has the same composition as the undried binder MOF mass.

[0226] Step (V) removes at least some residual solvent from the undried MOF monolithic (optionally washed adsorbent) to form a dried MOF monolithic. Step (e) may be carried out by gradually drying at a temperature below approximately 100°C, or below approximately 60°C, below approximately 40°C, or even at ambient temperature.

[0227] Optionally, the dried MOF monolithic material may be brought into contact with a washing solvent to remove unreacted material and / or reaction by-products and form a washed MOF monolithic material. This washing step may be performed once or more times. The washing solvent may be the same as the reaction solvent or may be different from the reaction solvent.

[0228] Step (VIII) activates the dried MOF monolithic material and forms an adsorbent by exposing the inactivated MOF monolithic material to a temperature above approximately 100°C, preferably under vacuum. Preferably, step (VIII) follows immediately after step (V or VII). Step (V or VII) can optionally be incorporated as the first part of step (VIII).

[0229] The wet MOF reaction mass is formed in step (I) and is a mixture of MOF material, residual unreacted MOF precursor and reaction solvent, and any reaction by-products. The term “unreacted MOF precursor” is used herein to describe all solid materials in the wet MOF reaction mass that are not MOF. The wet MOF reaction mass comprises (i) about 20% to about 70% metal-organic structure relative to the weight of the wet metal-organic structure reaction mass, (ii) about 3% to about 50% unreacted MOF precursor relative to the weight of MOF in the wet metal-organic structure reaction mass, and (iii) about 10% to about 70% reaction solvent relative to the weight of the wet metal-organic structure reaction mass.

[0230] Preferably, the wet structure mass contains about 20% to about 70%, or about 40% to about 60%, of the weight of the wet metal-organic structure reaction mass. Preferably, the wet MOF reaction mass contains about 3% to about 50%, or about 10% to about 25%, of the weight of the MOF in the wet MOF reaction mass, of the unreacted MOF precursor. Preferably, the wet MOF mass contains about 10% to about 70%, or about 20% to about 66%, or about 30% to about 60%, of the weight of the wet metal-organic structure reaction mass, of the reaction solvent. Preferably, the wet structure mass contains about 10% to about 50%, or less than about 20% to about 50%, of the reaction solvent, of the weight of the wet metal-organic structure reaction mass.

[0231] Preferably, the wet structural mass is not subjected to one or more washing and re-concentration steps after the initial formation.

[0232] When preparing a composition comprising at least two MOF monolithic bodies, when the second MOF monolithic body is prepared from the first MOF monolithic body (for example, by grinding the first MOF monolithic body), the composition may be obtained using the method of the present invention including an additional step of grinding some of the first dry MOF monolithic body to provide the second dry MOF monolithic body, and the second dry MOF monolithic body has a maximum particle size approximately equal to or less than the minimum particle size of the first dry MOF monolithic body.

[0233] Typically, the grinding step is performed after the extrusion step and before the activation step. For example, the grinding step can be carried out at any suitable point between extrusion and activation. As an example, grinding can be performed before or after removing at least some of the remaining first solvent or reaction solvent. As another example, grinding can be carried out before or after the optional use of a second solvent or washing solvent.

[0234] For example, the process is 1. Providing a wet binder MOF mass, wherein the wet binder MOF mass i. MOF, and ii. Based on the total weight of the wet binder MOF mass, about 50 wt% to about 95 wt% of a first solvent, and iii. An organic binder, wherein the binder may be added as a solution, dispersion, powder, or a mixture thereof, including providing; 2. Optionally, reducing the proportion of the first solvent in the wet binder MOF mass to provide an undried binder MOF mass; 3. Extruding and cutting the wet binder MOF mass or the undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more; 4. Removing at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dry MOF monolithic body; 5. To provide a second dried MOF monolithic body by grinding several first dried MOF monolithic bodies, wherein the second dried MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first dried MOF monolithic body. 6. Optionally, to provide optional first and second binder-reduced MOF monolithic materials by adding a second solvent to the first and second dried MOF monolithic materials to remove at least some of any residual first solvent, at least some of any unreacted reactants, and at least some of the organic binder from the first and second dried MOF monolithic materials. 7. Optionally, remove at least some of the second solvent from optional first and second binder-reduced MOF monoliths to provide optional first and second inactivated MOF monoliths. 8. Providing a composition comprising a first MOF monolithic and a second MOF monolithic by activating a first and second dried MOF monolithic or an optional first and second inactivated MOF monolithic by exposing the first and second dried MOF monolithic or an optional first and second inactivated MOF monolithic to a temperature exceeding approximately 100°C, wherein the second MOF monolithic has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first MOF monolithic.

[0235] Steps 6-8 may be carried out together for the first and second MOF monolithic components (i.e., for a mixture of the first and second MOF monolithic components), or the steps may be carried out separately for the first and second monolithic components (i.e., individually for the first and second MOF monolithic components). The first and second MOF monolithic components may be combined in either step 6 or 7, and in step 8, they may be combined before or after the activation process.

[0236] As mentioned above, the addition and removal of the second solvent are optional, so steps 6 and 7 are optional steps and may or may not be included.

[0237] When preparing a composition containing at least two MOF monoliths, if the second MOF monolith is prepared from the first MOF monolith, the composition is prepared in the following steps: i. A step of providing a wetting binder MOF mass, wherein the wetting binder MOF mass is a. MOF and, b. Based on the total weight of the MOF mass, a first solvent is added in an amount of approximately 50% to approximately 95% by weight, c. A step comprising providing an organic binder, wherein the binder may be added as a solution, dispersion, powder, or mixture thereof. ii. Optionally, the step of reducing the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass, iii. The step of extruding and cutting a wet binder MOF mass or an undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, iv. The step of removing at least some of the remaining first solvent from the first undried MOF monolithic to provide the first dried MOF monolithic, v. A step of providing a first binder-reduced MOF monolithic by adding a second solvent to the first dried MOF monolithic in order to remove at least some of any residual first solvent, at least some of any unreacted reactants, and at least some of the organic binder from the first dried MOF monolithic, vi. A step of providing a second binder-reduced MOF monolithic body by grinding several first binder-reduced MOF monolithic bodies, wherein the second binder-reduced MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first binder-reduced MOF monolithic body. vii. The step of removing at least some of the second solvent from the first and second binder-reduced MOF monoliths to provide the first and second inactivated MOF monoliths, viii. Alternatively, this may be obtained by following a method of the present invention comprising the step of activating the first and second inactivated MOF monoliths by exposing them to a temperature of about 100°C or higher, and providing a composition comprising the first MOF monolith and the second MOF monolith, wherein the second MOF monolith has a minimum particle diameter of the first MOF monolith and a maximum particle diameter of approximately that or less.

[0238] Steps vii and viii may be performed together for the first and second MOF monolithic components (i.e., for a mixture of the first and second MOF monolithic components), or the steps may be performed separately for the first and second MOF monolithic components (i.e., for each individual first and second MOF monolithic component). The first and second MOF components may be combined in steps vii and / or viii, and in step viii they may be combined before or after the activation process.

[0239] Other methods of the present invention may be adapted to include a grinding step in a similar manner. The grinding step may be performed at any stage after the extrusion step, preferably after the drying step (i.e., after the removal of the first solvent or reaction solvent and / or the removal of an optional second solvent or washing solvent), for example, the grinding may be performed on an undried first MOF monolithic, a first dried MOF monolithic, a first binder-reduced MOF monolithic, a first inactivated MOF monolithic and / or a first activated MOF monolithic. Preferably, the grinding step is performed on the first dried MOF monolithic and / or the first binder-reduced MOF monolithic.

[0240] The grinding step may be carried out in multiple stages of the disclosed method, for example, in both the first dried MOF monolith and the first binder-reduced MOF monolith.

[0241] A second MOF monolithic material may be prepared by milling and / or sieving a portion of the first MOF monolithic material. The composition may then be prepared by combining the first MOF monolithic material and the second MOF monolithic material, the second MOF monolithic material being formed by milling and / or sieving a portion of the first MOF monolithic material.

[0242] A preferred method for producing a second MOF monolithic is to grind or mill a portion of the first dried MOF monolithic and / or the first binder-reduced MOF monolithic to produce a second dried MOF monolithic and / or the second binder-reduced MOF monolithic. The same steps performed for the first dried MOF monolithic and / or the first binder-reduced MOF monolithic to produce the first MOF monolithic component may also be performed for the second dried MOF monolithic and / or the first binder-reduced MOF monolithic. These steps, or some of these steps, may be performed separately for the first and second MOF monolithic components, or the steps may be performed on a mixture of the first and second MOF monolithic components.

[0243] Typically, such extruded products are ground or milled after they have dried and before they are activated.

[0244] A suitable apparatus for grinding or milling extruded bodies is the Retsch SM300 cutting mill. The milled material can be directly blended with the first extruded body aggregate or sieved before addition. After separation techniques such as sieving, the material is too large to be returned to the mill for recycling.

[0245] The milled material may also be sieved to remove very small particles (i.e., fine particles) with a particle size of approximately 50 μm or less, or approximately 150 μm or less, before being blended with the first MOF monolithic component. Removing such fine particles makes it possible to avoid dust when handling the MOF monolith and / or composition. The fine particles can optionally be recycled into the MOF and / or MOF monolithic synthesis process.

[0246] MOF monolithic materials can be separated from the composition by sieving using a sieve with a mesh size approximately equal to or slightly smaller than the measured particle size of the MOF monolithic material. The nearest Tyler or US mesh size can be used. For example, for any particles that pass through the sieve by passing through the mesh head-on, a limited number of particles can be optionally and easily removed from the second MOF monolithic material by manual and visual inspection.

[0247] The proportion of the second MOF monolithic material in the composition can be determined by using a sieve having a mesh size approximately equal to or less than the minimum particle size of the first MOF monolithic material.

[0248] Typically, in the extrusion step of this method, the wet binder MOF mass or the undried binder MOF mass is extruded through an extruder having an orifice diameter of about 1 to about 5 mm.

[0249] In the step of adding a second solvent to the first dried MOF monolithic body (i.e., steps e and v), or adding a second solvent to the first and second dried MOF monolithic bodies (i.e., step 6) of a method, at least some of any remaining first solvent and at least some of any unreacted reactants are removed. Preferably, all of the remaining first solvent and unreacted reactants are removed, although in particular within the pores of the MOF monolithic body components, some of any remaining first solvent and some of any unreacted reactants may remain.

[0250] In the step of a method that includes adding a second solvent to the first dried MOF monolithic body (i.e., steps e and v), or adding a second solvent to the first and second dried MOF monolithic bodies (i.e., step 6), the amount of organic binder removed from the first dried MOF monolithic body or the first and / or second dried MOF monolithic bodies can vary.

[0251] For example, the second solvent can remove less than about 20 wt% of the organic binder from the first dried MOF monolithic body and the first and / or second dried MOF monolithic bodies, based on the total weight of the organic binder in each object.

[0252] For example, the second solvent can remove more than about 20 wt% of the organic binder from the first dried MOF monolithic body and the first and / or second dried MOF monolithic bodies, based on the total weight of the organic binder in each object.

[0253] The second solvent can remove up to about 15 wt%, such as up to about 10 wt%, such as up to about 5 wt% of the organic binder, based on the total weight of the remaining first solvent, unreacted reactants, and organic binder in each object.

[0254] Partial removal of the organic binder from a dried MOF monolithic is thought to result in a first and / or second MOF monolithic having a preferred porosity profile, for example, with improved levels of micropores and mesopores and a low level of macroporosity.

[0255] Furthermore, the above method is particularly advantageous because it does not require pre-drying of the MOF before using it to prepare MOF monoliths and / or compositions. For example, the wetting binder MOF mass may be provided immediately after the synthesis of the MOF, and the MOF and the first solvent are part of the MOF synthesis process. In this case, only the binder needs to be added. Thus, the MOF does not need to be pre-dried before use in the above method, thereby making the process more efficient and cost-effective.

[0256] Use of the composition The compositions of the present invention can be used for purposes such as gas extraction or gas capture. They can also be used for gas storage and / or gas delivery. For example, the compositions of the present invention may be used to extract, capture, store, and / or deliver gases such as waste gases from industrial processes. The compositions can be used to extract, capture, store, and / or deliver gases such as carbon dioxide from flue gases.

[0257] The compositions of the present invention may also be used to extract, capture, store, and / or deliver other gases or fluids such as hydrogen, krypton, methane, or water.

[0258] After use of the compositions of the present invention for gas capture, storage, and / or delivery, they may be regenerated and recycled for further and / or repeated use. For example, the compositions may be regenerated by activation to remove any remaining gases and / or adsorbents, and then recycled or reused for either the same or different applications.

[0259] gas-containing composition The compositions of the present invention may further contain gases such as carbon dioxide, hydrogen, krypton, methane, water, and mixtures thereof, preferably selected from carbon dioxide, hydrogen, krypton, methane, and mixtures thereof.

[0260] Those skilled in the art will understand that any suitable MOF can be selected for use in the composition (i.e., the MOF is suitable for the type of gas, adsorbent species, and / or application).

[0261] The composition may further contain hydrogen. If the composition further contains hydrogen, the first and / or second MOF monolithic may contain any suitable MOF. Preferably, the first and / or second MOF monolithic independently contains MOFs selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, and mixtures thereof.

[0262] The composition may further contain carbon dioxide. If the composition further contains carbon dioxide, the first and / or second MOF monolithic may contain any suitable MOF. Preferably, the first and / or second MOF monolithic independently contains MOFs selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, and mixtures thereof.

[0263] The composition may further contain krypton. If the composition further contains krypton, the first and / or second MOF monolithic may contain any suitable MOF. Preferably, the first and / or second MOF monolithic independently contains MOFs selected from MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, for example, MOF-74, more preferably MOF-74-Mg.

[0264] The composition may further contain methane. If the composition further contains methane, the first and / or second MOF monolithic may contain any suitable MOF. Preferably, the first and / or second MOF monolithic independently contains HKUST-1.

[0265] The composition may further contain water. If the composition further contains water, the first and / or second MOF monolithic may contain any suitable MOF. Preferably, the first and / or second MOF monolithic independently contains MOFs selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, aluminum fumarate, and mixtures thereof.

[0266] In some embodiments, the solid components of the first and / or second MOF monolithic body may consist essentially, or more specifically, of the MOF and a binder.

[0267] In a further embodiment, the solid component of the composition may consist essentially, or more specifically, of a first and / or second MOF monolithic body.

[0268] The term "solid components" may refer to solid materials other than liquids and / or gases (i.e., MOFs, MOF monoliths, and / or materials not adsorbed in and / or on the composition).

[0269] In other embodiments, the composition and / or the first and / or second MOF monolithic body may substantially contain no solid components other than the MOF and binder.

[0270] The term "substantially contained" means that the composition and / or the first and / or second MOF monolithic body contain less than 5% by weight, 4% by weight, 3% by weight, 2% by weight, or 1% by weight, for example, less than 0.5% by weight or 0.1% by weight, solid components other than MOF and binders.

[0271] Use of composition in gas storage containers A gas storage container comprising a composition is provided according to a further aspect of the present invention.

[0272] Gas storage containers may have a non-spherical shape.

[0273] The gas storage container may further include one or more of the following: a. Insulation material for exterior walls, b. Means for heating and cooling the composition, c. Internal baffle, d. Means for restraining the composition in a predetermined position, e. The composition is positioned at least 10 cm from the outer wall (this reduces temperature loss). f. Means for monitoring pressure and / or temperature, and / or g. A valve for controlling the flow of gas in and out.

[0274] Use of composition and / or gas storage container A further aspect of this disclosure provides the use of a gas storage container comprising the composition for gas intake, storage and / or release.

[0275] A further aspect of the present invention provides for the use of a composition for gas intake, storage, and / or release.

[0276] These uses are described below with reference to the use of gas storage containers containing compositions for gas intake, storage, and / or release. Those skilled in the art will understand that this description is also applicable and illustrative to the use of compositions for gas intake, storage, and / or release (whether contained in gas storage containers or not).

[0277] For example, a gas storage container can be used in a method that includes the following steps: a. Step of filling the gas storage container with gas, b. The step of storing the gas in a gas storage container, and / or c. The step of releasing gas from the gas storage container.

[0278] The steps of this method may be performed in any order, and this method may include one or more of these steps.

[0279] For example, compositions within gas storage containers can be used as part of gas purification, storage, and capture processes using any suitable technology, such as pressure swing (PSA) or temperature swing (TSA) adsorption processes and their variations such as VPSA (vacuum pressure swing adsorption).

[0280] Such a process operates by altering the pressure and / or temperature within a gas storage container so that the target gas (e.g., hydrogen, carbon dioxide, methane, water, and / or krypton) is adsorbed by or desorbed from a monolithic body.

[0281] For example, to fill and store hydrogen in monolithic particles, hydrogen gas is introduced into a container at high pressure (typically >5 bar) and low temperature (e.g., below 100K). This lowers the temperature of the MOF material and MOF monoliths, aiding in the adsorption of hydrogen onto the MOF or monolith. The cooled and pressurized hydrogen is typically supplied to the storage container until the pressure in the container reaches or approaches the pressure and temperature of the incoming gas. The monoliths are then filled with hydrogen and can be stored until needed. To remove hydrogen from the storage container, one or more valves are opened to allow the release of the pressurized gas. As the pressure decreases, the hydrogen desorbs from the MOF surface and can be removed through the valves. To aid in gas removal, heat can be applied to raise the temperature of the monolith and lower the pressure. Similar approaches are used for other gases such as methane, but the optimal pressure and temperature for adsorption and desorption differ depending on the gas.

[0282] The container can also be used as part of a purification or capture process. As part of a carbon capture process, a gas stream to be separated, such as a flue gas containing carbon dioxide or a gas stream containing krypton, passes through the gas storage container at high pressure and low temperature, e.g., >5 bar and about 20°C, e.g., ambient temperature. The target gas, e.g., carbon dioxide or krypton, is then adsorbed by an MOF monolithic body selected for its high selectivity for that gas compared to other components of the gas stream. The gas discharged from the gas storage container is depleted in the target gas and can be sent for further processing or released into the atmosphere. When the MOF is saturated with the target gas and adsorption stops, the gas stream is stopped. The adsorbed target gas, such as carbon dioxide or krypton, can then be desorbed from the MOF by any preferred method, such as raising the temperature of the MOF composition by using a heater, for example, in a TSA process, or lowering the pressure in the storage container by opening a valve and / or using a pressure pump, or both, in a PSA process. The target gas can be withdrawn through the opened valve and sent for further processing, such as underground capture.

[0283] Such processes may also be applicable to the extraction and / or storage of water, such as the extraction of water from the air. For example, moisture or water in the air (e.g., humid air or water vapor) may be captured, stored, and / or released by a gas storage container containing the composition. Thus, references to gases disclosed herein may also include water, moisture, and / or water vapor.

[0284] This composition is particularly suitable for gas sorption and storage for various gas separation and purification applications. Due to the porous nature of the MOF monolithic bodies in the composition, as well as other properties such as high bulk density, they are particularly suitable for exhibiting high volumetric gas capacity, which is important for gas storage and separation applications.

[0285] Those skilled in the art will understand that any suitable MOF can be selected for use in the composition, which is used for gas intake, storage and / or release (whether or not it is in a gas storage container).

[0286] MOFs may be selected based on their composition and / or the intended use of the gas storage container. For example, MOFs may have chemical compositions, porosity, pore size, etc., that are particularly suitable for specific gas storage and separation applications.

[0287] The gas may include hydrogen, carbon dioxide, methane, krypton, water, or mixtures thereof, for example, hydrogen, carbon dioxide, methane, krypton, or mixtures thereof.

[0288] Gas intake and / or release, a. Pressure swing process, and / or b. This can be achieved by a temperature swing process.

[0289] Gas storage containers can be used as part of a gas purification process.

[0290] Use for hydrogen storage If the gas contains hydrogen, for example, if the gas is hydrogen, the first and / or second MOF monolithic may contain any suitable MOF, preferably the first and / or second MOF monolithic independently contains MOFs selected from HKUST-1, ZIF-8, MOF-808, UiO-66, and mixtures thereof.

[0291] These MOFs are suitable for hydrogen uptake, storage, and release, and when used in the compositions of the present invention, they exhibit excellent performance, such as volumetric performance and cycle life.

[0292] If the gas contains hydrogen, for example, if the gas is hydrogen and the first and / or second MOF monolithic body contains any suitable MOF, preferably an MOF independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, and mixtures thereof, the temperature of the composition may vary from about -200 to about -100°C during intake and / or release of the gas. When the temperature is about -200°C, the pressure in the gas storage container may be about 10 bar or more. When the temperature is about -100°C, the pressure in the gas storage container may be about 1 bar or less.

[0293] If the gas contains hydrogen, for example, if the gas is hydrogen and the first and / or second MOF monolithic body contains any suitable MOF, preferably an MOF independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66 and mixtures thereof, the composition is approximately 0.4 to approximately 1.1 g / cm³ at 77 K and 10 atm. 3 For example, approximately 0.5 to 0.9 g / cm³ 3 For example, approximately 0.6 to 0.8 g / cm³ 3 MOF, and approximately 0.025 to 0.09 g / cm³ 3 For example, approximately 0.033 to 0.075 g / cm³ 3 For example, approximately 0.04 to 0.065 g / cm³ 3 It may contain the bulk volume composition of hydrogen.

[0294] Use in carbon dioxide storage If the gas contains carbon dioxide, for example, if the gas is carbon dioxide, the first and / or second MOF monolithic body may contain any suitable MOF, preferably one independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof. More preferably, the MOF is ZU-301 and / or UTSA-16. ZU-301 and UTSA-16 have demonstrated properties such as high volumetric performance, fast gas kinetics, and good stability, making them particularly suitable for carbon dioxide capture in flue gas purification applications.

[0295] If the gas contains carbon dioxide, for example, if the gas is carbon dioxide and the first and / or second MOF monolithic body contains any suitable MOF, preferably one independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof, the temperature of the composition may vary from about 0 to about 100°C during gas intake and / or release. When the temperature is about 20°C, the pressure in the gas storage container may be about 5 bar to about 10 bar. When the temperature is about 70°C, the pressure in the gas storage container may be about 1 bar or less.

[0296] If the gas contains carbon dioxide, for example, if the gas is carbon dioxide and the first and / or second MOF monolithic body contains any suitable MOF, preferably one independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof, then the composition has a concentration of about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 For example, approximately 0.5 to 0.9 g / cm³ 3 For example, approximately 0.6 to 0.8 g / cm³ 3 MOF, and approximately 0.03 g / cm³ 3 ~Approx. 0.14g / cm 3 For example, approximately 0.04 g / cm³ 3 ~Approx. 0.12g / cm3 For example, approximately 0.05 to 0.1 g / cm³ 3 It may contain the bulk volume composition of carbon dioxide.

[0297] If the gas entering the gas storage container contains carbon dioxide, the carbon dioxide content in the gas can range from approximately 0.1% to approximately 10% by weight, based on the total weight of the gas.

[0298] If the gas entering the gas storage container contains carbon dioxide, the carbon dioxide content in the gas can be approximately 10 to 70% by weight, based on the total weight of the gas.

[0299] Use for krypton storage If the gas contains krypton, for example, if the gas is krypton, the first and / or second MOF monolithic body may contain any suitable MOF, preferably MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, for example, an MOF independently selected from MOF-74, more preferably MOF-74-Mg.

[0300] If the gas contains krypton, for example, if the gas is krypton and the first and / or second MOF monolithic body contains any suitable MOF, preferably MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, for example, an MOF independently selected from MOF-74, preferably MOF-74-Mg, then the temperature of the composition may vary from about 0 to about 100°C during gas intake and / or release. If the temperature is about 20°C, the pressure in the gas storage container may be about 5 bar or more. If the temperature is about 100°C, the pressure in the gas storage container may be about 1 bar or less.

[0301] If the gas entering the gas storage container contains krypton, the krypton content of the gas may be approximately 90-99% by weight, based on the total weight of the gas.

[0302] If the gas contains krypton, for example, if the gas is krypton and the first and / or second MOF monolithic body contains any suitable MOF, preferably MOF-74, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, for example MOF-74, preferably MOF-74-Mg, then the composition has a concentration of about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 For example, approximately 0.5 to 0.9 g / cm³ 3 For example, approximately 0.6 to 0.8 g / cm³ 3 MOF, and approximately 0.03 g / cm³ 3 ~Approx. 0.14g / cm 3 For example, approximately 0.04 g / cm³ 3 ~Approx. 0.12g / cm 3 For example, approximately 0.05 to 0.1 g / cm³ 3 This may include the bulk volume composition of krypton.

[0303] Use for methane storage If the gas contains methane, for example, if the gas is methane, the first and / or second MOF monolithic body may contain any suitable MOF, preferably an MOF independently selected from HKUST-1.

[0304] If the gas contains methane, for example, if the gas is methane and the first and / or second MOF monolithic body contains any suitable MOF, preferably an MOF independently selected from HKUST-1, the temperature of the composition may vary from about 0 to about 100°C during gas intake and / or release. When the temperature is about 20°C, the pressure in the gas storage container may be about 5 bar or more. When the temperature is about 95°C or more, the pressure in the gas storage container may be about 1 bar or less.

[0305] If the gas contains methane, for example, if the gas is methane and the first and / or second MOF monolithic body contains any suitable MOF, preferably an MOF independently selected from HKUST-1, the composition should be about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm.3 For example, approximately 0.5 to 0.9 g / cm³ 3 For example, approximately 0.6 to 0.8 g / cm³ 3 MOF and approximately 0.03 g / cm³ 3 ~Approx. 0.14g / cm 3 For example, approximately 0.04 g / cm³ 3 ~Approx. 0.12g / cm 3 For example, approximately 0.05 to 0.1 g / cm³ 3 It may include the bulk volume composition of methane.

[0306] Used for collecting water If the gas contains water (e.g., humid air), for example, if the gas is water (e.g., water vapor), the first and / or second MOF monolithic body may contain any suitable MOF, preferably independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-NI, UiO-66-NH2, MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, aluminum fumarate, and mixtures thereof, preferably MOF-808.

[0307] Water extraction can be performed by directly capturing water from the air. For example, the intake step may involve water adsorbed onto the composition at high humidity (e.g., high relative humidity, RH, e.g., about 60 to about 100% RH) and / or low temperature (e.g., about -40 to about 30°C). The release step may involve water desorbed from the composition at low humidity (e.g., low RH, such as about 0 to about 40% RH) and / or high temperature (e.g., about 40 to about 80°C).

[0308] When the gas contains water, for example, when the gas is water and the first and / or second MOF monolithic body contains any suitable MOF, preferably, independently, HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, aluminum fumarate, and mixtures thereof, preferably MOF-808, the temperature of the composition may vary from about 0 to about 100 °C during gas uptake and / or release. When the temperature is about 20 °C, the pressure in the gas storage container may be about 5 bar or more. When the temperature is about 95 °C or higher, the pressure in the gas storage container may be about 1 bar or less.

[0309] When the gas contains water, for example, when the gas is water and the first and / or second MOF monolithic body contains any suitable MOF, preferably, independently, HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, aluminum fumarate, and mixtures thereof, preferably MOF-808, the composition is at 293K, 5 atm, about 0.4 to about 1.1 g / cm 3 , for example, about 0.5 to about 0.9 g / cm 3 , for example, about 0.6 to about 0.8 g / cm 3 of MOF and about 0.03 g / cm 3 ~ about 0.14 g / cm 3 , for example, about 0.04 g / cm 3 ~ about 0.12 g / cm 3 , for example, about 0.05 to about 0.1 g / cm 3 and may include a bulk volume composition of, for example, about 0.05 to about 0.1 g / cm.

Brief Description of the Drawings

[0311] Test method Microporous and mesoporous The level of microporosity and / or mesoporosity, or the microporosity and / or mesoporosity profile, of a MOF monolithic material can be determined by the test method ASTM D4641-17. A suitable instrument for performing ASTM D4641-17 is the ASAP 2020 Plus from Micromeritics Corporation.

[0312] Typically, a test sample (0.5 g) is heated to 300°C under vacuum to remove adsorbed gases and vapors from the surface. The nitrogen adsorption branch of the isotherm is then determined by placing the sample under vacuum, cooling it to the boiling point of liquid nitrogen (approximately 77.3 K), and then gradually adding a known amount of nitrogen gas at increasing pressure P to the sample in such an amount that the morphology of the adsorption isotherm is appropriately defined and reaches the saturation pressure of nitrogen.

[0313] Each additional dose of nitrogen is introduced into the sample only after the preceding dose of nitrogen has reached adsorption equilibrium with the sample.

[0314] Typically, equilibrium is reached when the gas pressure change is less than approximately 0.1 torr / 5-minute intervals. This continues until P0 (gas saturation pressure) is reached.

[0315] The data are typically plotted as a function of P / P0, representing the amount of adsorbed / desorbed gas (and the derived porosity profile). Desorption isotherms are determined by stepwise desorption of nitrogen from a saturated sample, while taking the same precautions applied under adsorption conditions to ensure desorption equilibrium. Microporosity is related to the volume of adsorbed gas at P / P0 values ​​<0.1, and mesoporosity is related to the volume of adsorbed gas at P / P0 values ​​between 0.1 and 0.98.

[0316] Macroporosity measurement To have MOF monolithic bodies with high volumetric performance for gas storage and separation applications, it is preferable that the first and / or second MOF monolithic bodies have a low level of macroporosity. In other words, the first and / or second MOF monolithic bodies may have a low level of macroporosity or low volume of macropores, proportional to the volume (i.e., envelope volume) of the first and / or second MOF monolithic bodies.

[0317] The macroporosity of MOF monolithic materials can be determined by mercury porosimetry. Methods based on N2 adsorption are suitable for microporosity and mesoporosity, but not for larger macropores. Mercury porosimetry can measure macropores, but not micropores or smaller mesopores.

[0318] Mercury porosity can be measured according to ASTM D4284-12. A suitable instrument for performing ASTM D4284-12 is the Micromeritics AutoPore VI 9510 from Micromeritics Corp, USA. Other suitable instruments include the PoreMaster series from Quantachrome. Unless otherwise specified by the instrument manufacturer, the default surface tension and contact angle of mercury are assumed to be 485 mN / m and 130°, respectively. In ASTM D4284-12, mercury is pressed into the pores under pressure. A sample size of approximately 0.2 g is preferably used. The MOF monolithic material is preferably fragmented and sieved between 710 microns and 250 microns, and the sieved material is used.

[0319] The pressure required to force mercury into the pores of the sample is inversely proportional to the pore size, according to Washburn's equation. All pores are assumed to be cylindrical for the purpose of characterization. The porosimeter increases the pressure of mercury in the sample holder, causing the mercury to penetrate increasingly smaller pores in the sample. AutoPore VI or other suitable instruments automatically convert the applied pressure to an equivalent pore diameter using Washburn's equation and the contact angle and surface tension values ​​described above.

[0320] The envelope volume can be measured using a method based on Archimedes' principle of volume displacement. The envelope volume of a sample is determined by the volume of mercury that displaces it at atmospheric pressure. At atmospheric pressure (101.325 kPa), mercury does not penetrate the internal pores, but only the external pores. Therefore, the volume of mercury that displaces an object at a pressure of 101 kPa can be used as the envelope volume.

[0321] As the applied pressure increases, the mercury is pushed into smaller internal pores. 292 atmospheres (2.96 × 10⁻¹⁰ 4 A pressure of kPa is sufficient to push mercury into pores larger than 50 nm. Therefore, the % level of macroporosity of the sample is 2.96 × 10⁻⁶.4 This is calculated by subtracting the %Hg penetration porosity at 101 kPa from the %Hg penetration porosity at kPa.

[0322] The volume of a MOF monolithic body can also be measured manually.

[0323] Determination of binder level The level of organic binder in MOF monolithic materials can be determined by thermogravimetric analysis based on weight loss at high temperatures.

[0324] The high temperature used (600°C) burns all organic species from the sample, leaving only metal oxide species. The difference in weight loss between a MOF sample and a MOF monolithic sample (MOF + binder) can be used to determine the level of binder in the sample.

[0325] The MOF monolithic material to be tested is first dried by heating at 150°C for 1 hour to remove the solvent. Next, the monolithic material is crushed, and a sample of the monolithic material (typically 1 g) is heated to 600°C, and the weight loss at a steady state (typically after 1 hour) is measured and normalized as a percentage of loss and a percentage of residue. A sample of the MOF material forming the monolithic material is dried and then heated under the same conditions, and the weight loss is normalized as a percentage of loss, thus determining the percentage of residue. The percentage of MOF in the monolithic material is obtained by dividing the percentage of residue of the monolithic material by the percentage of residue of the MOF material. The difference from 100% is the percentage of the binder level.

[0326] To measure the percentage weight loss of the binder upon contact with the second solvent, the samples before and after the binder removal step are tested as described above. This results in two levels of binder percentage: IABB% (Initial Adsorbent Binder Percentage) and RBABB% (Reduced Adsorbent Binder Percentage).

[0327] Therefore, the percentage reduction in binder is ((IABB% - RBABB%) / (IABB%) * 100.

[0328] BET area measurement The BET surface area of ​​a MOF monolithic material can be measured using ASTM method D3663-03, "Standard Test Method for Surface Area of ​​Catalysts and Catalyst Supports." The BET surface area is determined by measuring the volume of nitrogen gas adsorbed by the MOF monolithic sample at various low-pressure levels. The pressure difference resulting from introducing the MOF monolithic surface area into a constant volume of nitrogen in the test apparatus is measured and used to calculate the BET surface area. A suitable instrument for measuring BET surface area is the Micromeritics Corporation 3Flex, used according to the manufacturer's guidelines.

[0329] Envelope density The envelope density of a body is calculated by multiplying the weight of the object (in grams) by its envelope volume (cm³). 3 Envelope density can be measured by dividing by (units). ASTM D3766 defines envelope density as "the ratio of the mass of a particle to the sum of the volume of solid within each piece and the voids within each piece, i.e., the volume within a hypothetical, tightly fitting envelope that completely surrounds each piece." The envelope density of an object can be measured using different techniques, and the results are comparable. In case of significant discrepancies, the results from the powder pycnometer take precedence.

[0330] Envelope density can be measured by mercury porosimetry. At atmospheric pressure, mercury does not penetrate the internal pores. Therefore, the volume of mercury replaced by the substance at atmospheric pressure is the envelope volume. Dividing the weight of the sample by the envelope volume gives the envelope density. The use of mercury porosimetry is described above.

[0331] Preferably, a powder pycnometer, such as the GeoPyc Model 1360 from Micrometrics Instrument Corp, may also be used to measure the envelope volume and density of an object. If necessary, the envelope volume measured by these techniques may be used interchangeably with the envelope volume measured by mercury porosimetry. In case of any discrepancy, the measurement result from the powder pycnometer takes precedence.

[0332] For larger objects, the envelope volume can be determined manually. For example, the envelope density of an extruded body can be measured in micrometers to determine its thickness and length, thereby allowing the volume of the extruded body to be calculated. The weight of the extruded body (grams) can be used to determine its volume (cm³). 3 Dividing by ) yields the envelope density. Manual measurement of envelope density is possible for more uniform objects such as extruded bodies. To reduce experimental variability, multiple measurements (>10) should be taken and averaged.

[0333] bulk density The bulk density (tap density) of the composition can be determined by loading a weighted amount of sample into a cylinder and tapping it at least 50 times. The volume obtained from the filled material is then determined, and the bulk density is calculated by dividing the sample weight by the sample volume. The diameter of the cylinder must be several times (>3) the average length of any extruded body to allow filling. A cylinder with a diameter of approximately 3 cm or more is preferred. The depth of the packed layer must also exceed approximately 3 cm to allow filling.

[0334] Due to the size and properties of the composition, the amount of tapping or movement required to efficiently fill the material is limited. Increasing the amount of tapping and varying the tapping intensity, as in some standards, does not significantly alter the filling density.

[0335] Tap density may be defined by methods such as MPIF-46, ASTM B-527, or ISO 3953 tap density method.

[0336] Particle size measurement In the context of this disclosure, average particle diameter is understood by those skilled in the art to include weight-based average particle diameter or volume-based average particle diameter, which are average particle sizes characterized and defined from the particle size distribution by weight or volume, respectively.

[0337] As used herein, the term “volume-based average particle diameter” will be understood by those skilled in the art to include a distribution of particle sizes by volume, i.e., a distribution in which the fraction of each size class (relative amount) is defined, for example, as a volume fraction measured by laser diffraction.

[0338] The average particle diameter may refer to the volume-related cumulative distribution of "D50 particle size," where 50% of particles have a diameter smaller than the D50 particle size.

[0339] Preferably, the particle size of the second MOF monolithic body (i.e., an object with a particle aspect ratio close to approximately 1) is measured by laser diffraction.

[0340] The D50 particle size can be measured by laser diffraction, for example, using a Malvern Mastersizer 3000.

[0341] Appropriate methodologies for measuring particle size and particle size distribution by laser diffraction are detailed in ISO 13320:2020.

[0342] Preferably, the particle size of the first MOF monolithic body (i.e., an object having a particle aspect ratio of about 2 or more) is measured by dynamic image analysis as described below.

[0343] Measurement of aspect ratio (and particle size) The particle aspect ratio is the ratio of the length of a particle (e.g., an extruded body) to the width of the particle (e.g., an extruded body).

[0344] To determine the particle aspect ratio of an extruded body, two methods may be used. The particle aspect ratio of an individual extruded body can be determined by manual measurement of a number of individual extruded bodies using a caliper. To provide any statistically reliable data regarding an aggregate of objects, it is necessary to measure at least about 25, preferably more than about 50, randomly selected extruded bodies. However, this is very time-consuming and laborious.

[0345] More conveniently, the (maximum and minimum) particle diameters and the particle aspect ratio of an extrudate (the first MOF monolithic body) can be measured by dynamic image analysis. A suitable device is the Camsizer P4 of Microtrac MRB, which is operated according to the manufacturer's instructions. Such a device has been shown to be comparable to caliper measurements of samples.

[0346] Preferably, a sample of >50 mL is conveyed to the measurement zone by a vibrating chute and passes freely in front of a planar light source in free fall. The resulting shadow projection is photographed by a camera system and evaluated in real time. Thereby, the length and width of the extruded body, as well as its shape, can be measured simultaneously. The conveyance along the vibrating chute helps to align the extruded bodies for analysis.

[0347] The width of the extruded body is most conveniently defined as the minimum area bisector (X Ma min - minimum Martin diameter). This is feasible even if the extruded body is bent or partially rounded. The extrusion length or X stretch is conveniently defined as the square root of the value obtained by subtracting the square of the minimum Martin diameter (X Fe max ) from the square of the maximum Feret diameter (X Ma min ) The maximum Feret diameter (XFe max ) is the maximum distance between two parallel lines that are in contact with the object projection.

[0348] Therefore, the particle aspect ratio is X stretch / X Ma min This is the result.

[0349] The equipment such as the Camsizer P4 controls the length of the extruded molded body (X stretch ) and width (X ma min The distribution of the extruded article is given by the width of the extruded article being very monodispersible. The proportion of the composition containing the first MOF monolith is greater than the average width of the extruded article multiplied by the aspect ratio described in the claim (X stretch This can be determined by the proportion of the composition having ).

[0350] A preferred methodology for measuring particle size and particle size distribution by dynamic image analysis is described in ISO 13322-1 / 2.

[0351] In the context of this disclosure, the average particle aspect ratio will be understood by those skilled in the art to include either a weight-based average particle aspect ratio or a volume-based average particle aspect ratio, i.e., an average particle aspect ratio characterized and defined from a particle aspect ratio distribution by weight or volume, respectively. For example, the particle aspect ratio distribution may be a cumulative particle aspect ratio distribution, which is the proportion (based on weight or volume) of particles having an aspect ratio below a certain value. Preferably, the average particle aspect ratio is a volume-based average particle aspect ratio.

[0352] The average particle aspect ratio may be the "A50 aspect ratio," which is based on a volume-related cumulative distribution in which 50% of the particles have an aspect ratio less than the A50 particle aspect ratio.

[0353] Measurement of Young's modulus and hardness Young's modulus and hardness can be determined by nanoindentation, for example, using an MTS Nanoindenter XP placed in an isolation cabinet to block thermal fluctuations and acoustic interference.

[0354] Prior to indentation, the monolithic surface can be cold-mounted using epoxy resin and polished using a progressively finer diamond suspension. Indentation can be performed under a dynamically displacement-controlled "continuous stiffness measurement" mode. The mechanical properties E (elastic modulus) and H (hardness) are measured, for example, by a sinusoidal displacement of 2 nm at 45 Hz superimposed on the primary load signal of the system, as well as 5 × 10⁻⁶. -2 s -1 The surface penetration depth can be determined as a function of the load and unloading strain rate set to . Tests may be performed up to a maximum indentation depth of 1000 nm using a Berkovich (i.e., three-sided pyramidal) diamond tip with a radius of approximately 100 nm. The obtained raw data (load-displacement curve) can be analyzed using the Oliver and Pharr (2004) method, following previous studies on zeolite imidazolate structures [Tan et al (2010)], with Poisson's ratio set to 0.2. Data resulting from surface penetration less than 100 nm can be discarded due to incomplete tip-surface contact.

[0355] Determination of the proportions of the first and second MOF monolithic bodies in the composition. This can be most easily determined by sieving the composition using a mesh size equal to the width of the first MOF monolithic body or the next smallest Tyler or US mesh.

[0356] Specific embodiments of this disclosure are further described in the following non-limiting embodiments.

[0357] Example 1 Compositions containing UiO-66-NH2 were prepared from the first and second MOF monolithic materials described herein. Here, the metal ion of the MOF was Zr, and the organic linker of the MOF was 2-aminoterephthalate. One liter of a reaction mixture containing MOF(UiO-66-NH2) microcrystals with an average particle size of less than 900 nm, dispersed in a reaction solvent containing water and having a solids content of 10%, was prepared by the method described in the literature.

[0358] The sample was divided into four equal aliquots, and each aliquot was centrifuged at 5250 g for 15 minutes in Jeol JR15.

[0359] The supernatant was poured out of each sample flask, leaving a solid, moist layer at the bottom of the flask. Next, 250 g of methanol was added to each flask, and the sample was stirred to redisperse it and wash away the microcrystals.

[0360] Next, the flask was recentrifuged at 5250 g for 40 minutes to form a thick solid layer (wet structural mass) containing the MOF, methanol, and any residual reactants / solvents from the reaction mixture. The solid layer was analyzed and had a solid content of 27.5%.

[0361] Next, 280 g of the solid layer was mixed with 280 g of a 2.6 wt% methylcellulose aqueous solution to form a wet binder mass.

[0362] The solvent level was reduced by stirring the wet binder mass in a Kenwood kitchen stand. 5 g of pre-dried and ground UiO-66-NH2 powder was also added to thicken the mixture. The material was a very thick paste.

[0363] Next, the undried binder mass was extruded through a hand spaghetti maker with a 2 mm diameter orifice. The extruded bodies could be extruded without sticking to each other and were slowly dried under ambient conditions to obtain extruded bodies with an average width (thickness) of 1.8 mm. Samples of the extruded bodies were manually cut into separate pieces with lengths of approximately 4–5 mm and approximately 7–8 mm.

[0364] Next, the extruded bodies were further dried under ambient conditions (21°C) for 24 hours to form hard and robust extruded bodies. Approximately equal amounts of each length were collected, totaling 71g of cut extruded bodies.

[0365] Next, 20 g of each fragment was placed in 1000 mL of methanol (second solvent) for 48 hours to remove some of the binder. This was repeated with fresh methanol. The washed extruded bodies were removed from the methanol and dried under ambient conditions to obtain two sizes of fragments of the binder-reduced MOF monolithic body. These extruded body fragments were later combined in equal weight ratios to form the first MOF monolithic body.

[0366] Next, approximately 8g of each fragment was taken and combined with each other. The combined mixture was then ground in a mortar and pestle and sieved through a 500-250 micron screen sieve. These were the second MOF monolithic bodies.

[0367] Next, the first and second MOF monolithic bodies were activated by heating them in a vacuum oven at 105°C for 12 hours to obtain the final adsorbent.

[0368] The first MOF monolithic material was found to be 9.0% macroporous, 95.1% MOF content, and 0.55 g / cm³ as determined by mercury porosimetry. 3 The envelope density of (and therefore the relative density of 0.43), and 928m 2It was measured to have a BET area of ​​1 / g. This was the same for the second MOF monolithic material. No visible dust was generated even when the first MOF monolithic material was vigorously shaken.

[0369] Next, the first and second MOF monoliths were combined to form a composition containing 78% by weight of the first MOF monolith and 22% by weight of the second MOF monolith. This was prepared as a packed bed.

[0370] The composition contained a first MOF monolithic and a second MOF monolithic, with the maximum particle diameter (particle length) of the first MOF monolithic being approximately 4 mm to 8 mm, and the maximum particle diameter of the second MOF monolithic being 0.5 mm or less.

[0371] A comparative sample containing only the first MOF monolithic material was also prepared, and the maximum particle size (particle length) of the first MOF monolithic material was approximately 4 mm to 8 mm. The comparative sample was prepared as a packed bed.

[0372] By measuring the bulk density of the samples, the bulk density of compositions containing at least the first and second MOF monolithic bodies was compared with a comparative sample containing only the first MOF monolithic body.

[0373] Compositions containing the first and second MOF monoliths exhibited approximately 29% higher bulk density compared to a comparative sample containing only the first MOF monolith (Table 1). [Table 1]

[0374] Example 2 HKUST-1 compositions comprising the first and second MOF monolithic compounds described herein were prepared. The MOF of the first and second MOF monolithic compounds was HKUST-1, the metal ion of the MOF was Cu, and the organolinker of the MOF was benzene-1,3,5-tricarboxylate.

[0375] The first MOF monolithic material was prepared by extrusion using HKUST-1 as the MOF and methylcellulose as the binder. HKUST-1 was synthesized according to a protocol described in the literature and supplied as a 25% aqueous slurry. Methylcellulose binder was then added as a solution, and the mixture was partially dried. The partially dried material was then extruded through a Caleva extruder with a die plate having 3 mm holes to form extruded strands. The extruded bodies were cut to different lengths, further dried, and then washed in a solvent to remove excess binder. The extruded bodies were then further dried. In testing, the extruded bodies were found to have 11.1% macroporosity, 94% MOF composition, and an average particle width of 2.9 mm.

[0376] The aspect ratio of the extruded body containing the first MOF monolith was approximately 3.5 to 5 (measured using a hand caliper). The extruded body was filled into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the first MOF monolith was 0.58 g / cm³. 3 This was measured.

[0377] A second MOF monolithic material was prepared as follows: The partially dried HKUST-1 binder paste described above was spread on a tray and dried under ambient conditions for two days. The solid material was then ground in a Retsch cutting mill and sieved to obtain fractions of 0.85 mm to 0.45 mm. These fractions were used as the second MOF monolithic material.

[0378] The second MOF monolithic particle had a particle diameter of less than approximately 0.9 mm and a particle aspect ratio of approximately 1.

[0379] A blend of the first and second MOF monolithic bodies was prepared to obtain an HKUST-1 composition containing approximately 71.5% by weight of the first MOF monolithic body and approximately 28.5% by weight of the second MOF monolithic body. The particles were packed into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the HKUST-1 composition containing the first and second MOF monolithic bodies was 0.73 g / cm³. 3 This was measured.

[0380] Compositions containing the first and second MOF monoliths showed a 25.8% increase in bulk density compared to a comparative sample containing only the first MOF monolith (Table 2). This may be due to the increased available external surface area of ​​the composition, resulting from the increased bulk density and increased external area per unit mass. [Table 2]

[0381] Comparative Example 1 Comparative HKUST-1 compositions were prepared from the first MOF monolithic compound containing HKUST-1 described above in Example 2, and from a conventional MOF monolithic compound containing HKUST-1.

[0382] Conventional MOF monoliths had the same composition as the first MOF monolith containing HKUST-1, but the particle aspect ratio of the conventional MOF monoliths ranged from approximately 1.5 to approximately 3.5 (measured using a hand caliper). The particles were packed into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the conventional MOF monoliths was 0.63 g / cm³. 3 It was measured to show only a slight increase in bulk density compared to the first MOF monolithic body containing HKUST-1 with a particle aspect ratio of 3.5–5.

[0383] The comparative composition was prepared by combining a 50:50 mixture of a first MOF monolithic containing HKUST-1 and a conventional MOF monolithic containing HKUST-1. The bulk density of the comparative HKUST-1 composition was approximately 0.62 g / cm³. 3 That was the case.

[0384] This indicates that this combination of monolithic materials does not lead to a significant improvement in filling efficiency. Conventional MOF monolithic materials have a particle aspect ratio of approximately 1.5 to 3.5, making them unable to efficiently fill around extruded bodies with a larger aspect ratio (3.5 to 5).

[0385] Comparative Example 2 Comparative HKUST-1 compositions were prepared from a first MOF monolithic body containing HKUST-1 as described in Example 2 (i.e., having a diameter of approximately 2.9 mm) and a narrow MOF monolithic body containing HKUST-1. The particle width of the narrow MOF monolithic body was approximately 0.9 mm, and the maximum particle length of the narrow MOF monolithic body was approximately 10 mm.

[0386] The narrow-width MOF monolithic material containing HKUST-1 had the same composition as the first MOF monolithic material containing HKUST-1. The narrow-width MOF monolithic material was much thinner than the extruded version of the first MOF monolithic material. In particular, the particle length of the narrow-width MOF monolithic material was considerably longer than the particle width of the first MOF monolithic material.

[0387] The comparative composition was prepared by combining a 2.5:1 mixture of the first MOF monolithic and a narrow MOF monolithic. The particles were packed into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the comparative composition was 0.59 g / cm³. 3 This was measured.

[0388] This indicates that this combination of monolithic materials does not lead to a significant improvement in filling efficiency or an increase in bulk density. Despite the narrow MOF monolithic material having a smaller particle width compared to the first MOF monolithic material, it cannot efficiently fill around extruded bodies with a larger aspect ratio (3.5-5).

[0389] Example 3 UTSA-16 compositions comprising the first and second MOF monolithic bodies described herein were prepared. The MOF of the first and second MOF monolithic bodies was UTSA-16, the metal ion of the MOF was Co, and the organolinker of the MOF was a citrate.

[0390] The first MOF monolithic material was prepared by extrusion using ZU-301 as the MOF and methylcellulose as the binder. UTSA-16 was synthesized according to a protocol described in the literature and supplied as a 27% aqueous slurry. Methylcellulose binder was then added as a solution, and the mixture was partially dried under ambient conditions to form a deformable solid. The partially dried material was then extruded through a Caleva extruder with a die plate having 3 mm holes to form extruded strands. The extruded bodies were cut to different lengths and further dried. The extruded bodies were then dried further. In testing, the extruded bodies were found to have 9.1% macroporosity, 95% MOF composition, and an average particle width of 2.85 mm.

[0391] The aspect ratio of the extruded body containing the first MOF monolith was approximately 2 to 3.6 (measured using a hand caliper). The extruded body was filled into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the first MOF monolith was 0.88 g / cm³. 3 This was measured.

[0392] A second MOF monolithic material was prepared as follows: Partially dried UTSA-16 and binder material were further dried under ambient conditions until no further weight loss occurred. The hard solid material was then milled in a Retsch cutting mill and sieved to obtain fractions of 0.85 mm to 0.45 mm. These fractions were used as the second MOF monolithic material.

[0393] A blend of the first and second MOF monolithic bodies was prepared to obtain a first UTSA-16 composition containing the first and second MOF monolithic bodies in a 2.5:1 ratio (i.e., 71.5% by weight of the first MOF monolithic body and 28.5% by weight of the second MOF monolithic body). The particles were packed into a cylinder of known volume using tapping. After tapping for 1 minute, the bulk density of the first UTSA-16 composition containing the first and second MOF monolithic bodies was 1.03 g / cm³. 3 This was measured.

[0394] A blend of the first and second MOF monoliths was prepared to provide a second UTSA-16 composition containing the first and second MOF monoliths in a ratio of 1.64:1 (i.e., 62% by weight of the first MOF monolith and 38% by weight of the second MOF monolith). The particles were packed into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the second UTSA-16 composition containing the first and second MOF monoliths was 1.10 g / cm³. 3 This was measured.

[0395] A blend of the first and second MOF monolithic bodies was prepared to provide a third UTSA-16 composition containing the first and second MOF monolithic bodies in a ratio of 1.23:1 (i.e., 55% by weight of the first MOF monolithic body and 45% by weight of the second MOF monolithic body). The particles were packed into a cylinder of known volume using tapping. After tapping for 1 minute, the bulk density of the third UTSA-16 composition containing the first and second MOF monolithic bodies was 1.08 g / cm³. 3 This was measured.

[0396] This demonstrates that improvements in bulk density can be obtained for different ranges of first and second MOF monolithic ratios (Table 3). [Table 3]

[0397] Example 4 ZU-301 compositions comprising the first and second MOF monolithic compounds described herein were prepared. The MOF of the first and second MOF monolithic compounds was ZU-301, the metal of the MOF was Zn, and the organolinkers of the MOF were oxalate and 3-methyl-1H-1,2,4-triazole.

[0398] The first MOF monolithic material was prepared by extrusion using ZU-301 as the MOF and PVA as the binder. ZU-301 was synthesized according to a protocol described in the literature and supplied as a 25% aqueous slurry after washing and concentration steps. A 50:50 mixture of PVA and methylcellulose binder was then added as a powder mixture and blended with stirring. The resulting mixture was partially dried under ambient conditions to form a deformable solid in the same manner as other samples. The partially dried material was then extruded through a Caleva extruder with a die plate having 3 mm holes to form extruded strands. The extruded bodies were cut to different lengths, further dried, solvent washed in methanol, and then further dried. In testing, the extruded bodies were found to have 12.9% macroporosity, 92% MOF composition, and an average particle width of 2.88 mm.

[0399] The aspect ratio of the extruded body containing the first MOF monolith was approximately 2.5 to 4.8 (measured using a hand caliper). The extruded body was filled into a cylinder of known volume using tapping. After 1 minute of tapping, the bulk density of the first MOF monolith was 0.76 g / cm³. 3 This was measured.

[0400] A second MOF monolithic material was prepared as follows: The ZU-301 extruded material prepared above was milled using a Retsch cutting mill and sieved to obtain fractions of 0.85 mm to 0.45 mm. These fractions were used as the second MOF monolithic material.

[0401] A blend of the first and second MOF monolithic bodies was prepared to obtain a ZU-301 composition containing the first and second MOF monolithic bodies in a 3.5:1 ratio (i.e., 77.5% by weight of the first MOF monolithic body and 22.5% by weight of the second MOF monolithic body). The particles were packed into a cylinder of known volume using tapping. After tapping for 1 minute, the bulk density of the ZU-301 composition containing the first and second MOF monolithic bodies was 0.89 g / cm³. 3 This was measured.

[0402] Compositions containing the first and second MOF monolithic bodies showed an increase in bulk density compared to a comparative sample containing only the first MOF monolithic body (Table 4). [Table 4]

[0403] Example 5 For the selected MOFs, CO2 and N2 adsorption isotherms were performed at 20°C, and the results are shown in Figures 1-6. This demonstrates the excellent performance of these MOFs as CO2 scavenging materials.

[0404] Example 6 The kinetics of gas adsorption onto MOF monolithic materials and compositions were studied. The kinetics of gas adsorption are a function of the external surface area of ​​the MOF monolithic material and the diffusion coefficient of the gas passing through the MOF monolithic material.

[0405] While the use of larger MOF extruded bodies is practical for large-scale production, it may result in lower adsorption rates compared to smaller MOF extruded bodies. However, small MOF extruded bodies are not practical to manufacture on an industrial scale, as described herein.

[0406] Because practical industrial systems typically do not operate under equilibrium conditions due to the long time required, the initial gas adsorption rate is particularly important for actual adsorption systems.

[0407] Therefore, to characterize the adsorption rate for MOF monolithic bodies of different dimensions, DVS tests (at 20°C) were performed by measuring CO2 adsorption isotherms using CO2 levels of 5% (i.e., 50,000 ppm CO2), 10%, 20%, 30%, and 40%, and the time taken for the sample to reach 5% CO2 uptake was measured.

[0408] A first MOF monolithic body (referred to as a long extruded body) containing ZU-301 (having a particle width of 2.9 mm, a particle length of 7.2 mm, and a particle aspect ratio of 2.5) similar to that of Example 4 was prepared.

[0409] A comparative monolithic body containing ZU-301 (referred to as a short-extruded body) was prepared in the same manner as the long-extruded body, but it had a particle width of 2.9 mm, a particle length of 2.4 mm, and a particle aspect ratio of 0.83. Such monolithic bodies would not be practical to manufacture due to their short particle length and low aspect ratio.

[0410] Figure 7 shows the kinetics of CO2 uptake adsorption in long-extruded and short-extruded molded articles. This shows that, in contrast to the long-extruded molded article which took 237 minutes, the short-extruded molded article took 150 minutes to reach 5% CO2 uptake.

[0411] A second MOF monolithic body containing ZU-301 was prepared by crushing and sieving the first MOF monolithic extruded body to obtain fractions of 1 mm to 1.5 mm.

[0412] These second MOF monoliths took only 28 minutes to reach a 5% CO2 load. Furthermore, when a smaller second MOF monolith from Example 4 (i.e., sieved to give fractions of 0.85 mm to 0.45 mm) was tested, it took only 7 minutes to reach a 5% CO2 uptake and rapidly reached a 6.1% fill during the first cycle. Despite the favorable gas uptake characteristics, compositions containing only these second MOF monoliths are impractical and expensive to manufacture on a large scale due to the high level of grinding and sieving required, as well as the amount of fine particles generated that need to be recycled.

[0413] This demonstrates that the composition of Example 4 (i.e., having 77.5 wt% of the first MOF monolithic and 22.5 wt% of the second MOF monolithic) has an increased volumetric capacity not only due to a higher bulk density but also due to a further complementary increase in the initial adsorption rate.

[0414] For example, based on the data above, the composition of Example 4 is estimated to reach a 5 wt% CO2 load in about 188 minutes, which is significantly faster than the time required for the first MOF monolithic alone (i.e., 237 minutes). This, combined with a 10-20% volume increase per cycle due to the increased bulk density, reduces the cycle time by about 20%. Since these volume improvements are additive, such compositions of the present invention can reasonably be expected to result in an overall volume increase of about 30% per day compared to comparative samples.

[0415] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which this invention belongs.

[0416] Any listing or discussion of documents that are clearly previously published in this specification should not necessarily be considered an acknowledgment that such documents are part of the latest technology or common knowledge.

[0417] All embodiments and specific features of the Invention referred to herein may be interpreted alone or in combination with any other embodiments and / or specific features referred to herein without departing from the disclosure of the Invention (i.e., more specific embodiments and specific features disclosed herein are described herein).

[0418] As used herein, the term “comprises” has its usual meaning in the art, that is, that the components include, but are not limited to, the characteristics of the substance in question (i.e., including, among others). Thus, the term “comprises” includes a reference to the components that are essentially derived from the substance(s) in question.

[0419] As used herein, unless otherwise specified, the terms “consists essentially of” and “consisting essentially of” refer to the relevant component that makes up at least 80% (e.g., at least 85%, at least 90%, or at least 95%, e.g., at least 99%) of the specified substance(s) according to the relevant measure (e.g., by weight). The terms “consists essentially of” and “consisting essentially of” may be replaced with “consists of” and “consisting of,” respectively.

[0420] To avoid misunderstanding, the term "contains" also includes references to the "essentially consisting" (especially "consisting of") components of the substance(s) in question.

[0421] Whenever the word “approximately” is used herein in relation to absolute quantities such as weight, volume, size, diameter, or relative quantities (e.g., percentages) of individual components in a composition or components of a composition (including concentration and ratio), time frame, and temperature, etc., it should be understood that such variables are approximate and therefore may vary by ±10%, for example, ±5%, preferably ±2% (e.g., ±1%) from the actual figures expressed herein. This is true even when such figures are initially presented as percentages (for example, “approximately 10%” may mean ±10% of the number 10, which could be anywhere from 9% to 11%).

[0422] The following numbered sections summarize specific aspects of the present invention. 1. A composition comprising at least two MOF monolithic bodies, The composition comprises at least about 50% by weight of the first MOF monolithic body based on the total weight of the composition, The aforementioned first MOF monolithic body, Organic binders and, The first MOF monolithic body comprises at least about 80% by weight of MOF, based on the total weight of the first MOF monolithic body, The first MOF monolithic body has a macropore volume of approximately 15% or less of the envelope volume of the first MOF monolithic body and a particle aspect ratio of approximately 2 or more. The aforementioned second MOF monolithic body, A binder and MOF and, A composition wherein the second MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first MOF monolithic body. 2. The composition according to paragraph 1, wherein the binder of the second MOF monolithic compound is an organic binder. 3. The composition according to paragraph 1, wherein the second MOF monolithic body contains at least about 50% by weight of MOF based on the total weight of the second MOF monolithic body. 4. The composition according to paragraph 1, wherein the second MOF monolithic body comprises at least about 80% by weight of MOF and up to about 20% by weight of a binder, based on the total weight of the second MOF monolithic body. 5. The composition according to paragraph 1, wherein the second MOF monolithic body has a macropore volume of about 15% or less of the envelope volume of the second MOF monolithic body. 6. The composition according to paragraph 1, wherein the composition comprises, based on the total weight of the composition, at least about 70% by weight of the first MOF monolithic and / or up to about 30% by weight of the second MOF monolithic. 7. The composition according to paragraph 1, wherein the first MOF monolithic body has a macropore volume of about 12% or less of the envelope volume of the first MOF monolithic body, and / or the second MOF monolithic body has a macropore volume of about 12% or less of the envelope volume of the second MOF monolithic body. 8. The composition according to paragraph 1, wherein the particle aspect ratio of the first MOF monolithic body is about 3 or more. 9. The composition according to paragraph 1, wherein the first MOF monolithic body has a maximum particle diameter of about 1 mm or more and / or a minimum particle diameter of about 500 μm or more. 10. The composition according to paragraph 1, wherein the maximum particle size of the second MOF monolithic body is about 5 mm or less. 11. The composition according to paragraph 1, comprising about 10% by weight or less of an MOF material having a particle size of about 50 μm or less, based on the total weight of the composition. 12.About 0.3g / cm 3 The composition described in paragraph 1, having the above bulk density. 13. The first MOF monolithic and / or the second MOF monolithic are approximately 0.3 g / cm³ 3 The composition according to paragraph 1, having the above envelope density. 14. The composition according to paragraph 1, wherein the first MOF monolith and / or the second MOF monolith have a relative density of about 0.3 or more. 15. The composition according to paragraph 1, wherein the first MOF monolithic and / or the second MOF monolithic have a microporosity of about 40% or more based on total pore volume. 16. The first MOF monolithic body and / or the second MOF monolithic body are approximately 10 m 2 The composition described in paragraph 1, having a BET surface area of ​​1 / g or more. 17. The composition according to paragraph 1, further comprising a gas selected from hydrogen, carbon dioxide, methane, krypton, and mixtures thereof. 18. The composition according to paragraph 1, wherein the first and second MOF monolithic bodies comprise the same MOF and / or the same binder. 19. The composition according to paragraph 1, wherein the MOF of the first and / or second MOF monolithic is independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, and mixtures thereof. 20. The gas is A composition comprising hydrogen, wherein the first MOF monolithic body comprises an MOF selected from HKUST-1, ZIF-8, MOF-808, UiO-66 and mixtures thereof, The gas comprises carbon dioxide, and the first MOF monolithic body comprises an MOF selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof, The composition comprises an MOF in which the gas contains krypton and the first MOF monolithic body is MOF-74, and The composition according to paragraph 17, wherein the gas comprises methane and the first MOF monolithic body comprises an MOF which is HKUST-1. 21. A method for preparing the composition described in paragraph 1, a. A step of providing a wetting binder MOF mass, wherein the wetting binder MOF mass is i.MOF and, ii. Based on the total weight of the wetting binder MOF mass, a first solvent in an amount of about 50% to about 95% by weight, iii. Providing an organic binder, wherein the binder may be added as a solution, dispersion, powder, or mixture thereof, b. Optionally, the step of reducing the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass, c. The step of extruding and cutting the wet binder MOF mass or the undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, d. The step of removing at least some of the remaining first solvent from the first undried MOF monolithic to provide a first dried MOF monolithic, e. Optionally, the step of adding a second solvent to the first dry MOF monolithic to remove at least some of any residual first solvent, at least some of any unreacted reactants, and at least some of the organic binder from the first dry MOF monolithic to provide an optional first binder-reduced MOF monolithic, f. Optionally, the step of removing at least some of the second solvent from the optional first binder-reduced MOF monolith to provide an optional first inactivated MOF monolith, g. The step of activating the first dried MOF monolith or an optional first inactivated MOF monolith by exposing it to a temperature of approximately 100°C or higher, thereby providing a first MOF monolith; h. A method comprising the step of providing a composition by combining the first MOF monolithic body with a second MOF monolithic body, wherein the second MOF monolithic body is as defined in paragraph 1. 22. The method further comprises one or more steps for providing a second MOF monolithic body for use in step (h), wherein the step is A step of grinding several of the first dried MOF monolithic bodies to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first dried MOF monolithic body, and / or The method according to paragraph 21, comprising the step of grinding several of the optional first binder-reduced MOF monoliths to provide an optional second binder-reduced MOF monolith, wherein the optional second binder-reduced MOF monolith has a minimum particle diameter and a maximum particle diameter approximately less than or equal to that of the optional first binder-reduced MOF monolith. 23. A gas storage container comprising the composition described in paragraph 1. 24. One or more of the following: a. Insulation material for exterior walls, b. Means for heating and cooling the composition, c. Internal baffle, d. Means for restraining the composition in a predetermined position, e. The composition is in a shape such that it is about 10 cm or more from the outer wall. f. Means for monitoring pressure and / or temperature, and / or g. A gas storage container according to paragraph 23, including a valve for controlling the flow of gas in and out. 25. A method for filling, storing, and / or releasing gas into, and / or from, a gas storage container as described in paragraph 23. 26. The method according to paragraph 25, wherein the gas comprises hydrogen, carbon dioxide, methane, krypton, or a mixture thereof. 27. The method according to paragraph 25, wherein the method is part of a gas purification process. 28. The method according to paragraph 25, wherein the gas contains hydrogen, and the first MOF monolithic body comprises an MOF selected from HKUST-1, ZIF-8, MOF-808, UiO-66, and mixtures thereof. 29. The composition is found to be approximately 0.6 to approximately 0.8 g / cm³ at 77 K and 10 atm. 3 MOF, and approximately 0.04 to 0.065 g / cm³ 3 The method according to paragraph 28, comprising a bulk volume composition of hydrogen. 30. The method according to paragraph 25, wherein the gas comprises carbon dioxide, and the first MOF monolithic body comprises a MOF selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, and mixtures thereof. 31. The composition is found to be concentrated at approximately 0.6 to 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to 0.1 g / cm³ 3 The method according to paragraph 30, comprising the bulk volume composition of carbon dioxide. 32. The method according to paragraph 25, wherein the gas comprises krypton and the first MOF monolithic body comprises MOF-74. 33. The composition is found to be concentrated at approximately 0.6 to 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to 0.1 g / cm³ 3 The method according to paragraph 32, comprising the bulk volume composition of krypton. 34. The method according to paragraph 25, wherein the gas comprises methane and the first MOF monolithic body comprises HKUST-1. 35. The composition is found to be concentrated at approximately 0.6 to 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to 0.1 g / cm³ 3 The method according to paragraph 34, comprising the bulk volume composition of methane.

Claims

1. A composition comprising at least two MOF monolithic bodies, wherein the composition comprises at least about 50% by weight of a first MOF monolithic body based on the total weight of the solid composition, and the first MOF monolithic body is Organic binders and, The solid first MOF monolithic body comprises at least about 80% by weight of MOF, The first MOF monolithic body has a macropore volume of about 15% or less of the envelope volume of the first MOF monolithic body, a particle aspect ratio of about 2 or more, and a minimum particle diameter of about 1 mm or more. The second MOF monolithic body is A binder and MOF and, A composition wherein the second MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the first MOF monolithic body.

2. The composition according to claim 1, wherein the binder of the second MOF monolithic body is an organic binder, and optionally, the organic binder of the first and / or second MOF monolithic body is an organic polymer binder.

3. The composition according to claim 1 or 2, wherein the second MOF monolithic body comprises at least about 50% by weight of MOF based on the total weight of the solid second MOF monolithic body, and optionally the second MOF monolithic body comprises at least about 80% by weight of MOF and up to about 20% by weight of a binder.

4. The composition according to any one of claims 1 to 3, wherein the composition comprises, based on the total weight of the solid composition, about 50 to about 99.9% by weight of the first MOF monolithic and / or about 0.1 to about 50% by weight of the second MOF monolithic.

5. The composition according to any one of claims 1 to 4, wherein the first MOF monolithic body has a macropore volume of about 13% or less of the envelope volume of the first MOF monolithic body, and / or the second MOF monolithic body has a macropore volume of about 13% or less of the envelope volume of the second MOF monolithic body.

6. The composition according to any one of claims 1 to 5, wherein the particle aspect ratio of the first MOF monolithic body is about 2 to about 7.

7. The composition according to any one of claims 1 to 6, wherein the first MOF monolithic body has a maximum particle diameter of about 2 to about 35 mm, and / or the first MOF monolithic body has a minimum particle diameter of about 1 to about 5 mm, and / or the maximum particle diameter of the second MOF monolithic body is about 20 μm to about 3 mm.

8. Approximately 0.3 to approximately 1.5g / cm ３ It has a bulk density of and / or the first MOF monolithic and / or the second MOF monolithic is approximately 0.4 to approximately 2 g / cm³. ３ The composition according to any one of claims 1 to 7, wherein the envelope density is and / or the first MOF monolithic and / or the second MOF monolithic has a relative density of about 0.3 to about 1.

3.

9. The first MOF monolithic body and / or the second MOF monolithic body have a microporosity of about 40% to about 75% based on total pore volume, and / or the first MOF monolithic body and / or the second MOF monolithic body have a microporosity of about 0 to about 2,500 m ２ The composition according to any one of claims 1 to 8, having a BET surface area of ​​1 / g.

10. The composition according to any one of claims 1 to 11, wherein the ratio of the maximum particle diameter of the second MOF monolithic body to the minimum particle diameter of the first MOF monolithic body is about 0.05 to about 0.

95.

11. The composition according to any one of claims 1 to 10, wherein the composition further comprises a gas selected from hydrogen, carbon dioxide, methane, krypton, water, and mixtures thereof.

12. The composition according to any one of claims 1 to 11, wherein the first and second MOF monolithic bodies comprise the same MOF and / or the same binder.

13. The composition according to any one of claims 1 to 12, wherein the MOF of the first and / or second MOF monolithic is independently selected from MOFs comprising metal ions selected from transition metals, Si, Mg, Al, and mixtures thereof.

14. The composition according to any one of claims 1 to 13, wherein the MOF of the first and / or second MOF monolithic is independently selected from MOFs comprising carboxylic acids such as dicarboxylic acids, tricarboxylic acids and / or tetracarboxylic acids, azines such as diazines, azoles such as imidazoles and / or triazoles, and organic linkers comprising mixtures thereof.

15. The MOFs in the first and / or second MOF monolithic bodies are independently HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, UTSA-16, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH ２ A composition according to any one of claims 1 to 14, selected from MOF-74 / CPO-27, MOF-74-Mg / CPO-27-Mg, SIFSIX, aluminum fumarate, and mixtures thereof.

16. The composition wherein the gas contains hydrogen, and the first and / or second MOF monolithic body contains a suitable MOF. The composition wherein the gas contains carbon dioxide, and the first and / or second MOF monolithic body contains a suitable MOF. A composition wherein the gas contains krypton, and the first and / or second MOF monolithic body contains a suitable MOF, and The composition according to any one of claims 12 to 15, wherein the gas comprises methane and the first and / or second MOF monolithic body is selected from a composition comprising a suitable MOF.

17. A method for preparing the composition described in any one of claims 1 to 16, a. A step of providing a wetting binder MOF mass, wherein the wetting binder MOF mass is i. MOF and, ii. Based on the total weight of the wetting binder MOF mass, a first solvent in an amount of about 50% to about 95% by weight, iii. Providing a method comprising: an organic binder, wherein the binder may be added as a solution, dispersion, powder, or mixture thereof; b. Optionally, the step of reducing the proportion of the first solvent in the wetting binder MOF mass to provide an undried binder MOF mass, c. The step of extruding and cutting the wet binder MOF mass or the undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, d. The step of removing at least some of the remaining first solvent from the first undried MOF monolithic to provide a first dried MOF monolithic, e. Optionally, adding a second solvent to the first dried MOF monolithic to remove at least some of the optional residual first solvent, at least some of the optional unreacted reactants, and at least some of the organic binder from the first dried MOF monolithic to provide an optional first binder-reduced MOF monolithic; f. Optionally, the step of removing at least some of the second solvent from the optional first binder-reduced MOF monolithic to provide an optional first inactivated MOF monolithic, g. The step of activating the first dried MOF monolithic or an optional first inactivated MOF monolithic by exposing it to a temperature of about 100°C or higher to provide a first MOF monolithic, h. A method comprising the step of combining the first MOF monolithic body with a second MOF monolithic body to provide a composition, wherein the second MOF monolithic body is as defined in any one of claims 1 to 16.

18. A method for preparing the composition described in any one of claims 1 to 16, I. A step of forming a wet MOF reaction mass, wherein the wet MOF reaction mass is i. Based on the total weight of the wet MOF reaction mass, about 20% to about 70% by weight, or about 30% to about 60% by weight, or about 40% to about 50% MOF, ii. In the wet MOF reaction mass, approximately 3% to approximately 50%, approximately 8% to approximately 40%, or approximately 10% to approximately 30% of the weight of the MOF, an unreacted MOF precursor, and iii. A forming step comprising a reaction solvent comprising about 10% to about 70% by weight, preferably about 10% to about 60%, preferably about 10% to less than 50%, relative to the weight of the wet MOF reaction mass, II. The step of bringing the wet MOF reaction mass into contact with an organic binder to provide a wet binder MOF mass, III. Optionally, the step of reducing the proportion of the reaction solvent in the wetting binder MOF mass to provide an undried binder MOF mass, IV. The step of extruding and cutting the wet binder MOF mass or the undried binder MOF mass to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or more, V. The step of removing at least some of the remaining solvent from the first undried MOF monolithic to provide the first dried MOF monolithic, VI. Optionally, to remove at least a portion of the residual reaction solvent, at least a portion of any unreacted reactants, and / or at least a portion of the organic binder from the first dried MOF monolithic, the first dried MOF monolithic is brought into contact with a washing solvent to provide an optional first binder-reduced MOF monolithic; VII. Optionally, the step of removing at least some second solvent from the optional first binder-reduced MOF monolithic to provide an optional first inactivated MOF monolithic, VIII. The steps of activating the first dried MOF monolithic or the optional first inactivated MOF monolithic by exposing it to a temperature of approximately 100°C or higher to provide the first MOF monolithic, IX. A method comprising the step of providing a composition by combining the first MOF monolithic body with a second MOF monolithic body, wherein the second MOF monolithic body has a maximum particle diameter approximately equal to or less than the minimum particle diameter of the first MOF monolithic body.

19. The method further comprises one of a plurality of steps for providing a second MOF monolithic body for use in step (h) or step (IX), wherein the step is A step of grinding several of the first dried MOF monolithic bodies to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle diameter that is approximately equal to or less than the minimum particle diameter of the dried first MOF monolithic body, and / or The method according to claim 17 or 18, comprising the step of grinding several of the optional first binder-reduced MOF monoliths to provide an optional second binder-reduced MOF monolith, wherein the optional second binder-reduced MOF monolith has a minimum particle diameter and a maximum particle diameter substantially less than or equal to that of the optional first binder-reduced MOF monolith.

20. A gas storage container comprising the composition according to any one of claims 1 to 16.

21. One or more of the following: a. Insulation material for exterior walls, b. Means for heating and cooling the composition, c. Internal baffle, d. Means for restraining the composition in a predetermined position, e. The composition is in a shape such that it is about 10 cm or more from the outer wall. f. Means for monitoring pressure and / or temperature, and / or g. A gas storage container according to claim 20, comprising a valve for controlling the input and output flow of gas.

22. Use of the gas storage container according to claim 20 or 21 for gas intake, storage and / or release.

23. Use of the composition according to any one of claims 1 to 16 for gas intake, storage and / or release.

24. The use according to claim 22 or 23, wherein the gas comprises hydrogen, carbon dioxide, methane, krypton, water, or a mixture thereof.

25. The use according to any one of claims 22 to 24, wherein the use is part of a gas purification process.

26. The gas contains hydrogen, the first and / or second MOF monolithic body contains a suitable MOF, and optionally the composition is present in a concentration of about 0.4 to about 1.1 g / cm³ at 77 K and 10 atm. ３ MOF and approximately 0.025 to 0.09 g / cm³ ３ The use according to any one of claims 22 to 25, comprising the bulk volume composition of hydrogen.

27. The gas contains carbon dioxide, the first and / or second MOF monolithic body contains a suitable MOF, and optionally the composition is present in a concentration of about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. ３ MOF and approximately 0.03 to 0.14 g / cm³ ３ The use according to any one of claims 22 to 25, comprising the bulk volume composition of carbon dioxide. 【Request Item 28】 The gas contains krypton, the first and / or second MOF monolithic body contains a suitable MOF, and optionally, the composition has a bulk volume composition of about 0.4 to about 1.1 g / cm ３ of the MOF and about 0.03 to about 0.14 g / cm ３ of krypton at 293 K and 5 atm. Use according to any one of claims 22 to 25, comprising such a bulk volume composition. 【Request Item 29】 The gas comprises methane, the first and / or second MOF monolithic comprises a suitable MOF, and optionally the composition is present in a concentration of about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. ３ MOF and approximately 0.03 to 0.14 g / cm³ ３ The use according to any one of claims 22 to 25, comprising the bulk volume composition of methane. 【Request Item 30】 The gas contains water, the first and / or second MOF monolithic body contains a suitable MOF, and optionally the composition is concentrated at 293 K and 5 atm in an amount of about 0.4 to about 1.1 g / cm³. ３ MOF and approximately 0.03 to 0.14 g / cm³ ３ The use according to any one of claims 22 to 25, comprising the bulk volume composition of water.

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