Novel metal organic framework monolithic main body composition

Abstract

The present disclosure relates to a composition for use in a gas storage vessel, the composition comprising at least two MOF monolithic bodies, the at least two MOF monolithic bodies comprising at least about 50% by weight of a first MOF monolithic body and a second MOF monolithic body. And the MOF integral main body contains MOF and a binding agent. The first MOF monolithic body has a macropore volume of about 15% or less of an encapsulated volume of the first MOF monolithic body, a particle aspect ratio of about 2 or greater, and a minimum particle diameter of greater than or equal to about 1 mm. 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.

Description

[0001] This invention relates to monolithic metal-organic framework (MOF) compositions, methods for preparing such compositions, gas storage containers containing said compositions, and the use of such compositions in gas storage containers for the absorption, storage, and release of gases.

[0002] There has been, and will continue to be, a strong interest in using improved adsorbents for gas storage applications. Gas separation and purification processes are crucial for gas production and storage, as well as applications requiring gases with increased purity, such as air purification, electronics, fine chemicals, fuel cells, and power plants (Metal-Organic Frameworks: Applications from Catalysis to Gas Storage, Part 2: Gas Storage and Separation Applications, Wiley, June 2011, edited by D. Farrusseng). Adsorbent materials are materials that can adsorb and desorb specific substances (such as gases) under specific conditions. Solid adsorbents are highly porous, and the pores provide the mechanism for adsorbing the target substance.

[0003] MOF

[0004] Metal-organic frameworks (MOFs) are a class of adsorbent materials that can be used to adsorb, store, and desorb gases. Compared to current adsorbent materials such as zeolites and activated carbon, MOFs offer many performance advantages and are candidates for improved gas storage systems required for practical transport systems and applications such as gas separation, purification, and carbon capture. A specific characteristic of MOFs is their high selectivity for specific substances. MOFs can be modified to increase their selectivity for adsorbing specific substances by altering the organic linker and metal ions and fine-tuning their properties.

[0005] MOFs have been extensively studied for various gas storage and purification applications, such as carbon capture from air and flue gas, methane storage, hydrogen storage, gas separation and purification, and inert gas purification. MOFs are likely suitable for these applications because they typically possess high porosity, high surface area, and high selectivity, and are regenerable for continuous use, thus providing an efficient and environmentally friendly means for gas storage and purification. However, to date, treatment-related issues have often limited their industrial applications.

[0006] MOFs can be advantageous because they can be functionalized and fine-tuned to adsorb specific materials. For example, the unique properties of MOFs allow for fine-tuning of the shape, size, and chemical properties of the pores, making MOFs ideal for gas separation, storage, and purification processes (Eddaoudi et al., Science 2002, 295(5554), pp. 469-472).

[0007] Problems in the synthesis and production of MOF materials and substrates

[0008] MOF materials are almost universally synthesized as fine particles or grains, typically through sol-gel or mechanical synthesis techniques. If MOF materials are intended for use in high-volume industrial processes involving gas flow and low pressure drops, and where material handling is a concern, it is crucial to mold the fine powder particles of MOF materials into larger monolithic MOF bodies to avoid issues such as compaction and trenching.

[0009] These monolithic MOF bodies need to be mechanically robust and abrasion-resistant for industrial use, while still maintaining high adsorption performance. Ideally, these larger bodies also have high encapsulation and packing densities to increase the volumetric capacity of any storage container housing the monolithic MOF body. Volumetric capacity describes the adsorption capacity per unit container volume. Higher volumetric capacity means that a smaller and therefore cheaper or more space-efficient container can be used for a given application. The simultaneous requirement for both high bulk density and high adsorption performance (i.e., high porosity) appears to be contradictory.

[0010] A key challenge is to properly mold the less robust MOF materials into mechanically stable and robust monolithic bodies that still retain high accessibility, porosity, and surface area. Therefore, there is a strong interest in preparing dense monolithic MOF 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.

[0011] Using compression techniques such as tableting to form a monolithic MOF body can be problematic for many MOFs because they can lead to the collapse and elimination of smaller-scale porosity within the MOF grains forming the shaped body. For example, very high pressures often cause some or all of the micropores in the MOF material to collapse, which contribute significantly to the material's surface area and gas storage capacity (compared to macropores). These pressure-induced collapses of the micropores should be reduced or avoided.

[0012] Any process used to fabricate high-density MOF monolithic hosts needs to be able to operate at high rates. Any process that cannot be scaled up in an efficient and cost-effective manner has little commercial relevance. Industrial-scale gas storage and separation processes, such as carbon capture or hydrogen storage, will require large quantities of adsorbent material, which will need to be prepared in an efficient and cost-effective manner.

[0013] Therefore, the successful and large-scale application of monolithic MOF bodies for gas storage, purification, and carbon capture requires that monolithic MOF bodies simultaneously meet multiple quality parameters and processing requirements.

[0014] Importantly, monolithic MOFs possess both good adsorbent capacity and high packing density, enabling the creation of gas storage containers with high volumetric capacity suitable for use in gas separation, storage, and purification processes. However, there has been little focus on developing suitable quality MOF monolithic modules that can be fabricated using industrially relevant methods and efficiently filled into gas storage containers to produce high volumetric capacity. When scaling up from small-scale laboratory fabrication to industrial-scale production, many processes inherently become less efficient and / or produce less homogeneous products.

[0015] Various methods for producing adsorbent matrices containing MOFs have been described, such as granulation (WO2014118054), tableting (US7524444), and extrusion (WO2017089344). However, these methods can have various drawbacks that may lead to a variety of problems, including low density, high porosity levels, low surface area, high excipient or binder content, damage to the MOF structure leading to internal pore collapse, and additive clogging of pores in monolithic MOF matrices.

[0016] Several known processing methods for preparing MOF monolithic bulks (e.g., tableting) face various challenges. Known MOF monolithic bulks (such as tablets) can achieve high encapsulation densities. However, even if they maintain porosity during compaction and can be produced rapidly, their packing efficiency is typically low, resulting in lower packing density and reduced gas container volume efficiency.

[0017] Furthermore, most MOF powders typically have low bulk density and therefore poor flowability. If the MOF material is solvated to reduce porosity loss during compaction, the flowability is often even worse. Therefore, feeding MOFs at the desired rate into small, individual dies used to form tablets can be challenging. Such powders may also bridge on these dies, failing to flow in and fill them. Consequently, tablets often use additives to aid processing. However, this results in tablets with low levels of the active ingredient (i.e., MOF), leading to lower performance in monolithic MOF bulk tablets.

[0018] Many of the tableting problems described here also apply to roller compaction.

[0019] Other processing methods for preparing monolithic MOF bulks, such as granulation, also face drawbacks. For example, preparing monolithic MOF bulks with high packing and / or encapsulation densities via granulation is challenging. Adsorbent powders (such as MOFs) are typically difficult to handle and have low packing densities. Granulation processes often lack a strong compaction step during processing, resulting in granulated bulks that typically have high levels of porosity and low encapsulation densities. Furthermore, granulation processes require most or all of the adsorbent material to have been dried and processed into powder, for example, by spray drying. This can introduce unwanted high porosity and additional processing complexity.

[0020] The use of extrusion in monolithic body construction

[0021] Extrusion can be used to prepare monolithic MOF bodies and is widely reported in the art for the fabrication of MOF bodies (e.g., WO2014 / 118074). However, extrusion processing typically results in extrudates with lower filling efficiency and bulk density. This is due to the shape of the extrudate, particularly its typically high aspect ratio. The aspect ratio is the ratio of the length of the extrudate to its width / diameter. It is a metric that is practically only applicable to extrudates and other molded bodies. For example, if a monolithic body has a length of 10 mm and a width of 2 mm, the monolithic body will have a particle aspect ratio of 5. Most particles typically have an aspect ratio close to 1, and spheres will have an aspect ratio of 1. Some particles may be described as “ellipsoidal,” but ellipsoids are essentially deformed spheres and will generally have a smaller aspect ratio, such as less than 2.

[0022] The void fraction of extrudate filling a container typically increases linearly with the aspect ratio of the extrudate. The void fraction is the proportion of the volume in the container not filled by randomly packed extrudate and arises from the voids between the extrudate particles. The void fraction of randomly packed extrudate 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), pp. 3902-3911). A higher void fraction is obviously detrimental to the volumetric capacity of the gas container. However, large-scale production of extrudates with aspect ratios close to 1 is generally difficult for a variety of reasons and typically requires specialized processing equipment where the rheological properties of the extruded mixture are usually within certain parameters that may limit the composition.

[0023] Unlike other, more spherical particle forms, extrudates typically have different particle sizes and aspect ratios, especially in industrial-scale production. This often results in lower bulk density or higher void fraction.

[0024] Therefore, the volumetric properties of gas storage containers containing monolithic MOF extrusions containing adsorbents may be limited. In practice, producing extrusions with aspect ratios close to 1 at high rates is difficult and restrictive due to processing variability and material rheology. The higher the aspect ratio, the easier the extrusion is to produce. This is problematic because extrusion offers many processing advantages. Therefore, there is interest in developing compositions with properties that enable extrusion as a primary production process while offsetting some of the negative impacts associated with the use of extrusion.

[0025] These limitations include both packing density and adsorption kinetics. Initial adsorption kinetics are partly limited by the external surface area of ​​the MOF bulk. Gas diffuses into the MOF bulk through contact with its external surface. Adsorption kinetics can be important in separation processes because the cycle time can be very short. The rate at which the adsorbent can adsorb and release material is as important as the total capacity of the adsorbent. One example is the fast-cycle pressure swing adsorption process, which can be used for processes such as the adsorption and capture of carbon dioxide.

[0026] Meanwhile, extrusion could be a promising method for preparing monolithic MOF bodies if the limitations described herein can be overcome. Extrusion is a practical process because it facilitates the mixing of powders and liquids and forms extrudates by passing the materials through orifices in a die at the end of the extruder. The extruder can be a single-screw extruder (typically used in plastics processing) or a twin-screw extruder. Twin-screw extruders (rotating in the same or opposite directions) allow for intense mixing of materials such as MOF powders and binders, and are therefore the preferred choice for this application.

[0027] The inventors have discovered that MOF monolithic matrix compositions that combine beneficial chemical and physical properties with the shape and size distribution of the monolithic matrix can yield optimized adsorbent products that are easier to produce on an industrial scale.

[0028] This invention relates to a monolithic MOF (Metal-Oxide-Foil) composition, a method for preparing the composition, a gas storage container comprising the composition, and the use of the gas storage container. The inventors have discovered that it is feasible to manufacture such a composition, which possesses advantageous gas absorption, storage, separation, and / or release properties, and can be used to provide gas storage containers with improved volumetric properties and efficient gas dynamics.

[0029] MOFs can vary depending on the gas storage or purification application and the type of gas or adsorbent involved. For example, for carbon capture applications, selecting an MOF with high absorption and selectivity for carbon dioxide is preferred.

[0030] The selection of MOFs can also be based on the environmental and conditions experienced by the monolithic MOF body and the stability of the MOF (such as its thermal, chemical, and / or mechanical stability). For example, in gas purification and / or storage applications involving high temperatures and / or the presence of certain substances (such as water or streams), MOFs with high thermal and chemical stability are preferred. For instance, in carbon capture from flue gas, the gas stream may contain water, and therefore, MOFs with high stability to water are preferred.

[0031] Maintaining the porosity of MOFs during processing is important. MOFs are generally not very robust due to the nature of the ligand-metal ionic bonds that form the pore structure. These bonds depend on metal coordination chemistry rather than stronger covalent or ionic bonds. Applying external pressure can deform and break down the pores of MOFs, thus reducing the surface area available for gas adsorption. Different MOFs have different levels of stability and strength, depending on characteristics such as their composition and crystal structure.

[0032] Another advantage is that the monolithic MOF body possesses suitable characteristics for providing rapid gas absorption and release kinetics. One aspect of this is that the distance between the internal and external surfaces of the monolithic MOF body should not be too large. Otherwise, diffusion kinetics will be limited. A maximum distance of less than 2.5 mm, 2 mm, or less than 1 mm is advantageous. In this way, the gas can diffuse rapidly into the interior of the monolithic MOF body. Furthermore, the gas will need to be able to flow easily into the gas storage container and surround the monolithic body within the container. Therefore, the efficient filling of the monolithic MOF body in the gas storage container must also allow for rapid gas kinetics.

[0033] Due to the increased external surface area of ​​the extrudate, extrudates with smaller diameters appear to have potential advantages, which would improve adsorption kinetics, for example, in rapid cyclic pressure swing adsorption processes. For instance, an extrudate with a cross-sectional diameter of 2 mm and an aspect ratio of 3 would have a surface area to volume ratio 3.2 times that of a 4 mm diameter extrudate, which also has an aspect ratio of 3. An extrudate with a cross-sectional diameter of 1 mm and an aspect ratio of 3 would have a surface area to volume ratio 11.2 times that of a 4 mm diameter extrudate, which also has an aspect ratio of 3. However, extrudates with smaller diameters present several challenges, as described herein.

[0034] The monolithic MOF matrix must also be robust enough to withstand agitation during normal use and prevent excessive dust generation. Typically, the MOF matrix comprises MOF and a binder to improve robustness and resistance to mechanical abrasion. Such binders can be inorganic, such as hydrated alumina, or organic polymers, such as PVA. However, including binders in the monolithic MOF matrix can lead to problems such as pore blockage and / or dilution of the active adsorbent material. Therefore, developing monolithic MOF matrices with good mechanical stability, high surface area, high porosity, and high volumetric capacity is of great significance.

[0035] The MOF monolithic host itself must also possess favorable properties, especially low macroporosity. Larger macropores do not significantly contribute to the adsorption capacity of the adsorbent host; they merely reduce density. Efficiently filling a highly macroporous adsorbent host in an efficient manner is almost meaningless. The overall porosity in a gas storage vessel is a combination of the packing void fraction and the macroporosity of the MOF monolithic host itself. Both of these issues need to be addressed to minimize the packing void fraction.

[0036] The problems solved by the compositions of this invention are widely applicable to most MOFs and binders, as well as a wide range of processes.

[0037] According to an aspect of the present invention, a composition is provided comprising:

[0038] At least two MOF monolithic bodies,

[0039] 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);

[0040] The first MOF monolithic body includes:

[0041] Organic adhesives; and

[0042] Based on the total weight of the first MOF monolithic body (i.e., the body excluding gas, liquid and / or fluid), at least about 80% by weight of MOF;

[0043] The first MOF monolithic host has a macropore volume of 15% or less of the encapsulation volume of the first MOF monolithic host, a particle aspect ratio of about 2 or greater, and a minimum particle size greater than or equal to about 1 mm.

[0044] The second MOF monolithic body includes:

[0045] Adhesives; and

[0046] MOF;

[0047] Furthermore, the second MOF monolithic body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first MOF monolithic body.

[0048] Production of the composition

[0049] According to a further aspect of the invention, a method is provided for manufacturing a composition comprising at least two MOF monolithic bodies.

[0050] The example method includes the following steps:

[0051] a. Providing a wettable adhesive MOF block, the wettable adhesive MOF block comprising:

[0052] i.MOF;

[0053] ii. Based on the total weight of the wetted binder MOF bulk, approximately 50% to approximately 95% by weight of the first solvent; and

[0054] iii. An organic binder, wherein the binder can be added as a solution, dispersion, powder, or mixture thereof;

[0055] b. Optionally, reduce the proportion of the first solvent in the wetted binder MOF block to provide an undried binder MOF block;

[0056] c. Extruding and cutting wet binder MOF blocks or undried binder MOF blocks to provide a first undried MOF monolithic body with a particle aspect ratio of about 2 or greater;

[0057] d. Remove at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body;

[0058] e. Optionally, a second solvent is added to the first dried MOF monolithic matrix to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic matrix to provide an optional MOF monolithic matrix with reduced first binder;

[0059] f. Optionally, at least some of the second solvent is removed from the MOF monolithic body reduced by the optional first binder to provide an optional first unactivated MOF monolithic body;

[0060] g. Activating the first dried MOF monolithic body or the optional first unactivated MOF monolithic body by subjecting it to a temperature of about 100°C or greater to provide a first MOF monolithic body; and

[0061] h. Combining a first MOF monolithic body with a second MOF monolithic body to provide a composition, wherein the second MOF monolithic body is as described herein and has a maximum particle size that is about less than or equal to the minimum particle size of the first MOF monolithic body.

[0062] An alternative method will be described later in this specification.

[0063] The method of the present invention may further include one or more steps to provide a second MOF monolithic body used in step (h), wherein the steps include:

[0064] Grinding some of the first dried MOF monolithic body to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first dried MOF monolithic body; and / or

[0065] Some of the optional first binder-reduced MOF monolithic bodies are milled to provide an optional second binder-reduced MOF monolithic body, wherein the optional second binder-reduced MOF monolithic body has a maximum particle size that is about less than or equal to the minimum particle size of the optional second binder-reduced MOF monolithic body.

[0066] Provided the size and composition requirements are met, the second monolithic MOF body can be fabricated using other processes. For example, if the first monolithic MOF body comprises an activated extrudate with a particle width of about 2 mm, the second monolithic MOF body may comprise aggregates or particles with a particle size equal to or less than about 2 mm.

[0067] A preferred method for producing the second MOF monolithic body is to grind and sieve portions of the first MOF monolithic body to an appropriate size. The second MOF monolithic body can then be blended with the first MOF monolithic body.

[0068] According to a further aspect of the invention, a gas storage container comprising the composition is provided.

[0069] According to a further aspect of this disclosure, a gas storage container comprising the composition is provided for use in the absorption, storage and / or release of gases.

[0070] According to a further aspect of this disclosure, the composition is provided for use in the absorption, storage, and / or release of gases.

[0071] MOF monolithic body and composition

[0072] The inventors have unexpectedly discovered a composition that overcomes one or more of the disadvantages associated with compositions in the prior art.

[0073] Specifically, the compositions of the present invention have high packing density and provide rapid adsorption and desorption kinetics, while also being suitable for industrial production and for use in gas adsorption applications.

[0074] The inventors have found that large-scale production of extrudates with reduced diameters or thinner profiles is challenging because thinner extrudates often clump together and form agglomerates after extrusion. Therefore, MOF compositions are advantageous, as they can be more easily manufactured on an industrial scale while still possessing adsorption kinetics and capacity suitable for many adsorption processes, particularly carbon capture and hydrogen storage.

[0075] Unbound by theory, agglomeration of thin extrudates is considered to be due to the weight reduction of the smaller diameter extrudate. According to agglomeration theory, the tendency for two bodies to bond together after impact is largely influenced by the size and mass of the bodies. The larger the body, the more momentum and kinetic energy needs to be dissipated to keep the bodies together. In practice, this means that larger bodies will tend to bounce apart after impact, while smaller bodies (such as smaller diameter extrudates) will remain stuck together. In any large-scale process, a significant amount of extrudate-extrudate interaction is unavoidable and will often result in a large portion of the smaller diameter extrudates agglomerated and difficult to separate. Limiting the number of orifices on the stencil to ensure that the extrudates are far enough apart to avoid contact will reduce productivity to unfeasible levels. Making the extrudate mixture sufficiently "dry" and non-sticky so that the smaller diameter extrudates will not adhere to each other will typically result in very high extrusion pressures (which can lead to MOF or body damage) and stencil blockage.

[0076] The inventors have unexpectedly discovered that MOF extrudates should have a minimum particle width / diameter for practical large-scale manufacturing.

[0077] Furthermore, the inventors have discovered that the presence of the second monolithic MOF host can simultaneously increase gas adsorption / desorption kinetics and increase the gas adsorption capacity of the MOF composition, especially due to the efficient packing arrangement of the first and second monolithic MOF hosts.

[0078] Limiting the proportion of the second MOF monolithic host in the composition will also prevent excessive pressure drop when using the composition during gas adsorption.

[0079] Furthermore, producing a second, smaller monolithic MOF matrix can be more difficult than producing the first monolithic MOF matrix. Producing a second monolithic MOF matrix with a reduced particle size, such as through granulation or extrusion, typically involves processes involving milling and / or sieving. Such production processes generally result in high levels of fine particles (which require recycling) and low yields. Therefore, it is advantageous to avoid high levels of the second monolithic MOF matrix in the composition.

[0080] Therefore, a balance was achieved between ease of mass production and the dynamic and volumetric properties of the MOF monolithic body.

[0081] Furthermore, unlike other MOF bodies that contain inorganic binders or none at all, the monolithic MOF body of the present invention contains sufficient organic binders to ensure suitable robustness. For example, binder-free extruded MOF bodies are typically too fragile for industrial-scale applications.

[0082] Including a second MOF monolithic host in the composition will also promote heat transfer through the composition due to the increased number of contact points between the MOF monolithic host particles, and will also provide a favorable gas adsorption profile, especially during desorption. For example, the gas release rate in the second MOF monolithic host will be faster than that in the first MOF monolithic host, which will provide a more consistent gas flow.

[0083] A "monolithic MOF matrix" refers to a molded matrix with a solid, uniform, and continuous external and internal structure, containing a high proportion of MOF material and exhibiting a high encapsulation density. These materials differ from a MOF matrix in that the MOF material is deposited on the surface of a substrate or incorporated into a thin film of another material. A monolithic MOF matrix does not contain individual MOF particles or MOF grains.

[0084] The MOF monolithic body of the compositions of the present invention comprises MOF and a binder. These MOF monolithic bodies are combined to provide MOF monolithic body compositions that are more efficient for filling gas storage containers. MOF monolithic bodies are generally available in forms that are easy to mass-produce.

[0085] The first MOF monolithic body comprises an organic binder; and the total weight of the solid-based first MOF monolithic body (i.e., a body excluding gases, liquids and / or fluids) is at least about 80% by weight of MOF.

[0086] The first MOF monolithic body may comprise, by weight of at least about 80% by weight of a solid-based first MOF monolithic body (i.e., a body excluding gases, liquids, and / or fluids) and up to about 20% by weight of a binder, such as about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of an organic binder, such as about 80 to about 96% by weight of MOF and about 4 to about 20% by weight of an organic binder, such as about 90 to about 95% by weight of MOF and about 5 to about 10% by weight of an organic binder, such as about 94 to about 95% by weight of MOF and about 5 to about 6% by weight of an organic binder.

[0087] The second MOF monolithic body comprises adhesive and MOF.

[0088] The second MOF monolithic body may include an adhesive; and the total weight of the solid-based second MOF monolithic body (i.e., a body excluding gases, liquids, and / or fluids) includes at least about 50% by weight of MOF, such as an adhesive, and at least about 70% by weight of MOF, such as an adhesive, and at least about 80% by weight of MOF, such as at least about 80% by weight of MOF and up to about 20% by weight of adhesive, such as about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of adhesive, such as about 85 to about 96% by weight of MOF and about 4 to about 15% by weight of adhesive, such as about 90 to about 95% by weight of MOF and about 5 to about 10% by weight of adhesive, such as about 94 to about 95% by weight of MOF and about 5 to about 6% by weight of adhesive.

[0089] The first MOF monolithic body may consist essentially of MOF and an organic binder (or be composed of the same) and / or the second MOF monolithic body may consist essentially of MOF and an binder (or be composed of the same).

[0090] The first MOF monolithic body may consist substantially of (or consist of): based on the total weight of the first MOF monolithic body, about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of organic binder, and / or the second MOF monolithic body may consist substantially of (or consist of): based on the total weight of the solid second MOF monolithic body (i.e., the body excluding gases, liquids and / or fluids), about 80 to about 98% by weight of MOF and about 2 to about 20% by weight of binder.

[0091] The first MOF monolithic body and the second MOF monolithic body may contain the same adhesive and / or the same MOF, or they may contain different adhesives and / or different MOFs.

[0092] Preferably, the MOFs of the first and second monolithic MOF bodies are the same. Preferably, the adhesives of the first and second monolithic MOF bodies are the same. More preferably, the MOFs of the first and second monolithic MOF bodies are the same and exist in the same amount, and the adhesives of the first and second monolithic MOF bodies are the same and exist in the same amount.

[0093] The composition comprises at least two monolithic MOF bodies. The composition may comprise more than two monolithic MOF bodies.

[0094] The composition may consist essentially of a first monolithic MOF host and a second monolithic MOF host. The composition may also consist essentially of a first monolithic MOF host, a second monolithic MOF host, and optionally a gas.

[0095] The composition may consist of a first monolithic MOF host and a second monolithic MOF host. The composition may also consist of a first monolithic MOF host, a second monolithic MOF host, and optionally a gas.

[0096] 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 composition may comprise up to 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).

[0097] The composition comprises, 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 a first MOF monolithic body, such as at least about 60% by weight, such as at least about 70% by weight, or about 50% to about 99.9% by weight, such as about 55% to about 99.9% by weight, such as about 60% to about 99.9% by weight, such as about 80% to about 99.9% by weight, such as about 82% to about 99.5% by weight, such as about 85% to about 99% by weight, such as about 88% to about 98% by weight, such as about 92% to about 97% by weight, such as about 94% to about 96% by weight.

[0098] The composition may contain up to about 45% 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), such as up to about 40% by weight, for example up to about 30% by weight, or about 0.1 to about 50% by weight, such as 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, such as about 0.5 to about 18% by weight, for example about 1 to about 15% by weight, such as 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.

[0099] For example, the composition may comprise, 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 a first MOF monolithic body and up to about 45% by weight of a second MOF monolithic body, such as at least about 60% by weight of the first MOF monolithic body and up to about 40% by weight of the second MOF monolithic body, such as at least about 70% by weight of the first MOF monolithic body and up to about 30% by weight of the second MOF monolithic body, or about 50 to about 99.9% by weight of the first MOF monolithic body and about 0.1 to about 50% by weight of the second MOF monolithic body, such as about 55 to about 99.9% by weight of the first MOF monolithic body and about 0.1 to about 45% by weight of the second MOF monolithic body, such as about 60 to about 99.9% by weight of the first MOF monolithic body and about 0.1% by weight of the second MOF monolithic body. The second MOF monolithic body comprises about 40% by weight, such as about 80% to about 99.9% by weight of the first MOF monolithic body and about 0.1% to about 20% by weight of the second MOF monolithic body, such as about 82% to about 99.5% by weight of the first MOF monolithic body and about 0.5% to about 18% by weight of the second MOF monolithic body, such as about 85% to about 99% by weight of the first MOF monolithic body and about 1% to about 15% by weight of the second MOF monolithic body, such as about 88% to about 98% by weight of the first MOF monolithic body and about 2% to about 12% by weight of the second MOF monolithic body, such as about 92% to about 97% by weight of the first MOF monolithic body and about 3% to about 8% by weight of the second MOF monolithic body, such as about 94% to about 96% by weight of the first MOF monolithic body and about 4% to about 6% by weight of the second MOF monolithic body.

[0100] 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 body and about 1 to about 50% by weight of a second MOF monolithic body, for example, about 55 to about 98% by weight of a first MOF monolithic body and about 2 to about 45% by weight of a second MOF monolithic body, or about 70 to about 97% by weight of a first MOF monolithic body and about 3 to about 30% by weight of a second MOF monolithic body.

[0101] The composition may contain a low amount of a second MOF monolithic body. For example, the composition may contain about 80 to about 99% by weight of a first MOF monolithic body and about 1 to about 20% 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), such as about 90 to about 98% by weight of the first MOF monolithic body and about 2 to about 10% by weight of the second MOF monolithic body, such as about 94 to about 97% by weight of the first MOF monolithic body and about 3 to about 6% by weight of the second MOF monolithic body.

[0102] The first and second MOF monolithic substrates may have the same, similar, or different properties. For example, the following characteristics of the two MOF monolithic substrates may be the same and some of the same properties (e.g., adsorbent type, surface area, porosity (such as microporosity and / or mesoporosity), encapsulation density, relative density, etc.).

[0103] The first and second MOF monolithic bodies may have different characteristics and / or properties (e.g., the amount of MOF and / or binder, the type of MOF and / or binder, surface area, porosity, microporosity, mesoporosity, macroporosity, encapsulation density, relative density, etc.).

[0104] In some respects, the first and second monolithic MOF bodies may comprise different MOFs. The second monolithic MOF body may have functionalities complementary to the first monolithic MOF body that are beneficial for gas storage and separation applications. For example, when the composition is used for gas absorption, storage, and / or release, the second monolithic MOF body may act as a scavenger to remove gases and / or compounds.

[0105] Specifically, the second monolithic MOF body may comprise a MOF that can be used as a water scavenger (e.g., wherein the MOF preferentially adsorbs water rather than other gases, such as CO2) or a sulfur scavenger (e.g., wherein the MOF preferentially adsorbs sulfur compounds rather than other gases, such as methane). Thus, the second monolithic MOF body can increase volumetric capacity and remove certain gases or compounds from the gas stream.

[0106] In this respect, it is preferred that the composition comprises a low content of the second MOF monolithic body. For example, the composition may comprise about 90 to about 99.9% by weight of the first MOF monolithic body and about 0.1 to about 10% by weight of the second MOF monolithic body based on the total weight of the solid composition (i.e., the composition excluding gases, liquids and / or fluids), such as about 95 to about 99% by weight of the first MOF monolithic body and about 1 to about 5% by weight of the second MOF monolithic body, for example, about 97 to about 98.5% by weight of the first MOF monolithic body and about 3 to about 1.5% by weight of the second MOF monolithic body.

[0107] The composition may contain more than two MOF monolithic bodies having the same or different features and properties as the first MOF monolithic body and / or the second MOF monolithic body.

[0108] Optimized monolithic body and issues related to the use of adhesives

[0109] Unbound by theory, it is proposed that binders are essential for providing robustness and resistance to mechanical abrasion in monolithic MOF bodies. Furthermore, the partial or complete application of binders as a solution or paste can facilitate extrusion. Binders produce monolithic MOF bodies (such as extrudates) with high strength and abrasion resistance. Advantageously, binders allow the monolithic MOF bodies to be suitably shaped into bodies with specific particle shapes, particle size distributions, and particle aspect ratios.

[0110] The inventors have discovered that the process selection, binder, and MOF combination of this disclosure can produce MOF monolithic bodies with optimal properties such as porosity (especially high porosity), 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 using the preferred process, relatively low levels of binder can impart good mechanical robustness to the MOF monolithic bodies.

[0111] Using binders and extrusion processing to obtain MOF monolithic matrices can provide compositions with customized and tunable multimodal particle size distributions (e.g., multimodal shape and / or size distributions) and high filling efficiency, while also being robust enough to avoid breakage of the MOF monolithic matrices. Therefore, the multimodal distribution is achieved in a controlled manner, for example through controlled preparation and / or processing. This provides a controlled multimodal shape and / or size distribution that is not due to the brittleness of the matrix.

[0112] The first MOF monolithic body and / or the second MOF monolithic body may have an elastic modulus (e.g., Young's modulus, E) of about 0.5 to about 100 GPa, such as about 1 to about 50 GPa, for example about 2 to about 20 GPa.

[0113] The first MOF monolithic body and / or the second MOF monolithic body may have a hardness H of about 100 to about 5000 MPa, for example about 200 to about 2500 MPa, such as about 400 to about 1500 MPa.

[0114] Young's modulus and hardness values ​​can be determined using standard characterization methods (e.g., by nanoindentation).

[0115] A low level of binder can be achieved by using an organic polymer binder in the MOF matrix and contacting the dried MOF matrix with a second solvent prior to activation to remove a portion of the initially added organic polymer binder. Depending on the total amount of organic polymer binder added, the amount of organic polymer binder removed can be less than 20%, or greater than or equal to 20%.

[0116] Unbound by theory, it is believed that removing the organic polymer binder from the dried MOF monolithic body removes at least a portion of the organic polymer binder most easily accessible to solvents. This is considered to be the organic polymer binder coated on the surface of the MOF grains, which is likely to clog pores but is least involved in binding the MOF grains together. The inventors believe that the organic binder in closest contact with the MOF grains will dissolve the slowest because it is the least accessible to solvents. Therefore, the remaining organic polymer binder is considered to be the most effective at binding the MOF particles together.

[0117] Furthermore, this process allows for the limitation of the macroporosity of MOF monolithic matrix by controlling the amount of organic polymer binder removed from the dried MOF monolithic matrix.

[0118] Unbound by theory, removing the organic polymer binder from the dried MOF monolithic bulk portion is considered to produce a MOF monolithic bulk with a preferred porosity profile, characterized by high levels of microporosity and mesoporosity, but without high levels of macroporosity. This makes it particularly suitable for gas storage due to the combination of high density, high and useful porosity, and BET surface area. Other processes typically result in even higher levels of macroporosity and high levels of microporosity and mesoporosity, and therefore lower monolithic bulk density.

[0119] In this application, the standard IUPAC pore size definition is used to define three size ranges. Micropores are pores smaller than about 2 nm. Mesopores are pores with a size from about 2 nm to about 50 nm. Macropores are pores larger than about 50 nm. Macropores have very small adsorption capacities and do not contribute to the adsorption capacity of the material. Pore size is an important factor because it determines the accessibility of substances into the pores. Pores also facilitate the transport of substances throughout the entire MOF monolithic matrix.

[0120] The monolithic MOF host can be microporous, or in other words, the monolithic MOF host has micropores. The micropores of the monolithic MOF host can be provided by the MOF itself; that is, the MOF can have micropores. The presence of micropores in the monolithic MOF host is advantageous because it can produce properties conducive to gas adsorption, storage, separation, and purification.

[0121] In some embodiments, the monolithic MOF matrix has mesopores (i.e., pores larger than micropores but smaller than macropores). Mesopores can facilitate the transport of matter and / or fluids throughout the monolithic MOF matrix. Specifically, mesopores can provide rapid gas dynamic transport throughout the monolithic MOF matrix. Preferably, the monolithic MOF matrix contains mesopores.

[0122] Based on the total pore volume as measured by N2 adsorption, the first MOF monolithic host and / or the second MOF monolithic host can have a high level of microporosity. Based on the total pore volume as measured by N2 adsorption, the first MOF monolithic host and / or the second MOF monolithic host can have a microporosity of about 40% or greater, for example, about 40% to about 75%.

[0123] The macroporosity of a substrate can be defined as the ratio of the volume of macropores in the substrate to the encapsulation volume of the substrate.

[0124] Macroporosity can be measured using mercury intrusion porosimetry. However, mercury intrusion porosimetry cannot measure microporosity and mesoporosity. The pressure required to inflate mercury into very small micropores and mesopores exceeds the capabilities of existing equipment. Conversely, nitrogen adsorption cannot detect larger pores.

[0125] The first MOF monolithic body has a macropore volume of about 15% or less of the encapsulation volume of the first MOF monolithic body, said macropore volume may be about 13% or less of the encapsulation volume of the first MOF monolithic body, such as about 12% or less, such as about 10% or less, such as about 7% or less, such as about 5% or less, or about 0.1 to about 15%, such as about 0.2 to about 13%, such as about 0.5 to about 10%.

[0126] The second MOF monolithic body has a macropore volume of about 15% or less of the encapsulation volume of the second MOF monolithic body, such as about 13% or less, for example about 12% or less, such as about 10% or less, for example about 7% or less, such as about 5% or less, or about 0.1 to about 15%, such as about 0.2 to about 13%, for example about 0.5 to about 10%.

[0127] The large pore volume of the second MOF monolithic host can be relatively low relative to the encapsulation volume of the second MOF monolithic host.

[0128] The first MOF monolithic body may have a macropore volume of about 15% or less of the encapsulation volume of the second MOF monolithic body, said macropore volume may be about 12% or less of the encapsulation volume of the second MOF monolithic body, such as about 10% or less, for example about 7% or less, such as about 5% or less.

[0129] The macroporosities of the first and second monolithic MOF bodies may be different or the same. Preferably, the first and second monolithic MOF bodies have the same macroporosity (i.e., the ratio of macropore volume to the encapsulation volume of the first and second monolithic MOF bodies).

[0130] The surface area / unit mass available for gas adsorption is the BET surface area, as described below, which is measured by nitrogen adsorption at 77 K. Ideally, the MOF monolithic body has a high surface area and porosity. The surface area of ​​the MOF monolithic body determines its volumetric capacity, and therefore, it is preferred that the MOF monolithic body has a high surface area such that, when filled in a gas storage container, the MOF monolithic body has a high surface area / unit volume within the gas storage container.

[0131] The first MOF monolithic host and / or the second MOF monolithic host may have a BET surface area, as measured by N2 adsorption, said BET surface area being approximately 0 m². 2 / g or greater, such as about 10m 2 / g or larger, such as about 100m 2 / g or greater, for example, about 200m 2 / g or greater, such as about 300m 2 / g or greater, for example, about 400m 2 / g or greater, such as about 700m 2 / g or greater, for example, about 1000m 2 / g or greater, such as approximately 1500m 2 / g or greater, or approximately 0 to approximately 4,000 m 2 / g, such as about 0 to about 2,500m 2 / g, such as about 100 to about 2,000m 2 / g.

[0132] Some MOF materials may have a low BET surface area but still exhibit high absorption of other gases, such as hydrogen, methane, carbon dioxide, krypton and / or water.

[0133] Providing MOF monolithic bodies with high microporosity, low macroporosity, high BET surface area, and a high percentage (by weight) of MOF offers specific benefits because these characteristics provide advantageous performance for gas separation, purification, and storage applications. MOF monolithic body extrusions can possess these characteristics and are therefore particularly well-suited for use in these applications.

[0134] Due to the industrial feasibility of this process, the use of MOF monolithic bodies prepared by extrusion is advantageous. Using MOF monolithic body extrudates with the properties defined above offers further benefits, and the packing characteristics of the entire extrudate group have been further optimized to further improve the performance of MOF-containing gas storage containers.

[0135] The need to store as much gas as possible in a gas storage container of a given volume means that the bulk density of the MOF monolithic body is very important, as are the properties of the individual MOF body, such as composition and surface area.

[0136] Using a monolithic MOF body with the properties defined above has further benefits, wherein the stacking properties of the composition have been further optimized to further improve the performance of the MOF in gas storage containers when provided as a composition.

[0137] When a monolithic MOF matrix is ​​filled into a gas storage container, the bulk density of the MOF matrix is ​​an important parameter. A higher bulk density of the MOF composition in a gas storage container is beneficial to the volumetric capacity and performance of the gas storage container. This results in the adsorption and / or storage of higher levels of gas within a given volume. Maximizing the filling efficiency of the monolithic MOF matrix to increase the bulk density can improve the volumetric performance of gas storage containers used in gas separation, purification, and storage applications. As stated earlier, the filling efficiency of extrudates is generally poor.

[0138] This 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. The MOF monolithic bodies can be multimodal in shape and / or size distribution. Multimodal means that the composition comprises at least two MOF monolithic bodies, wherein the at least two MOF monolithic bodies may have different shape and size characteristics.

[0139] The non-uniform shape of some MOF monolithic bodies (such as extrudates) makes them difficult to define using simple measures such as particle size and / or particle shape. Instead, the particles of MOF monolithic bodies can be defined using parameters such as particle aspect ratio, elongation, and / or particle roundness ratio.

[0140] The inventors have determined that higher fill density and packing density can be best achieved by using a combination of at least two MOF monolithic bodies with different sizes and shape distributions.

[0141] The first MOF monolithic body has a particle aspect ratio of about 2 or greater, for example, the particle aspect ratio may be about 3 or greater, such as about 2 to about 7, for example, about 3 to about 7. Further particle aspect ratios of the first MOF monolithic body include about 2.4 or greater, about 2.5 or greater, about 2.6 or greater, or about 2 to about 6, such as 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 process reasons stated above, it is not preferable to mass-produce monolithic bodies with an aspect ratio of less than 2 by extrusion. In addition, a large aspect ratio will result in very poor filling and is not preferred. For example, particle aspect ratios greater than 20, greater than 10, or greater than 7, or sometimes greater than 5, may have poor filling density.

[0142] The shape of the first MOF monolithic body does not have to be spherical, sheet-like, and / or ellipsoidal. For example, in some aspects, the aspect ratio of the particles of the first MOF monolithic body cannot be less than 3, such as less than 2.5. Specifically, when the first MOF monolithic body is an extruder, it may not have a spherical, sheet-like, or elliptical shape.

[0143] The first monolithic MOF matrix exhibits poor filling efficiency and therefore a lower bulk density. The second monolithic MOF matrix particles can be fitted into the voids between the first monolithic MOF matrix particles. For the second monolithic MOF matrix, it is important that its particle size is less than or equal to the width of the extruded first monolithic MOF matrix. The aspect ratio of the second monolithic MOF matrix will be close to 1 (typical for most particles), but this is not a critical parameter for efficient filling; rather, it is the particle size required to fit into the available voids. The improved bulk density of the resulting composition leads to higher volumetric properties when filled into gas storage containers. The filling arrangement can depend on particle size, particle shape, particle aspect ratio, and / or the relative amounts of the first and / or second monolithic MOF matrix particles.

[0144] Monolithic bodies with high particle aspect ratios (i.e., extrudates) are generally easier to mass-produce, and therefore having high levels of such monolithic material in the composition is generally advantageous. Therefore, the composition preferably comprises a larger amount of a first MOF monolithic body with a higher particle aspect ratio compared to the second MOF monolithic body.

[0145] The first monolithic MOF host has a higher particle aspect ratio than the second monolithic MOF host. The first monolithic MOF host may have a larger particle size than the second monolithic MOF host.

[0146] Specifically, the second MOF monolithic body has a maximum particle size that is approximately less than or equal to the minimum particle size of the first MOF monolithic body.

[0147] In some respects, the ratio of the maximum particle size of the second MOF monolithic body to the minimum particle size of the first MOF monolithic body may be about 1 or less, such as about 0.05 to about 0.95, for example about 0.1 to about 0.75, such as about 0.15 to about 0.5.

[0148] The maximum and / or minimum particle size of the first and / or second monolithic MOF matrix can refer to particle size, particle length, and / or particle width.

[0149] When the first MOF monolithic body has a high aspect ratio (e.g., a particle aspect ratio of about 2 or greater, particularly the particle aspect ratio disclosed herein for the first MOF monolithic body (e.g., a typical extruder), the minimum particle size of the first MOF monolithic body can refer to the particle width.

[0150] When using extrusion methods to prepare the first monolithic MOF body, the minimum particle size (width / thickness in this context) of the first monolithic MOF body can be based on measurements of the extrudate. Extrudates may shrink upon drying, and therefore the orifice diameter is not always a reliable indicator of extrudate thickness. For example, particle size may shrink by about 10% upon drying, so the particle size of the dried extrudate may be about 10% smaller than the particle size of the originally prepared extrudate. For clarity, references to the particle size of the monolithic MOF body will refer to the particle size of the final dried monolithic MOF body. However, extrudates prepared using a specific orifice will be consistent in thickness.

[0151] Using the extrusion method described herein, the particle width of the first MOF monolithic body can be greater than or equal to about 500 μm, for example greater than or equal to about 750 μm, such as greater than or equal to about 900 μm, such as greater than or equal to about 1 mm, such as about 1 to about 5 mm, such as about 1 to about 3 mm, or any value as disclosed herein with respect to the minimum particle size of the first MOF monolithic body.

[0152] The minimum particle size (e.g., particle width) of the first MOF monolithic body may be greater than or equal to about 1 mm, greater than or equal to about 1.5 mm or about 2 mm, or about 0.5 mm to about 10 mm, such as about 0.75 mm to about 5 mm, such as about 1 to about 5 mm, such as about 1 to about 3 mm, or about 1.5 to about 5 mm, such as about 2 to about 5 mm, such as about 2 to about 4 mm.

[0153] Preferably, the first MOF monolithic body may have a minimum particle size greater than or equal to about 1 mm.

[0154] More preferably, the first MOF monolithic body may have a minimum particle size of about 2 to about 5 mm.

[0155] The first MOF monolithic body may have a maximum particle size (e.g., particle length) greater than or equal to about 2 mm, such as about 2 mm to about 100 mm, such as about 2 mm to about 50 mm, such as about 2 mm to about 35 mm, such as about 2 mm to about 30 mm, such as about 2.25 mm to about 25 mm, such as about 2.5 mm to about 15 mm, such as about 2.75 mm to about 10 mm, such as about 3 mm to about 10 mm.

[0156] Specifically, when the minimum particle size of the first monolithic MOF body is about 1 to about 5 mm, the maximum particle size can be about 2 to about 35 mm, such as about 3 to about 25 mm, preferably about 3 to about 15 mm. When the minimum particle size of the first monolithic MOF body is about 1.5 to about 5 mm, the maximum particle size can be about 3 to about 35 mm, such as about 4 to about 25 mm, preferably about 4.5 to about 20 mm. When the minimum particle size of the first monolithic MOF body is about 2 to about 5 mm, the maximum particle size can be about 4 to about 35 mm, such as about 6 to about 25 mm.

[0157] The second monolithic MOF body typically has a particle aspect ratio close to 1. When the aspect ratio of the second monolithic MOF body is close to 1 (e.g., about 1 to about 2, such as about 1 to about 1.5, such as about 1 to about 1.2, such as about 1 to about 1.1), the maximum and / or minimum particle sizes of the second monolithic MOF body can be substantially the same or close. When the aspect ratio of the second monolithic MOF body is close to 1, the maximum and / or minimum particle sizes of the second monolithic MOF body can refer to the particle size.

[0158] The second MOF monolithic matrix can have a maximum particle size smaller than the minimum particle size of the first MOF monolithic matrix.

[0159] The maximum particle size of the second MOF monolithic body can be less than or equal to about 5 mm, such as less than or equal to about 3 mm, such as less than or equal to about 1 mm, such as about 20 μm to about 1 mm, 3 mm or 5 mm, or about 50 μm to about 5 mm, such as about 50 μm to about 3 mm, such as about 100 μm to about 2 mm, such as about 50 μm to about 1 mm, such as about 150 μm to about 1 mm.

[0160] The minimum particle size of the second MOF monolithic body can be greater than or equal to 20 μm, such as greater than or equal to 50 μm, such as about 20 μm to about 5 mm, such as about 50 μm to about 5 mm, such as about 50 μm to about 3 mm, such as about 100 μm to about 2 mm, such as about 50 μm to about 1 mm, such as about 150 μm to about 1 mm.

[0161] In the context of this disclosure, particle size may refer to the mean particle size. Similarly, particle aspect ratio may refer to the mean particle aspect ratio.

[0162] In the context of this disclosure, maximum particle size may refer to the mean maximum particle size, which is the average of the maximum diameters of the first MOF monolithic host particle and / or the second MOF monolithic host particle.

[0163] In the context of this disclosure, minimum diameter may refer to the mean minimum particle size, i.e., the mean of the minimum diameters of the first MOF monolithic host particle and / or the second MOF monolithic host particle.

[0164] The mean particle size and the mean particle aspect ratio can be determined using methods and instruments well known to those skilled in the art. Further details are described in the Methods section below.

[0165] Bulk density is not the only important parameter for the gas storage and purification performance of gas storage containers. Gases need to be able to flow through the packed bed without excessive pressure drop to achieve rapid gas dynamics during gas adsorption and separation. Therefore, it is important to leave some gaps between the monolithic MOF bulks. This means that the composition does not contain too many small particles that could block all the gaps between the monolithic MOF bulks. Therefore, limiting the proportion of a second monolithic MOF bulk in the composition helps to avoid high pressure drop problems.

[0166] Since the first monolithic adsorbent body has a form and particle aspect ratio that are easier to produce on an industrial scale (e.g., by extrusion), it is preferred that the composition contains a higher proportion of the first MOF monolithic body compared to the second MOF monolithic body.

[0167] Furthermore, it is preferred that the composition does not contain excessively small MOF monolithic bulk and / or MOF material particles, as very small particles (known as fine particles or fine materials) may block all gaps between the MOF monolithic bulk. If the composition contains too much MOF monolithic bulk and / or too small MOF particles, it may cause excessive pressure drop and slowed gas dynamics during the use of the MOF monolithic bulk when filling a gas storage container. In addition, too many fine particles may result in excessive dust when handling the MOF monolithic bulk.

[0168] In the context of this disclosure, MOF materials should be understood as MOF monolithic hosts or MOF particles having a particle size of less than about 20 μm (i.e., individual, loose MOF particles, or portions that are mostly MOF and do not form a monolithic MOF host). For example, MOF particles may consist essentially of MOF (with only small amounts of other substances, such as binders, present).

[0169] The composition may contain about 10% by weight or less of MOF material with a particle size of less than about 20 μm based on the total weight of the solid composition (i.e., the composition excluding gases, liquids and / or fluids), such as about 5% by weight or less, for example about 2% by weight or less, such as about 1% by weight or less, for example about 0.1% by weight or less, or about 0.01% to about 10% by weight, such as about 0.05% to about 5% by weight, such as about 0.1% to about 2% by weight.

[0170] The need to store as much gas as possible in a given volume of gas storage container means that the bulk density of the composition is very important. The higher the bulk density, the more material can be packed into the usable working volume. The bulk density of the bulk group varies depending on the density of the individual bulks (often defined as encapsulation density) and how the bulks are packed together within the bulk. If the MOF monolithic bulk has a shape that makes packing it together inefficient, then including a MOF monolithic bulk with a high individual encapsulation density makes little sense. 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 bulk; therefore, compositions with high surface area and high bulk density can have a high surface area / unit volume, resulting in compositions with preferred volumetric performance when used in gas storage containers.

[0171] Bulk density can be defined as the mass of the MOF monolithic matrix divided by the total volume occupied by these MOF monolithic matrices, or in other words, the mass of the composition divided by the total volume occupied by the composition.

[0172] The composition may have a bulk density of about 0.3 g / cm³. 3 Or larger, for example, about 0.5 g / cm³ 3 Or even larger, such as about 0.6 g / cm³ 3 Or even higher, for example, about 0.7 g / cm³ 3 Or even larger, such as about 0.8 g / cm³ 3 Or even larger, for example, about 0.9 g / cm³ 3 Or larger, such as about 0.3 to about 3 g / cm³ 3 For example, approximately 0.3 to approximately 1.5 g / cm³ 3 .

[0173] For the avoidance of doubt, 'bulk density' can refer to 'untaped density' (i.e., the density of a material or powder when it settles freely) or 'taped density' (i.e., the maximum density a material achieves when vibrated under specific conditions). Preferably, bulk density is tapped density.

[0174] Untamped density and tamped density can be similar. For example, extrudates typically have high aspect ratios and poor filling, and therefore tamping has little effect on bulk density.

[0175] Preferably, the MOF monolithic host has a high encapsulation density in order to minimize the volume of the MOF monolithic host required for a given gas adsorption process.

[0176] Encapsulation density can depend on the crystal structure of the adsorbent and the MOF, which can vary depending on the gas storage and separation application, and therefore the encapsulation density of the monolithic MOF body can depend on the application.

[0177] The first MOF monolithic matrix and / or the second MOF monolithic matrix can have an encapsulation density of approximately 0.3 g / cm³. 3 Or even larger, such as about 0.4 g / cm³ 3 Or even higher, for example, about 0.6 g / cm³ 3 Or even larger, such as about 0.7 g / cm³ 3 Or even higher, for example, about 0.8 g / cm³ 3 Or even higher, such as about 1 g / cm³ 3 Or larger, such as about 0.3 to about 3 g / cm³ 3 For example, approximately 0.4 to approximately 2 g / cm³ 3 .

[0178] Furthermore, the relative density of the monolithic MOF bulk is an important parameter for defining the porosity of the monolithic MOF bulk and the accessibility of the pores in the MOF bulk associated with the porosity. Relative density can be defined as the ratio of the encapsulation density of the monolithic MOF bulk to the crystal density of the MOF. The crystal density of a MOF is the theoretical density of a single MOF crystal. The crystal densities of many MOFs have been calculated and are available in the Cambridge Structure Database (CSD).

[0179] Whether the internal pores of a MOF monolithic matrix collapse during processing is typically indicated by the relative density of the resulting MOF monolithic matrix. Different MOFs can have different crystal densities depending on their structure. If the encapsulation density of the MOF monolithic matrix is ​​greater than the crystal density (i.e., relative density > 1), this is likely due to the collapse of internal pores. The higher the relative density (above 1), the more the internal pores will collapse, and the lower the adsorption capacity. A relative density greater than 1 implies a wasteful loss of porosity, as such a high value can only be achieved by destroying some of the useful pores. Therefore, it is preferable that the relative density of the MOF monolithic matrix not be too high to avoid inefficient internal pore collapse in the MOF.

[0180] However, the relative density of a monolithic MOF should generally not be much less than 1, as this leads to poor volumetric efficiency. Very low relative densities typically indicate an excessive level of undesirable large pores. Relative densities much less than 1 (such as less than 0.3) imply the presence of excessive porosity, mostly in the form of larger (and therefore less useful) pores (i.e., macropores) within the bulk.

[0181] The first MOF monolithic body and / or the second MOF monolithic body may have a relative density of about 0.3 or greater, for example, about 0.3 to about 1.7, such as about 0.5 to about 1.5, or about 0.3 to about 1.3, preferably about 0.7 to about 1.2.

[0182] MOF and binder

[0183] The MOF of the second MOF monolithic body may be the same as or different from the MOF of the first MOF monolithic body. Preferably, the MOF of the second MOF monolithic body is the same as the MOF of the first MOF monolithic body.

[0184] The MOF with the first and / or second monolithic MOF host structures can be independently selected from MOFs, wherein the metal ions of the MOFs are selected from elements and mixtures thereof in Groups 1a, 11a, 13a, 14a to 15a, and 15b to 15b of the periodic table. The metal ions can 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 can also be selected from transition metals, Si, Mg, Al, and mixtures thereof. Preferably, the metal ions are selected from Zr, Zn, Al, Fe, Ti, Nb, Ni, Cu, Mg, Co, Cr, Mn, Si, and mixtures thereof. More preferably, the metal ion is selected from Zr, Zn, Nb, Ni, Cu, Nb, Si, Ti, and mixtures thereof. For example, the metal ion may be selected from Zn. 2+ 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 its mixtures and combinations. Metal ions can be provided by salts of metal ions, such as ZrCl4.

[0185] Transition metals here can be understood as chemical elements in the d-block of the periodic table (i.e., groups 3 to 12, including Zn, Pd, and Pt, as well as Sc and Y).

[0186] The MOF with the first monolithic MOF host and / or the MOF with the second monolithic MOF host can be independently selected from zeolite imidazole ester framework (i.e., ZIF), mixed metal MOFs (such as Si, Ni, Fe, Ti and / or Zn mixed metal MOFs) and mixtures thereof.

[0187] The organic linker of a MOF can be at least a monodentate organic linker, or a derivative thereof. Preferably, the organic linker of the MOF is, for example, a monodentate and / or bidentate organic linker, wherein the organic linker exists in the MOF in a partially deprotonated or fully deprotonated form. Alternatively, the organic ligand can be a polydentate organic ligand capable of donating two or more pairs of electrons in a complexation 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 a pair of electrons to form two or more sub-coordinate bonds. Preferably, the oxygen atom may be present as a carboxylate or a nitro group. Preferably, the nitrogen atom may be present as an amino group. Typically, the multiple organic ligands may be aromatic carboxylates, aromatic amines, and / or aromatic nitro groups.

[0188] The MOF of the first monolithic MOF body and / or the MOF of the second monolithic MOF body may be independently selected from MOFs containing organic links, the organic links 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 mixtures thereof.

[0189] The MOF of the first monolithic MOF body and / or the MOF of the second monolithic MOF body may be independently selected from MOFs containing organic joints, wherein the organic joints are selected from: fumaric acid, oxalic acid, citric acid, succinic acid, phthalic acid (e.g., terephthalic acid, 1,3-phthalic acid), naphthalenedicarboxylic acid, biphenyl dicarboxylic acid (e.g., 4,4'-biphenyl dicarboxylic acid (BPDC)), terphenyl dicarboxylic acid (e.g., p-terphenyl-4,4”-dicarboxylic acid), azine (e.g., pyrazine), bipyridine dicarboxylic acid (e.g., 2,2'- Bipyridine-5,5'-dicarboxylic acid), benzotricarboxylic acid (e.g., 1,2,3-, 1,2,4- and 1,3,5-benzotricarboxylic acid (BTC)), benzotetracarboxylic acid, dihydroxyterephthalic acid (e.g., 2,5-dihydroxyterephthalic acid (DHBDC)), azoles (e.g., imidazoles, such as 2-methylimidazolium, 4,5-dichloroimidazolium, 2-imidazolium carboxaldehyde); triazoles, such as 1,2,4-triazoles), pyrene (e.g., tetra(terebenzoic acid)pyrene), porphyrins (e.g., tetra(4-carboxyphenyl)porphyrin), and mixtures thereof.

[0190] Preferably, the organic linkers of the MOF of the first monolithic MOF host and / or the MOF of the second monolithic MOF host are independently selected from terephthalic acid, aminoterephthalic acid, 1,3,5-benzenetricarboxylic acid, 2-methylimidazolium, oxalic acid, citric acid, 1,2,4-triazole, pyrazine, 2,5-dihydroxyterephthalic acid and mixtures thereof.

[0191] The MOF of the first monolithic MOF host and / or the MOF of the second monolithic MOF host can be independently selected from UiO-66, UiO-66-NH2, UiO-67, UiO-68, NU-1000, PCN-222, MOF-808, ZU-301, zirconium fumarate, ZIF-8, ZIF-67, ZIF-71 and ZIF-90, aluminum fumarate, MIL-53, CAU-10, MIL-160(Al) and 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.

[0192] The MOF of the first monolithic MOF host and / or the MOF of the second monolithic MOF host can be selected independently, for example, from 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.

[0193] MOFs can vary depending on the gas storage or purification application and the type of gas or adsorbent involved. For example, for carbon capture applications, selecting an MOF with high absorption and selectivity for carbon dioxide is preferred.

[0194] The MOF with the first monolithic MOF host and / or the MOF with the second monolithic MOF host can be independently selected from MOFs suitable for the type of gas or adsorbent involved.

[0195] The selection of MOFs can also be based on the environmental and conditions experienced by the monolithic MOF body and the stability of the MOF (such as its thermal, chemical, and / or mechanical stability). For example, in gas purification and / or storage applications involving high temperatures and / or the presence of certain substances (such as water or streams), MOFs with high thermal and chemical stability are preferred. For instance, in carbon capture from flue gas, the gas stream may contain water, and therefore, MOFs with high stability to water are preferred.

[0196] Maintaining the porosity of MOFs during processing is important. MOFs are generally not very robust due to the nature of the ligand-metal ionic bonds that form the pore structure. These bonds depend on metal coordination chemistry rather than stronger covalent or ionic bonds. Applying external pressure can deform and break down the pores of MOFs, thus reducing the surface area available for gas adsorption. Different MOFs have different levels of stability and strength, depending on characteristics such as their composition and crystal structure.

[0197] For clarity, references to MOF include derivatives of the MOF, including derivatives of the organic linker, and variations, combinations, and mixtures of the metal ions and / or metal clusters used. For example, references to CPO-27 may include CPO-27-Ni, CPO-27-Mg, CPO-27-Co, or other variants (i.e., wherein the metal ions in the MOF are different), and references to UiO-66 may include UiO-66-NH2, UiO-66-Br, UiO-66-OH, or other variants (i.e., wherein the organic linker in the MOF is different).

[0198] Furthermore, references to MOFs may include MOFs that are part of the same class of meshes but have the same secondary building units (SBUs) and topology but differ in the length, functionalization, and / or pore size of the organic joints. For example, references to IRMof-1 may include IRMof-8, IRMof-11, IRMof-18 (i.e., MOFs with different lengths, functionalizations, and / or links of the organic joints).

[0199] The adhesive can be any adhesive that provides adhesion to the monolithic MOF body, such as providing mechanical and chemical stability and robustness.

[0200] The binder for the second MOF monolithic matrix can 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.

[0201] The binder for the first monolithic MOF body is an organic binder. Preferably, the organic binder for the first monolithic MOF body is an organic polymer binder.

[0202] Preferably, the binder for the first MOF monolithic body and / or the second MOF monolithic body is an organic polymer binder.

[0203] More preferably, the adhesive of the second MOF monolithic body is the same as the organic adhesive of the first MOF monolithic body (preferably an organic polymer adhesive).

[0204] The binder may not be highly soluble in water, and may even be insoluble in water. For example, a hydrophobic binder can advantageously provide hydrophobic properties to the first MOF monolithic body and / or the second MOF monolithic body. In this way, when the first MOF monolithic body and / or the second MOF monolithic body are used in gas separation and storage applications where the gas stream contains water, the first MOF monolithic body and / or the second MOF monolithic body (e.g., the first MOF monolithic body and / or the second MOF monolithic body) can preferentially adsorb other gases (e.g., carbon dioxide) in the gas stream than water.

[0205] The adhesive is soluble in an aqueous mixture of water and solvent, or soluble in a non-aqueous solvent.

[0206] The first MOF monolithic matrix and / or the second MOF monolithic matrix may be modified after synthesis, for example by modifying the binder, to provide the first MOF monolithic matrix and / or the second MOF monolithic matrix with hydrophobic properties.

[0207] Preferably, when preparing the first MOF monolithic body and / or the second MOF monolithic body using the method of this disclosure with an organic binder, the solubility of the organic binder in the first solvent is the same as or higher than the solubility of the organic binder in the second solvent. When using this method, a second solvent is added to the first dried MOF monolithic body and / or the second dried MOF monolithic body to remove some of the organic binder from the first dried MOF monolithic body and / or the second dried MOF monolithic body, providing a MOF monolithic body with reduced first binder and / or a MOF monolithic body with reduced second binder. Typically, dissolved organic binder material can diffuse from the first dried MOF monolithic body and / or the second dried MOF monolithic body into the second solvent. Therefore, it is preferable that the solubility of the organic binder in the second solvent is lower than its solubility in the first solvent.

[0208] Unbound by theory, it is believed that removing the organic binder from the first and / or second dry MOF monolithic matrix removes the most accessible organic binder, which is the least involved in binding adsorbent particles together and, rather, most likely to clog the pores of the adsorbent in the first and / or second dry MOF monolithic matrix. In this way, MOF monolithic matrices with reduced first and / or second binders can be prepared, exhibiting a more accessible pore system (e.g., higher BET surface area and higher porosity). Therefore, MOF monolithic matrices prepared using this process can have better volumetric properties, and particularly a more accessible pore system, allowing for faster gas flow and dynamics throughout the MOF monolithic matrix.

[0209] Preferably, the polymeric organic binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyvinylpyrrolidone (PVP), polyimide (PI), polyvinyl formal, polyacrylates (including polyacrylic acid), polycarboxylate, polylactic acid, polyethylene glycol, polypropylene glycol, poly(1,4-phenylene ether sulfone) (PFEES), polydimethylsiloxane (PDMS), polytetrahydrofuran (PTHF), polyolefins, polyamides, biopolymer-based materials (such as polysaccharide gums, including xanthan gum, guar gum, alginate, chitosan), cellulose-based polymers (such as cellulose, cellulose acetate, hydroxypropyl methylcellulose (HPMC), methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropyl methylcellulose phthalate (HPMCP)) and mixtures thereof. Preferably, the binder is selected from PVA and cellulose-based polymers (especially methylcellulose) and mixtures thereof.

[0210] Polymer organic binders can be hydrophobic polymer organic binders.

[0211] MOF monolithic body and composition preparation

[0212] The composition can be prepared using any suitable preparation process.

[0213] Furthermore, the MOF in the compositions of the present invention can be manufactured using any process and / or can be purchased from any commercial source.

[0214] The inventors have developed methods for preparing the compositions of the present invention involving extrusion. When the compositions are prepared, for example, by these methods and packaged into gas storage containers, the compositions exhibit excellent volumetric and kinetic properties, high volumetric capacity, high gas absorption, and / or high selectivity.

[0215] Using this extrusion method to form MOF monolithic bodies is particularly advantageous because it offers excellent scalability and can be implemented on an industrial scale.

[0216] The method described provides a monolithic MOF body with high MOF content, high microporosity, and low macroporosity, thereby offering excellent volumetric performance for gas storage. Using a monolithic MOF body with high microporosity, low macroporosity, high BET surface area, and including a high level of MOF in gas storage containers offers specific benefits.

[0217] However, extrudates produced on an industrial scale typically have low bulk density due to poor filling efficiency caused by the high aspect ratio of the extrudate. The method of the present invention is particularly useful because producing extrudates with high filling efficiency at industrial rates is challenging.

[0218] Using these methods to prepare monolithic MOFs avoids the generation of fine particles. A major limitation in preparing milled monolithic MOFs is likely the generation of high levels of unwanted fine particles. This could be a significant problem when implemented on an industrial scale.

[0219] The first monolithic MOF matrix and / or the second monolithic MOF matrix can be extruded (i.e., in the form of an extruded material) or produced from an extruded material. Preferably, the first monolithic MOF matrix and / or the second monolithic MOF matrix are prepared by extrusion. More preferably, the first monolithic MOF matrix is ​​an extruded material.

[0220] The term extrudate can be understood as particles prepared by extrusion.

[0221] The first monolithic MOF matrix and / or the second monolithic MOF matrix can be prepared by a process that does not include milling.

[0222] Although compositions can be formed by combining the components in any order and / or performing the steps in any order, the best results for preparing MOF monolithic bodies are obtained when the methods of this disclosure are followed as described below.

[0223] A method is provided for preparing a composition comprising at least two MOF monolithic bodies, the method comprising the following steps:

[0224] a. Provide a wet-adhesive MOF block, the wet-adhesive MOF block comprising:

[0225] i.MOF;

[0226] ii. Based on the total weight of the wetted binder MOF bulk, approximately 50% to approximately 95% by weight of the first solvent; and

[0227] iii. An organic binder, wherein the binder can be added as a solution, dispersion, powder or mixture thereof;

[0228] b. Optionally, reduce the proportion of the first solvent in the wetted binder MOF block to provide an undried binder MOF block;

[0229] c. Extruding and cutting wet binder MOF blocks or undried binder MOF blocks to provide a first undried MOF monolithic body with a particle aspect ratio of about 2 or greater;

[0230] d. Remove at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body;

[0231] e. Optionally, a second solvent is added to the first dried MOF monolithic matrix to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic matrix to provide an optional MOF monolithic matrix with reduced first binder;

[0232] f. Optionally, at least some of the second solvent is removed from the MOF monolithic body reduced by the optional first binder to provide an optional first unactivated MOF monolithic body;

[0233] g. Activating the first dried MOF monolithic body or the optional first unactivated MOF monolithic body by subjecting it to a temperature of about 100°C or greater to provide a first MOF monolithic body; and

[0234] h. Combining a first MOF monolithic body with a second MOF monolithic body to provide a composition, wherein the second MOF monolithic body has a maximum particle size that is about less than or equal to the minimum particle size of the first MOF monolithic body.

[0235] The first solvent may comprise one or more substances, such as 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 comprise 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).

[0236] If the wet binder MOF block is too soft or too wet to form (i.e., extrude and cut) the first undried MOF monolithic body, step b can be performed to reduce the proportion of the first solvent in the wet binder MOF block to provide the undried binder MOF block.

[0237] Steps e and f are optional. For example, the composition can be prepared without adding or removing the second solvent, wherein at least a portion of the organic binder (and at least a portion of the residual first solvent and at least a portion of any unreacted reactants) is not removed. Specifically, when the first MOF monolithic body and / or the second MOF monolithic body are prepared from certain MOFs (such as UTSA-16, MOF-808, and / or ZU-301), optional steps e and f of the method can be omitted. This simplifies the process, resulting in a faster and / or cheaper preparation method. Preferably, steps e and f are included in the method.

[0238] The first MOF monolithic body prepared in this way can be combined with the second MOF monolithic body in step h to provide the composition.

[0239] The second MOF monolithic body can be added at any step after step c, and is not necessarily required to be added in step h. Preferably, after step f, the second MOF monolithic body component is added in the form of a second unactivated MOF monolithic body, and the first unactivated MOF monolithic body and the second unactivated MOF monolithic body are activated together.

[0240] It should be understood that the terms "first MOF monolithic host component and / or second MOF monolithic host component" and "related first MOF monolithic host component and / or second MOF monolithic host component" are used here to refer to the form in which the first MOF monolithic host and / or second MOF monolithic host will be in a given method step.

[0241] A method for preparing the composition of the present invention is also provided, the method comprising the following steps:

[0242] i. Forming a wetted metal-organic framework (MOF) reactant, wherein the wetted metal-organic framework reactant comprises MOF, unreacted MOF precursor and reaction solvent;

[0243] ii. Contact the moistened MOF reactive bulk with the binder to form a moistened binder bulk;

[0244] iii. Dry the wet adhesive bulk portion to form an undried adhesive MOF bulk;

[0245] iv. Form the undried binder mass into an undried MOF monolithic body;

[0246] v. Remove at least some of the remaining solvent from the undried MOF monolithic matrix to form a dried MOF monolithic matrix;

[0247] vi. Activate the dry adsorbent body by subjecting it to a temperature greater than about 100°C to form the adsorbent body.

[0248] Preferably, the method includes:

[0249] I. Forming a moistened MOF reaction mass, wherein the moistened MOF reaction mass comprises:

[0250] i. Based on the total weight of the moistened MOF reactant, about 20% to about 70%, or about 30% to about 60% or about 40% to about 50% of MOF;

[0251] ii. By weight of MOF in the moistened MOF reactant, approximately 3% to approximately 50%, approximately 8% to approximately 40%, or approximately 10% to approximately 30% of unreacted MOF precursor; and

[0252] iii. The reaction solvent, by weight of the moistened MOF reaction mass, is about 10% to about 70% by weight, preferably about 10% to about 60%, preferably about 10% to less than about 50%;

[0253] II. Contact the moistened MOF reactive block with the organic binder to provide a moistened binder MOF block;

[0254] III. Optionally, the proportion of reactive solvent in the wetted binder MOF block can be reduced to provide an undried binder MOF block;

[0255] IV. Extruding and cutting wet binder MOF blocks or undried binder MOF blocks to provide a first undried MOF monolithic body with a particle aspect ratio of about 2 or greater;

[0256] V. Remove at least some of the remaining solvent from the first undried MOF monolithic matrix to provide a first dried MOF monolithic matrix;

[0257] VI. Optionally, the first dried MOF monolithic body is contacted with a washing solvent 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 body, to provide an optional first binder-reduced MOF monolithic body;

[0258] VII. Optionally, at least some of the second solvent is removed from the MOF monolithic body reduced by the optional first binder to provide an optional first unactivated MOF monolithic body;

[0259] VIII. Activating the first dried MOF monolithic body or optionally the first unactivated MOF monolithic body by subjecting it to a temperature of about 100°C or greater to provide a first MOF monolithic body; and

[0260] IX. Combining a first MOF monolithic body with a second MOF monolithic body to provide a composition, wherein the second MOF monolithic body has a maximum particle size that is about less than or equal to the minimum particle size of the first MOF monolithic body.

[0261] The terms “unreacted precursor material” and “reaction byproduct” in steps I and ii refer to unreacted materials and byproducts used in the preparation of MOF and / or present in the MOF reaction mixture after the preparation of MOF, and which are not MOF themselves.

[0262] The advantage of this method is that it allows the use of MOF reaction mixtures to prepare compositions and / or first MOF monolithic bodies and / or second MOF monolithic bodies without the need to wash and / or process the MOF reaction mixture.

[0263] This method (i.e., providing a moistened MOF block and / or contacting the moistened MOF block with an organic binder to provide a moistened binder MOF block) can be used in any of the methods of the present invention.

[0264] The second MOF monolithic body of the composition of the present invention can be prepared using a method similar to that described herein, or it can be provided from another source. For example, the second MOF monolithic body can be obtained from a commercial source.

[0265] In this way, a second MOF monolithic matrix with different compositions and / or properties can be combined with a first MOF monolithic matrix. This can produce compositions with excellent volumetric properties, kinetic properties, and stability.

[0266] Preferably, step (I) is carried out by contacting a metal-organic framework precursor material (preferably two or more metal-organic framework precursor materials) with a reaction solvent to form a wetted MOF reactive bulk. Preferably, at least some of the precursor materials are in solid form. Preferably, no further reaction steps are carried out after contact. Preferably, the wetted MOF reactive bulk is not subjected to any washing or concentration steps. Preferably, the wetted MOF reactive bulk is not subjected to any solvent exchange process. Preferably, the wetted MOF reactive bulk is used directly after preparation.

[0267] Suitable conditions for such a contact reaction are entirely within the purview of those skilled in the art. For example, such a contact reaction may be carried out at temperatures less than about 100°C, such as about 20°C to about 100°C, or about 50°C to about 90°C, for a duration of more than about 30 minutes, or more than about 1 hour, or more than about 2 hours, or more than about 4 hours, or less than about 2 days, or less than about 1 day, or less than about 18 hours, and optionally shearing may be performed during the reaction period to form a moistened metal-organic framework reactive mass.

[0268] Suitable equipment includes Sigma or Z-blade high-torque mixers or screw mixers. Strong shearing contributes to homogeneity of the mixture and reduces the resulting particle size. Alternatively, equipment such as the Cyclomixer from Hosokawa Micron can be used.

[0269] The conditions of the reaction mixture used to form the wet MOF reaction mass, such as the type and concentration of the solvent, temperature, and reaction time, can vary, allowing for the high-yield formation of a wide variety of MOFs. Equipment such as twin-screw extruders is not preferred because the short residence time limits the process flexibility 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.

[0270] One option is to partially mix the different precursors with the reaction solvent before adding them together under stirring. For example, ZU-301 can be prepared by: (i) preparing a dispersion / slurry of basic zinc carbonate in water under 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 and stirring vigorously at high temperature for several hours.

[0271] The moistened MOF reaction bulk can have a solids content of about 20% to about 75% by weight, or about 25% to about 60% by weight, or about 30% to about 50% by weight. Conventional adsorbent bulk synthesis via dilute sol-gel may only achieve a solids content of 8% by weight or less, while the method of the present invention can achieve a high solids content without centrifugation. The reaction bulk is held under reaction conditions for a sufficiently long time to ensure that most of the precursors have reacted.

[0272] Step (II) involves contacting the moistened MOF reactive block with an adhesive (preferably a polymeric organic adhesive) to form a moistened adhesive MOF block.

[0273] The binder may be in solution form (if soluble in a suitable solvent), or it may be added 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-solventization of the binder increases the interaction and effectiveness of the binder with the wetted MOF reactive bulk compared to addition as a pure powder, while limiting the amount of additional solvent required. Adding soluble organic polymer binders as solutions can be very effective for the dispersion and subsequent properties of the binder (thus limiting the amount required), but significantly increases the amount of solvent that needs to be removed subsequently. The binder is typically mixed with the wetted MOF reactive bulk and subjected to prolonged mixing to ensure homogeneity.

[0274] The binder (preferably a polymeric organic binder) can be partially solvated, preferably by premixing with one or more solvents selected from: water, DMSO, short-chain alcohols (C1 to C4) (including methanol, ethanol and propanol), short-chain (C1 to C4) organic acids (including formic acid and acetic acid, glycols) and mixtures thereof.

[0275] The binder can be added to the wetted MOF reactive block 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% of the weight of the MOF in the wetted MOF reactive block.

[0276] The adhesive may be provided as a solution or dispersion of about 67% by weight, for example, by adding 20g of adhesive to 30g of solvent. Alternatively, the adhesive may be provided as a solution or dispersion of about 4% to 70% by weight, or a solution or dispersion of about 10% to about 50% by weight, or a solution or dispersion of about 30% to about 40% by weight.

[0277] The binder is in contact with the moistened MOF reactive block at a binder-to-MOF ratio of about 1:19, or about 1:15, or about 1:12, or about 1:7, or about 1:5, or about 1:4, or about 1:3.

[0278] Preferably, step (II) follows immediately after step (I).

[0279] Step (III) involves partially drying the wet adhesive block to form an undried adhesive block. Step (III) involves removing at least some (but not all) of the reaction solvent from the wet adhesive block to form the undried adhesive block.

[0280] Step (III) can be implemented in several different ways. The wet binder block can be further dried before cutting. This can be done, for example, in a scraped film evaporator or a heated high-torque mixer, and the resulting undried binder block is then cut and formed into smaller bodies. The wet binder block can be dried on a flat surface to form an undried binder block, which is then cut in a cutting mill or slitting machine or other suitable cutting equipment. Such methods are examples of removing (e.g., evaporating) at least some, but not all, of the reactive solvent from the wet binder block to form the undried binder block.

[0281] For example, step (III) can be carried out by: (i) evaporating the solvent; and / or (ii) adding an adsorbent material having a lower solvent level than the wet binder block to the wet binder block, wherein the adsorbent material is selected from one or more of silica, zeolite, activated carbon, graphene, metal-organic framework or combinations thereof.

[0282] Preferably, step (III) is carried out at about 20°C to about 80°C, or about 40°C to about 60°C for at least about one day, or at least about two days, or at least about three days.

[0283] Typically, the undried binder mass formed by reducing the reactive solvent level in step (III) takes 10 seconds. -1 Its viscosity at 25°C is approximately 3.0 x 10⁻⁶. 5 mPa·s to approximately 3.0 x 10⁻⁶ mPa·s 6 mPa·s. For example, undried binder blocks within 10 seconds prior to any cutting step. -1 And the viscosity at 25°C is >approximately 4.0 x 10⁻⁶. 5 mPa·s. The undried binder block retains enough solvent to deform under pressure and impact, thus allowing it to be rounded, for example, in a rounding machine. Typically, this occurs within 10 seconds. -1 At 25°C, the viscosity of the undried binder block is less than approximately 1.25 x 10⁻⁶. 6 mPa.s.

[0284] Optionally, steps (II) and (III) may be performed simultaneously or sequentially.

[0285] Step (IV) forms the undried MOF monolithic body. Step (IV) is performed by extrusion and cutting. The undried MOF monolithic body typically has the same composition as the undried binder MOF block.

[0286] Step (V) removes at least some of the remaining solvent from the undried MOF monolithic matrix (optionally a washed adsorbent matrix) to form a dried MOF monolithic matrix. Step (e) can be carried out by gradual drying at a temperature less than about 100°C or less than about 60°C, less than about 40°C, or even at ambient temperature.

[0287] Optionally, the dried MOF monolithic matrix can be contacted with a washing solvent to remove unreacted material and / or reaction byproducts and form a washed MOF monolithic matrix. This washing step can be performed once or more. The washing solvent can be the same as the reaction solvent, or it can be different from the reaction solvent.

[0288] Step (VIII) activates the dried MOF mass under vacuum by subjecting the unactivated MOF monolithic mass to a temperature greater than about 100°C to form the adsorbent mass. Preferably, step (VIII) follows immediately after step (V or VII). Step (V or VII) may optionally be integrated as the initial part of step (VIII).

[0289] The wetted MOF reactive mass is formed in step (I) and is a mixture of MOF material, residual unreacted MOF precursor, and reaction solvent plus any reaction byproducts. The term "unreacted MOF precursor" is used herein to describe all non-MOF solid material in the wetted MOF reactive mass. The wetted MOF reactive mass comprises: (i) about 20% to about 70% of the metal-organic framework by weight of the wetted metal-organic framework reactive mass; (ii) about 3% to about 50% of the unreacted MOF precursor by weight of the MOF in the wetted metal-organic framework reactive mass; and (iii) about 10% to about 70% of the reaction solvent by weight of the wetted metal-organic framework reactive mass.

[0290] Preferably, the wetted framework bulk comprises about 20% to about 70%, or about 40% to about 60% of the metal-organic framework by weight of the wetted metal-organic framework reactant. Preferably, the wetted MOF reactant comprises about 3% to about 50%, or about 10% to about 25% of the unreacted MOF precursor by weight of the MOF in the wetted MOF reactant. Preferably, the wetted MOF bulk comprises about 10% to about 70%, or about 20% to about 66%, or about 30% to about 60% of the reaction solvent by weight of the wetted metal-organic framework reactant. Preferably, the wetted framework mass comprises about 10% to about 50%, or about 20% to less than about 50% of the reaction solvent by weight of the wetted metal-organic framework reactant.

[0291] Preferably, the moistened skeleton block does not undergo one or more washing and reconcentration steps after initial formation.

[0292] In the case of preparing a composition comprising at least two monolithic MOF bodies, wherein the second monolithic MOF body is prepared from the first monolithic MOF body (e.g., by grinding the first monolithic MOF body), the composition can be obtained using the method of the present invention, the method comprising the additional step of grinding some of the first dried monolithic MOF body to provide a second dried monolithic MOF body, wherein the second dried monolithic MOF body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first dried monolithic MOF body.

[0293] Typically, the milling step is performed after the extrusion step and before the activation step. For example, the milling step can be performed at any suitable point between the extrusion and activation steps. As an example, milling can be performed before or after removing at least some of the remaining first solvent or reaction solvent. As another example, milling can be performed before or after optionally using a second solvent or washing solvent.

[0294] For example, the method may include:

[0295] 1. Provide a wet-adhesive MOF block, which includes:

[0296] i.MOF;

[0297] ii. Based on the total weight of the wetted binder MOF bulk, approximately 50% to approximately 95% by weight of the first solvent; and

[0298] iii. An organic binder, wherein the binder can be added as a solution, dispersion, powder or mixture thereof;

[0299] 2. Optionally, the proportion of the first solvent in the wetted binder MOF block can be reduced to provide an undried binder MOF block;

[0300] 3. Extrude and cut wet binder MOF blocks or undried binder MOF blocks to provide a first undried MOF monolithic body with a particle aspect ratio of about 2 or greater;

[0301] 4. Remove at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body;

[0302] 5. Grinding some of the first dried MOF monolithic body to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first dried MOF monolithic body;

[0303] 6. Optionally, a second solvent is added to the first dried MOF monolithic body and the second dried MOF monolithic body to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic body and the second dried MOF monolithic body, to provide an optional first binder-reduced MOF monolithic body and an optional second binder-reduced MOF monolithic body;

[0304] 7. Optionally, at least some of the second solvent is removed from the optional first binder-reduced MOF monolithic body and the optional second binder-reduced MOF monolithic body to provide the optional first unactivated MOF monolithic body and the optional second unactivated MOF monolithic body;

[0305] 8. Activating the first dried MOF monolithic body and the second dried MOF monolithic body, or optionally the first unactivated MOF monolithic body and the optional second unactivated MOF monolithic body, by subjecting them to a temperature greater than about 100°C, to provide a composition comprising the first MOF monolithic body and the second MOF monolithic body, wherein the second MOF monolithic body has a maximum particle size that is about equal to or smaller than the minimum particle size of the first MOF monolithic body.

[0306] Steps 6 to 8 can be performed simultaneously on the first monolithic MOF host component and the second monolithic MOF host component (i.e., on a mixture of the first monolithic MOF host component and the second monolithic MOF host component), or the steps can be performed separately on the first monolithic host component and the second monolithic host component (i.e., on the first monolithic MOF host component and the second monolithic MOF host component individually). The first monolithic MOF host component and the second monolithic MOF host component can be combined in any of steps 6 and 7, and can be combined in step 8 before or after the activation process.

[0307] As described above, the addition and removal of the second solvent are optional, making steps 6 and 7 optional steps that may be included or omitted.

[0308] In the case of preparing a composition comprising at least two monolithic MOF bodies, wherein the second monolithic MOF body is prepared from the first monolithic MOF body, the composition may alternatively be obtained according to the method of the present invention, the method comprising the following steps:

[0309] i. Providing a wettable adhesive MOF block, the wettable adhesive MOF block comprising:

[0310] a.MOF;

[0311] b. Based on the total weight of the wetted binder MOF bulk, approximately 50% to approximately 95% by weight of a first solvent; and

[0312] c. An organic binder, wherein the binder can be added as a solution, dispersion, powder, or mixture thereof;

[0313] ii. Optionally, reduce the proportion of the first solvent in the wetted binder MOF block to provide an undried binder MOF block;

[0314] iii. Extruding and cutting the wet binder MOF block or the undried binder MOF block to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or greater;

[0315] iv. Remove at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body;

[0316] v. Add a second solvent to the first dried MOF monolithic matrix to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic matrix to provide a MOF monolithic matrix with reduced first binder;

[0317] vi. Grind some of the first binder-reduced MOF monolithic body to provide a second binder-reduced MOF monolithic body, wherein the second binder-reduced MOF monolithic body has a maximum particle size that is approximately equal to or less than the minimum particle size of the second binder-reduced MOF monolithic body.

[0318] vii. Removing at least some of the second solvent from the MOF monolithic matrix reduced by the first binder and the MOF monolithic matrix reduced by the second binder to provide the first unactivated MOF monolithic matrix and the second unactivated MOF monolithic matrix;

[0319] viii. Activating the first unactivated MOF monolithic body and the second unactivated MOF monolithic body by subjecting them to a temperature of about 100°C or greater, to provide a composition comprising the first MOF monolithic body and the second MOF monolithic body, wherein the second MOF monolithic body has a maximum particle size that is about less than or equal to the minimum particle size of the first MOF monolithic body.

[0320] Steps vii and viii can be performed simultaneously on the first monolithic MOF host component and the second monolithic MOF host component (i.e., on a mixture of the first monolithic MOF host component and the second monolithic MOF host component), or the steps can be performed separately on the first monolithic MOF host component and the second monolithic MOF host component (i.e., on individual first monolithic MOF host components and the second monolithic MOF host component). The first MOF host component and the second MOF host component can be combined in steps vii and / or viii, and can be combined in step viii before or after the activation process.

[0321] Other methods of the present invention can be modified in a similar manner to include a grinding step. In the disclosed methods, the grinding step can be performed at any stage after the extrusion step, preferably after the drying step (i.e., after removing the first solvent or reaction solvent and / or optionally removing the second solvent or washing solvent). For example, grinding can be performed on a first undried MOF monolithic body, a first dried MOF monolithic body, a first binder-reduced MOF monolithic body, a first unactivated MOF monolithic body, and / or a first activated MOF monolithic body. Preferably, the grinding step is performed on the first dried MOF monolithic body and / or the first binder-reduced MOF monolithic body.

[0322] In the disclosed method, the grinding step can be performed in multiple stages, for example, both on the first dried MOF monolithic body and on the first binder-reduced MOF monolithic body.

[0323] A second MOF monolithic matrix can be prepared by milling and / or sieving a portion of the first MOF monolithic matrix. Subsequently, a composition can be prepared by combining the first MOF monolithic matrix and the second MOF monolithic matrix, wherein the second MOF monolithic matrix is ​​formed by milling and / or sieving a portion of the first MOF monolithic matrix.

[0324] A preferred method for producing the second MOF monolithic body is to grind or mill a portion of the first dried MOF monolithic body and / or the first binder-reduced MOF monolithic body to produce a second dried MOF monolithic body and / or a second binder-reduced MOF monolithic body. The same steps performed on the first dried MOF monolithic body and / or the first binder-reduced MOF monolithic body to produce the first MOF monolithic body component can also be performed on the second dried MOF monolithic body and / or the first binder-reduced MOF monolithic body. These steps, or some of these steps, can be performed on the first MOF monolithic body component and the second MOF monolithic body component separately, or the steps can be performed on a mixture of the first MOF monolithic body component and the second MOF monolithic body component.

[0325] Such extrudates are typically ground or milled after they have dried but before they have been activated.

[0326] Suitable equipment for grinding or milling extrudates includes the Retsch SM300 cutting mill. The milled material can be directly blended with the first extrudate group or screened before addition. After separation techniques such as screening, material that is too large to be recycled back into the mill is removed.

[0327] The milled material can also be sieved before being blended into the first MOF monolithic matrix component to remove very small particles (i.e., fine particles) having a particle size of about 50 μm or smaller, or about 150 μm or smaller. Removing such fine particles avoids dust during the processing of the MOF monolithic matrix and / or composition. The fine particles can optionally be recycled back into the MOF and / or MOF monolithic matrix through the synthesis process.

[0328] The MOF monolithic body can be separated from the composition by sieving using a sieve with an aperture size approximately equal to or slightly smaller than the measured particle size. The closest Tyler or US sieve aperture size can be used. If any particles pass through the sieve (e.g., by passing through the sieve aperture at the end), a limited number of particles can optionally be easily removed from the second MOF monolithic body by manual and visual inspection.

[0329] The proportion of the second MOF monolithic matrix in the composition can be determined by using a sieve with a mesh size approximately equal to or smaller than the minimum particle size of the first MOF monolithic matrix.

[0330] Typically, in the extrusion step of the method, wet binder MOF blocks or undried binder MOF blocks are extruded through an extruder with an orifice diameter of about 1 to about 5 mm.

[0331] In the steps of the method including adding a second solvent to a first dried MOF monolithic matrix (i.e., steps e. and v.) or adding a second solvent to a first dried MOF monolithic matrix and a second dried MOF monolithic matrix (i.e., step 6.), at least a portion of any residual first solvent and at least a portion of any unreacted reactants are removed. Preferably, all residual first solvent and unreacted reactants are removed, but any portion of residual first solvent and any portion of unreacted reactants may still remain, particularly in the pores of the MOF monolithic matrix components.

[0332] In the steps of the method including 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 dried MOF monolithic body and the second dried MOF monolithic body (i.e., step 6.), the amount of organic binder removed from the first dried MOF monolithic body or from the first dried MOF monolithic body and / or the second dried MOF monolithic body may be different.

[0333] For example, the second solvent can remove less than about 20% by weight of organic binder from the first dried MOF monolithic matrix and the first dried MOF monolithic matrix and / or the second dried MOF monolithic matrix, based on the total weight of the organic binder in the respective matrix.

[0334] For example, the second solvent can remove more than about 20% by weight of organic binder from the first dried MOF monolithic matrix and the first dried MOF monolithic matrix and / or the second dried MOF monolithic matrix, based on the total weight of the organic binder in the respective matrix.

[0335] The second solvent can remove residual first solvent, unreacted reactants, and about 15% by weight or less (such as about 10% by weight or less, for example about 5% by weight or less) of the organic binder based on the total weight of the organic binder in the respective body.

[0336] Removing the organic binder from the dried MOF monolithic body is considered to produce a first MOF monolithic body and / or a second MOF monolithic body with a preferred porosity profile (e.g., with enhanced levels of micropores and mesopores and lower levels of macropores).

[0337] Furthermore, the above method is particularly advantageous because it eliminates the need for pre-drying of MOFs before using them to prepare monolithic MOF bodies and / or compositions. For example, a wettable binder MOF mass can be provided directly after MOF synthesis, where the MOF and the first solvent are part of the MOF synthesis process. In this case, only the binder needs to be added. In this way, the MOF does not require pre-drying before use in the above method, making the process more efficient and cost-effective.

[0338] Use of the composition

[0339] 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 transport. For example, the compositions of the present invention can be used to extract, capture, store, and / or transport gases from industrial processes, such as exhaust gases. The compositions can be used to extract, capture, store, and / or transport gases, such as carbon dioxide, from flue gas.

[0340] The compositions of the present invention can also be used to extract, capture, store and / or transport other gases or fluids, such as hydrogen, krypton, methane or water, for example hydrogen, krypton or methane.

[0341] After gas capture, storage, and / or delivery using the compositions of the present invention, they can be regenerated and recycled for further and / or reuse. For example, the compositions can be regenerated by activation to remove any residual gases and / or adsorbates, and then recycled or reused in the same or different applications.

[0342] Compositions containing gases

[0343] The compositions of the present invention may further comprise gases, such as those selected from carbon dioxide, hydrogen, krypton, methane, water, and mixtures thereof, preferably carbon dioxide, hydrogen, krypton, methane, and mixtures thereof.

[0344] Those skilled in the art should understand that any suitable MOF can be selected for use in the composition (i.e., the MOF is suitable for the gas type, adsorbent, and / or application).

[0345] The composition may further contain hydrogen. When the composition further contains hydrogen, the first monolithic MOF body and / or the second monolithic MOF body may contain any suitable MOF. Preferably, the first monolithic MOF body and / or the second monolithic MOF body contain MOFs independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, and mixtures thereof.

[0346] The composition may further comprise carbon dioxide. When the composition further comprises carbon dioxide, the first monolithic MOF host and / or the second monolithic MOF host may comprise any suitable MOF. Preferably, the first monolithic MOF host and / or the second monolithic MOF host comprise MOFs independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, and mixtures thereof.

[0347] The composition may further contain krypton. When the composition further contains krypton, the first monolithic MOF host and / or the second monolithic MOF host may contain any suitable MOF. Preferably, the first monolithic MOF host and / or the second monolithic MOF host contain MOFs independently selected from MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, such as MOF-74, more preferably MOF-74-Mg.

[0348] The composition may further comprise methane. When the composition further comprises methane, the first monolithic MOF host and / or the second monolithic MOF host may comprise any suitable MOF. Preferably, the first monolithic MOF host and / or the second monolithic MOF host independently comprise HKUST-1.

[0349] The composition may further contain water. When the composition further contains water, the first monolithic MOF matrix and / or the second monolithic MOF matrix may contain any suitable MOF. Preferably, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain MOFs 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.

[0350] In some respects, the solid components of the first MOF monolithic body and / or the second MOF monolithic body may consist essentially of MOF and binder, or more specifically, of MOF and binder.

[0351] In a further aspect, the solid component of the composition may consist substantially of a first MOF monolithic host and / or a second MOF monolithic host, or more specifically, consist of a first MOF monolithic host and / or a second MOF monolithic host.

[0352] The term "solid component" can refer to solid materials other than liquids and / or gases (i.e., materials not adsorbed on and / or on MOFs, MOF monolithic bodies and / or compositions).

[0353] In other respects, the composition and / or the first MOF monolithic body and / or the second MOF monolithic body may be substantially free of solid components other than MOF and binder.

[0354] The term “substantially free” means that the composition and / or the first MOF monolithic matrix and / or the second MOF monolithic matrix contain less than 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt% of solid components other than MOF and binder, such as less than 0.5 wt% or 0.1 wt%.

[0355] Use of the composition in gas storage containers

[0356] According to a further aspect of this disclosure, a gas storage container comprising the composition is provided.

[0357] Gas storage containers can have non-spherical shapes.

[0358] Gas storage containers may further include one or more of the following:

[0359] a. Thermal insulation material of the external wall;

[0360] b. Apparatus for heating and cooling the composition;

[0361] c. Internal baffle;

[0362] d. A device for holding a composition in place;

[0363] e. A shape in which the composition is at least 10 cm away from the outer wall (this reduces temperature loss);

[0364] f. Devices for monitoring pressure and / or temperature; and / or

[0365] g. A valve that controls the input and output flow of gas.

[0366] Use of the composition and / or gas storage container

[0367] According to a further aspect of this disclosure, a gas storage container comprising the composition is provided for use in the absorption, storage and / or release of gases.

[0368] According to a further aspect of the invention, the composition is provided for use in the absorption, storage and / or release of gases.

[0369] The following description refers to the use of gas storage containers containing the described composition for the absorption, storage, and / or release of gases. Those skilled in the art will understand that this discussion also applies to and illustrates uses of the composition for the absorption, storage, and / or release of gases (whether or not in a gas storage container).

[0370] For example, a gas storage container can be used in a method that includes the following steps:

[0371] a. Filling a gas storage container with gas;

[0372] b. Storing the gas in a gas storage container; and / or

[0373] c. Release gas from the gas storage container.

[0374] The steps of this method can be performed in any order, and the method may include any one or more of these steps.

[0375] For example, the composition in a gas storage container can be used as part of a gas purification, storage and capture process using any suitable technology as part of a pressure swing (PSA) or temperature swing (TSA) adsorption process and its variants, such as VPSA (vacuum pressure swing adsorption).

[0376] Such processes operate by altering the pressure and / or temperature within the gas storage container, causing the target gas (e.g., hydrogen, carbon dioxide, methane, water, and / or krypton) to be adsorbed from or desorbed from the monolithic host.

[0377] For example, to load and store hydrogen into a monolithic host particle, hydrogen gas is introduced into a container at high pressure (typically >5 bar) and low temperature (e.g., below 100 K). This lowers the temperature of the MOF material and the MOF monolithic host, and facilitates hydrogen adsorption into the MOF or monolithic host. Typically, cooled and pressurized hydrogen is fed into the storage container until the pressure inside the container reaches or approaches the pressure and temperature of the incoming gas. The monolithic host is then loaded with hydrogen for storage until needed. To remove hydrogen from the storage container, one or more valves are opened to allow the release of pressurized gas. As the pressure decreases, hydrogen desorbs from the MOF surface and can be removed through the valves. To assist in gas removal, heat can be applied to increase the temperature of the monolithic host and the pressure can be reduced. Similar methods are used for other gases, such as methane, but the optimal pressure and temperature for adsorption and desorption will vary depending on the gas.

[0378] The container can also be used as part of a purification or capture process. The gas stream to be separated (such as carbon dioxide-containing flue gas as part of a carbon capture process, or a krypton-containing gas stream) is passed through a gas storage container under high pressure and low temperature—for example, at >5 bar and about 20°C (e.g., ambient temperature). The target gas (e.g., carbon dioxide or krypton) is then adsorbed through a monolithic MOF body, which has been selected to have high selectivity for the gas stream compared to other components in the gas stream. The gas exiting the gas storage container is now depleted in the target gas and can be sent for further treatment or vented to the atmosphere. The gas stream stops when the MOF is saturated with the target gas and stops adsorption. The adsorbed target gas (such as carbon dioxide or krypton) can then be desorbed from the MOF by any suitable method, such as increasing the temperature of the MOF composition (e.g., by using a heater) for TSA processes, or reducing the pressure in the storage container by opening a valve and / or using a pressure pump or both for PSA processes. The target gas can be extracted through the opened valve and sent for further treatment, such as underground capture.

[0379] Such processes can also be applied to the collection and / or storage of water, such as collecting water from the air. For example, moisture or water in the air (e.g., humid air or water vapor) can be captured, stored, and / or released by a gas storage container containing the composition. Therefore, references to gases as disclosed herein may also include water, moisture, and / or water vapor.

[0380] The compositions are particularly well-suited for adsorbing and storing gases for a variety of gas separation and purification applications. Due to the porous nature of the MOF monolithic matrix within the compositions, as well as other properties such as high packing density, they are particularly well-suited for exhibiting high gas volumetric capacity, which is important for gas storage and separation applications.

[0381] Those skilled in the art should understand that any suitable MOF can be selected for use in a composition (whether or not in a gas storage container) for the absorption, storage and / or release of a gas.

[0382] MOFs can be selected based on the intended use of the composition and / or 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.

[0383] The gas may contain hydrogen, carbon dioxide, methane, krypton, water, or mixtures thereof, such as hydrogen, carbon dioxide, methane, krypton, or mixtures thereof. The gas may be (or may consist substantially of) hydrogen, carbon dioxide, methane, krypton, water, or mixtures thereof, such as hydrogen, carbon dioxide, methane, krypton, or mixtures thereof.

[0384] The absorption and / or release of gases can be achieved through the following:

[0385] a. Pressure oscillation process; and / or

[0386] b. Temperature fluctuation process.

[0387] Gas storage containers can be used as part of a gas purification process.

[0388] Uses for hydrogen storage

[0389] When the gas contains hydrogen, for example, when the gas is hydrogen, the first monolithic MOF body and / or the second monolithic MOF body may contain any suitable MOF. Preferably, the first monolithic MOF body and / or the second monolithic MOF body contain MOFs independently selected from HKUST-1, ZIF-8, MOF-808, UiO-66 and mixtures thereof.

[0390] These MOFs are suitable for the absorption, storage and release of hydrogen, and when used in the compositions of the present invention, they exhibit excellent properties such as volumetric performance and cycle life.

[0391] When the gas contains hydrogen, for example, when the gas is hydrogen, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66, and mixtures thereof. During gas absorption and / or release, the temperature of the composition can vary from about -200°C to about -100°C. When the temperature is about -200°C, the pressure inside the gas storage container can be greater than or equal to about 10 bar. When the temperature is about -100°C, the pressure inside the gas storage container can be less than or equal to about 1 bar.

[0392] When the gas contains hydrogen, for example, when the gas is hydrogen, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably independently selected from HKUST-1, ZIF-8, MOF-808, ZU-301, UiO-66 and mixtures thereof, and the composition may contain about 0.4 to about 1.1 g / cm³ at 77 K and 10 atm. 3 (such as about 0.5 to about 0.9 g / cm³) 3 For example, approximately 0.6 to approximately 0.8 g / cm³ 3 MOF and approximately 0.025 to approximately 0.09 g / cm³ 3 (such as about 0.033 to about 0.075 g / cm³) 3 For example, approximately 0.04 to approximately 0.065 g / cm³ 3 The bulk volume composition of hydrogen gas.

[0393] Uses for carbon dioxide storage

[0394] When the gas contains carbon dioxide, for example, when the gas is carbon dioxide, the first monolithic MOF body and / or the second monolithic MOF body may contain any suitable MOF, preferably 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 exhibit properties such as high volumetric performance, rapid gas dynamics, and good stability that are particularly suitable for carbon dioxide capture in flue gas purification applications.

[0395] When the gas contains carbon dioxide, for example, when the gas is carbon dioxide, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2, and mixtures thereof. During gas absorption and / or release, the temperature of the composition can vary from about 0°C to about 100°C. When the temperature is about 20°C, the pressure inside the gas storage container can be about 5 bar to about 10 bar. When the temperature is about 70°C, the pressure inside the gas storage container can be less than or equal to about 1 bar.

[0396] When the gas contains carbon dioxide, for example, when the gas is carbon dioxide, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably independently selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof, and the composition may be contained at about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 (such as about 0.5 to about 0.9 g / cm³) 3 For example, approximately 0.6 to approximately 0.8 g / cm³ 3 MOF and approximately 0.03 g / cm³ 3 Approximately 0.14 g / cm³ 3 (such as approximately 0.04 g / cm³) 3 To approximately 0.12 g / cm 3 For example, approximately 0.05 to approximately 0.1 g / cm³ 3 The bulk volume composition of carbon dioxide.

[0397] When the gas entering the gas storage container contains carbon dioxide, the carbon dioxide content of the gas can be from about 0.1 to about 10% by weight based on the total weight of the gas.

[0398] When the gas entering the gas storage container contains carbon dioxide, the carbon dioxide content of the gas can be from about 10 to about 70% by weight based on the total weight of the gas.

[0399] Uses for storing krypton

[0400] When the gas contains krypton, for example when the gas is krypton, the first monolithic MOF host and / or the second monolithic MOF host may contain any suitable MOF, preferably a MOF independently selected from MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1 and mixtures thereof, such as MOF-74, more preferably MOF-74-Mg.

[0401] When the gas contains krypton, for example, when the gas is krypton, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably a MOF independently selected from MOF-74, MOF-74-Mg, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1, and mixtures thereof, such as MOF-74, preferably MOF-74-Mg. During gas absorption and / or release, the temperature of the composition can vary from about 0°C to about 100°C. When the temperature is about 20°C, the pressure inside the gas storage container can be greater than or equal to about 5 bar. When the temperature is about 100°C, the pressure inside the gas storage container can be less than or equal to about 1 bar.

[0402] When the gas entering the gas storage container contains krypton, the krypton content of the gas can be approximately 90 to approximately 99% by weight based on the total weight of the gas.

[0403] When the gas contains krypton, for example, when the gas is krypton, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably a MOF independently selected from MOF-74, CALF-20, TIFSIX-3-Ni, NbOFFIVE-1 and mixtures thereof, such as MOF-74, preferably MOF-74-Mg, and the composition may contain about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 (such as about 0.5 to about 0.9 g / cm³) 3 For example, approximately 0.6 to approximately 0.8 g / cm³ 3 MOF and approximately 0.03 g / cm³ 3 Approximately 0.14 g / cm³ 3 (such as approximately 0.04 g / cm³) 3 To approximately 0.12 g / cm 3 For example, approximately 0.05 to approximately 0.1 g / cm³ 3 The krypton gas accumulation volume composition.

[0404] Uses for methane storage

[0405] When the gas contains methane, for example when the gas is methane, the first monolithic MOF body and / or the second monolithic MOF body may contain any suitable MOF, preferably a MOF independently selected from HKUST-1.

[0406] When the gas contains methane, for example, when the gas is methane, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably a MOF independently selected from HKUST-1. During gas absorption and / or release, the temperature of the composition can vary from about 0°C to about 100°C. When the temperature is about 20°C, the pressure inside the gas storage container can be greater than or equal to about 5 bar. When the temperature is greater than or equal to about 95°C, the pressure inside the gas storage container can be less than or equal to about 1 bar.

[0407] When the gas contains methane, for example, when the gas is methane, the first monolithic MOF matrix and / or the second monolithic MOF matrix contain any suitable MOF, preferably a MOF independently selected from HKUST-1, and the composition may contain about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 (such as about 0.5 to about 0.9 g / cm³) 3 For example, approximately 0.6 to approximately 0.8 g / cm³ 3 MOF and approximately 0.03 g / cm³ 3 Approximately 0.14 g / cm³ 3 (such as approximately 0.04 g / cm³) 3 To approximately 0.12 g / cm 3 For example, approximately 0.05 to approximately 0.1 g / cm³ 3 The bulk volume composition of methane.

[0408] Uses for water collection

[0409] When the gas contains water (e.g., humid air), such as when the gas is water (e.g., water vapor), the first monolithic MOF body and / or the second monolithic MOF 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.

[0410] Water collection can be carried out by capturing water directly from the air. For example, the absorption step may include adsorbing water into the composition at high humidity (e.g., at high relative humidity RH, such as about 60% RH to about 100% RH) and / or low temperature (e.g., about -40°C to about 30°C). The release step may include desorbing water from the composition at low humidity (e.g., at low RH, such as about 0% RH to about 40% RH) and / or high temperature (e.g., about 40°C to about 80°C).

[0411] When the gas contains water, for example, when the gas is water, the first monolithic MOF matrix and / or the second monolithic MOF matrix 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. During gas absorption and / or release, the temperature of the composition can vary from about 0°C to about 100°C. When the temperature is about 20°C, the pressure inside the gas storage container can be greater than or equal to about 5 bar. When the temperature is greater than or equal to about 95°C, the pressure inside the gas storage container can be less than or equal to about 1 bar.

[0412] When the gas contains water, for example, when the gas is water, the first monolithic MOF matrix and / or the second monolithic MOF matrix 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, and the composition may be contained in amounts of about 0.4 to about 1.1 g / cm³ at 293 K and 5 atm. 3 (such as about 0.5 to about 0.9 g / cm³) 3 For example, approximately 0.6 to approximately 0.8 g / cm³ 3 MOF and approximately 0.03 g / cm³ 3 Approximately 0.14 g / cm³ 3 (such as approximately 0.04 g / cm³) 3 To approximately 0.12 g / cm 3 For example, approximately 0.05 to approximately 0.1 g / cm³ 3 ( ) water volume composition. Attached Figure Description

[0413] Figure 1 The CO2 and N2 isotherms of ZU-301 measured at 20°C are shown.

[0414] Figure 2 The CO2 and N2 isotherms of TIFSIX measured at 20°C are shown.

[0415] Figure 3 The CO2 and N2 isotherms of UTSA-16 measured at 20°C are shown.

[0416] Figure 4 The CO2 and N2 isotherms of CALF-20 measured at 20°C are shown.

[0417] Figure 5 The CO2 and N2 isotherms of NbOFFIVE measured at 20°C are shown.

[0418] Figure 6 The CO2 and N2 isotherms of CPO-27 measured at 20°C are shown.

[0419] Figure 7 CO2 adsorption isotherms obtained from DVS tests (at 20°C) on long and short extrudates corresponding to Example 6 using CO2 levels of 5%, 10%, 20%, 30%, and 40%.

[0420] Test methods

[0421] Microporosity and mesoporosity

[0422] The microporosity and / or mesoporosity levels, or microporosity and / or mesoporosity profiles, of a monolithic MOF body can be determined by test method ASTM D4641-17. Suitable equipment for performing ASTM D4641-17 includes the ASAP 2020Plus from Micromeritics Corporation.

[0423] Typically, the 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 at an increased pressure P to the sample in an amount sufficient to define the adsorption isotherm and reach the nitrogen saturation pressure.

[0424] Each additional dose of nitrogen is introduced into the sample only after the previous dose of nitrogen has reached adsorption equilibrium with the sample.

[0425] Typically, equilibrium is reached if the change in gas pressure is no greater than approximately 0.1 Torr / 5 minutes. This state continues until P0 (gas saturation pressure) is reached.

[0426] Data are typically plotted as the amount of gas adsorbed / desorbed (and the resulting porosity curve) varying with P / P0. Desorption isotherms are determined by desorbing nitrogen from a saturated sample in a stepwise manner, taking the same precautions applied under adsorption conditions to ensure desorption equilibrium. Microporosity is associated with the volume of gas adsorbed at P / P0 values ​​< 0.1, while mesoporosity is associated with the volume of gas adsorbed at P / P0 values ​​between 0.1 and 0.98.

[0427] Large porosity measurement

[0428] To enable the monolithic MOF matrix to possess high volumetric performance for gas storage and separation applications, it is preferable that the first and / or second monolithic MOF matrix have low levels of macroporosity. In other words, the first and / or second monolithic MOF matrix may have low levels of macroporosity or low macropore volume proportional to the volume (i.e., encapsulation volume) of the first and / or second monolithic MOF matrix.

[0429] The macroporosity of a monolithic MOF can be determined by mercury porosimetry. Methods based on N₂ adsorption are suitable for micropores and mesopores, but not for larger macropores. Mercury porosimetry can measure macropores, but cannot measure micropores or small mesopores.

[0430] Mercury porosity values ​​can be measured according to ASTM D4284-12. Suitable equipment for implementing ASTM D4284-12 includes the Micromeritics AutoPore VI 9510 from Micromeritics, Inc. Other suitable equipment includes the PoreMaster series from Quantachrome. Unless otherwise specified by the equipment manufacturer, the default surface tension and contact angle for mercury are 485 mN / m and 130°, respectively. In ASTM D4284-12, mercury is indented into the pores under pressure. A sample size of approximately 0.2 g is preferred. It is preferable to crush the monolithic MOF and sieve it between 710 microns and 250 microns, using the sieved material.

[0431] According to the Washburn equation, the pressure required to force mercury into the pores of a sample is inversely proportional to the pore size. For characterization purposes, all pores are assumed to be cylindrical. The porosimeter increases the pressure of the mercury within the sample holder, causing the mercury to penetrate increasingly smaller sample pores. AutoPore VI or other suitable devices will automatically convert the applied pressure into an equivalent pore diameter using the Washburn equation and the contact angle and surface tension values ​​given above.

[0432] Encapsulation volume can be measured using a technique based on Archimedes' principle of volume displacement. The encapsulation volume of the sample is determined by the volume of mercury displaced under atmospheric pressure. At atmospheric pressure (101.325 kPa), mercury does not penetrate the internal pores, only the external pores. Therefore, the volume of mercury displaced by the bulk at 101 kPa can be used as the encapsulation volume.

[0433] As the applied pressure increases, the mercury is forced into smaller internal pores. 292 atmospheres (2.96 x 10⁻⁶) 4 A pressure of (kPa) is sufficient to force mercury into pores of 50 nm and larger. Therefore, the macroporosity % level of the sample is 2.96 x 10⁻⁶. 4 The percentage of Hg intrusion into the porosity at 101 kPa is subtracted from the percentage of Hg intrusion into the porosity at 101 kPa.

[0434] The volume of the MOF monolithic body can also be measured manually.

[0435] Determination of adhesive level

[0436] The level of organic binder in a monolithic MOF matrix can be determined by thermogravimetric analysis based on weight loss at high temperatures.

[0437] The high temperature (600°C) used will burn away all organic matter in the sample, leaving only metal oxides. The difference in weight loss percentage between the MOF sample and the MOF monolithic matrix (MOF plus binder) sample can be used to determine the binder level in the sample.

[0438] First, the MOF monolithic matrix being tested is heated to 150°C for 1 hour to remove solvent and dry. The matrix is ​​then crushed, and a sample of the monolithic matrix 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 to a loss % and a residual %. A sample of the MOF material forming the monolithic matrix is ​​dried and then heated under the same conditions, with the weight loss normalized to a loss % to obtain the residual %. The MOF% in the monolithic matrix is ​​equal to the residual % of the monolithic matrix divided by the residual % of the MOF material. The difference from 100% represents the binder level.

[0439] To measure the weight loss of the binder after contact with the second solvent, samples were tested before and after the binder removal step, as described above. This will produce the binder level %, namely IABB% (initial adsorbent bulk binder %) and RBABB% (reduction of binder from adsorbent bulk binder %).

[0440] Therefore, the percentage loss of adhesive is ((IABB%-RBABB%) / (IABB%))*100.

[0441] BET area measurement

[0442] The BET surface area of ​​a monolithic MOF host can be measured using ASTM 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 on the MOF host sample at various low pressure levels. The pressure difference caused by a fixed volume of nitrogen introduced into the test apparatus to measure the MOF host surface area is used to calculate the BET surface area. Suitable equipment for measuring the BET surface area includes the Micromeritics Corporation 3Flex, used according to the manufacturer's guidelines.

[0443] Encapsulation density

[0444] The encapsulation density of the subject can be calculated by dividing the weight of the subject (in grams) by its encapsulation volume (in cm³). 3 The encapsulation density is measured in units of _____. In ASTM D3766, encapsulation density is defined as "the ratio of the volume of particles to the sum of the volume of solids in each block and the voids within each block (i.e., within a tightly fitted imaginary encapsulation completely surrounding the solids of each block)." Encapsulation density of a bulk can be measured using different techniques, and the results are comparable. In case of significant discrepancies, results from powder specific gravity bottles are preferred.

[0445] Encapsulation density can be measured using mercury porosimetry. At atmospheric pressure, mercury does not penetrate the internal pores. Therefore, the volume of mercury displaced by the bulk at atmospheric pressure is the encapsulation volume. Dividing the sample weight by the encapsulation volume yields the encapsulation density. The use of mercury porosimetry has been described above.

[0446] Preferably, a powder pyrometer (such as the GeoPyc Model 1360 from Micrometrics Instruments) is used to measure the encapsulation volume and density of the body. If necessary, the encapsulation volume measured by these techniques can be used interchangeably with that measured by mercury intrusion porosimetry. If discrepancies exist, the powder pyrometer results are preferred.

[0447] For larger bodies, the encapsulation volume can also be determined manually. The encapsulation density of the extrudate can be measured in micrometers to measure the thickness and length of the extrudate, thus allowing the calculation of the extrudate volume. The extrudate weight (in grams) is divided by the extrudate volume (in cm³). 3 Encapsulation density is calculated in units of 10. For more homogeneous matrices, such as extrudates, encapsulation density can be measured manually. Multiple measurements (>10) should be performed and averaged to reduce experimental variability.

[0448] Bulk density

[0449] The bulk density (tap density) of the composition can be determined by loading a weighed sample into a cylinder and tapping it at least 50 times. The resulting volume of the filler material is then determined, and the bulk density is calculated by dividing the sample weight by the sample volume. The cylinder diameter needs to be several times (>3) larger than the average length of any extrusion to allow for filling. Container cylinders with a diameter of approximately 3 cm or greater are suitable. The depth of the packing bed also needs to be greater than approximately 3 cm to allow for filling.

[0450] Due to the size and properties of the composition, only a limited amount of compaction or movement is required to efficiently fill the bulk. Increasing the amount of compaction and different intensities of compaction, such as in some standards, does not significantly change the filler density.

[0451] Tap density can be defined using methods such as MPIF-46, ASTM B-527, or ISO 3953 tap density methods.

[0452] Particle size measurement

[0453] In the context of this disclosure, those skilled in the art will understand that mean particle size includes weight-based mean particle size or volume-based mean particle size, i.e., mean particle size characterized and defined by particle size distribution by weight or volume, respectively.

[0454] As used herein, those skilled in the art should understand that the term 'volume-based mean particle size' includes mean particle size characterized and defined by a volume-based particle size distribution, which is the distribution in which the existing fraction (relative quantity) in each size class is defined as a volume fraction as measured, for example, by laser diffraction.

[0455] Mean particle size can refer to the cumulative distribution of the "D50 size" volume, where 50% of the particles have a diameter smaller than the D50 size.

[0456] Preferably, the particle size of the second MOF monolithic host (i.e., a host with a particle aspect ratio close to about 1) is measured by laser diffraction.

[0457] D50 particle size can be measured by laser diffraction, for example using a Malvern Mastersizer 3000.

[0458] ISO 13320:2020 details suitable methods for measuring particle size and particle size distribution by laser diffraction.

[0459] Preferably, the particle size of the first MOF monolithic body (i.e., a body with a particle aspect ratio of about 2 or greater) is measured by dynamic image analysis as described below.

[0460] Measurement of aspect ratio (and particle size)

[0461] The aspect ratio of a particle is the ratio of the length of a particle (e.g., an extrudate) to the width of the particle (e.g., an extrudate).

[0462] Two methods can be used to determine the particle aspect ratio of an extruder. The particle aspect ratio of an individual extruder can be determined by manually measuring a large number of individual extruders using calipers. This requires measuring at least about 25, preferably more than about 50 randomly selected extruders to provide any statistically reliable data about the main set. However, this is very slow and laborious.

[0463] More conveniently, the (maximum and minimum) particle size and aspect ratio of the extrudate (first MOF monolithic bulk) can be measured via dynamic image analysis. A suitable device is the Microtrac MRB Camsizer P4, operated according to the manufacturer's instructions. This device has been proven to be comparable to caliper measurements of the sample.

[0464] Samples (preferably >50 mL) are conveyed into the measurement area via a vibrating flow channel, where they fall freely in front of a planar light source. The resulting shadow projections are captured by a camera system and evaluated in real time. This allows for the simultaneous measurement of the extrudate's length and width, as well as its shape. Conveying the extrudate along the vibrating flow channel facilitates alignment for analysis.

[0465] The width of the extrudate is most conveniently defined as the bisector of the minimum area (X). Ma min –Minimum Martin diameter). This is feasible even if the extrudate is bent or partially rounded. Extrudate length or X stretch Conveniently defined as the maximum Feret diameter (X) Fe max Square minus the minimum Martin diameter (X) Ma min The square root of the product of squares. Maximum Fretter diameter (X) Fe max () is the longest distance between two parallel lines that are in contact with the main body's projection.

[0466] Therefore, the aspect ratio of the particle is X. stretch / X Ma min .

[0467] Devices such as the Camsizer P4 will provide the extrusion length (X). stretch ) and width (X ma min The distribution of extrudate width will be highly monodisperse. The proportion of the composition containing the first MOF monolithic body can be determined by the extrudate length (X). stretch The proportion of the composition that is greater than the average width of the extrudate multiplied by the required aspect ratio is used to determine this.

[0468] ISO 13322-1 / 2 describes a suitable method for measuring particle size and particle size distribution by means of dynamic image analysis.

[0469] In the context of this disclosure, those skilled in the art will understand that the mean particle aspect ratio includes a weight-based mean particle aspect ratio or a volume-based mean particle aspect ratio, i.e., a mean particle aspect ratio characterized and defined by 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, wherein the cumulative particle aspect ratio distribution is the fraction of particles (based on weight or volume) with aspect ratios less than a certain value. Preferably, the mean particle aspect ratio is a volume-based mean particle aspect ratio.

[0470] The average particle aspect ratio can be the “A50 aspect ratio” based on the volume-dependent cumulative distribution, where 50% of the particles have an aspect ratio smaller than the A50 particle aspect ratio.

[0471] Measurement of Young's modulus and hardness

[0472] Young's modulus and hardness can be determined by nanoindentation, for example using MTS Nanoindenter XP, which is located in an isolation cabinet to shield against thermal fluctuations and acoustic interference.

[0473] Prior to indentation, the monolithic surface can be cold-mounted with epoxy resin and polished using an increasingly fine diamond suspension. Indentation can be performed in a "continuous stiffness measurement" mode with dynamic displacement control. The E (elastic modulus) and H (hardness) mechanical properties can be determined based on the surface penetration depth, for example, by using a 2nm sinusoidal displacement at 45Hz superimposed on the system's main load signal and set to 5x10. -2 s -1The loading and unloading strain rates. Tests with a maximum indentation depth of 1000 nm can be performed using a Berkovich (i.e., trihedral conical) diamond tip with a radius of approximately 100 nm. Based on previous work on zeolite imidazole salt frameworks [Tan et al. (2010)], the raw data (load-displacement curves) obtained can be analyzed using the Oliver and Pharr (2004) method with a Poisson's ratio set to 0.2. Data resulting from surface penetration of less than 100 nm may be discarded due to imperfect tip-surface contact.

[0474] Determination of the ratio of the first MOF monolithic host and the second MOF monolithic host in the composition

[0475] This can be most easily determined by sieving the composition using a sieve size equal to the width of the first MOF monolithic body or the next smallest Tyler or US sieve aperture.

[0476] Some embodiments of this disclosure will be further described in the following non-limiting examples:

[0477] Example 1

[0478] Compositions comprising UiO-66-NH2 were prepared from a first and a second monolithic MOF host as described herein, wherein the metal ion of the MOF is Zr and the organic linker of the MOF is 2-aminoterephthalate. A 1-liter reaction mixture comprising MOF (UiO-66-NH2) crystals with an average particle size less than 900 nm dispersed in a reaction solvent containing water and having a solids content of 10% was prepared by a method described in the literature.

[0479] The sample was divided into four equal parts, and each part was centrifuged in a Jeol JR15 at 5250g for 15 minutes.

[0480] Pour the supernatant from each sample flask, leaving a wet solid layer at the bottom. Then add 250 g of methanol to each flask and stir the sample to redisperse and wash the crystals.

[0481] The flask was then centrifuged again at 5250g for 40 minutes to form a thick solid layer (wet skeleton block) containing MOF, methanol, and any residual reactants / solvents in the reaction mixture. Analysis showed that the solid layer had a solids content of 27.5%.

[0482] Then, 280g of the solid layer was mixed with 280g of a 2.6% by weight aqueous solution of methylcellulose to form a wet binder block.

[0483] The solvent level was reduced by stirring the moistened adhesive block in a Kenwood kitchen rack. 5g of pre-dried and ground UiO-66-NH2 powder was also added to thicken the mixture. The resulting material is a very thick paste.

[0484] The undried binder block was then extruded through a manual pasta machine with an orifice of 2 mm diameter. The extrudate was extruded without adhering to each other and slowly dried under ambient conditions to obtain an extrudate with an average width (thickness) of 1.8 mm. Samples of the extrudate were manually cut into individual portions of approximately 4-5 mm and 7-8 mm in length.

[0485] The extrudate was then further dried under ambient conditions (21°C) for 24 hours to form a hard, robust extrudate. A total of 71g of cut extrudate was collected, with each segment being approximately equal in length.

[0486] Then, 20g of each fraction was placed in 1000ml of methanol (a second solvent) for 48 hours to remove the binder portion. This process was repeated with fresh methanol. The washed extrudate was removed from the methanol and allowed to dry under ambient conditions to obtain two sizes of fractions of the MOF monolithic body with reduced binder. These extrudate fractions were later mixed in equal weight ratios to form the first MOF monolithic body.

[0487] Then take about 8g of each small part and combine them together. Then grind the combined mixture with a pestle and mortar and sieve it between a 500-micron and a 250-micron sieve. These are the second MOF monolithic bodies.

[0488] Then, the first and second MOF monolithic substrates were activated by heating them to 105°C in a vacuum oven for 12 hours to obtain the final adsorbent substrate.

[0489] The first MOF monolithic matrix, measured by mercury porosimetry, has a macroporosity of 9.0%, a MOF content of 95.1%, and a density of 0.55 g / cm³. 3 The encapsulation density (therefore a relative density of 0.43) and 928 m 2 / g BET area. The same applies to the second MOF monolithic body. Vigorous shaking of the first MOF monolithic body produced no visible dust.

[0490] The first and second monolithic MOF matrix were then mixed to form a composition comprising 78 wt% of the first monolithic MOF matrix and 22 wt% of the second monolithic MOF matrix. This was prepared as a packed bed.

[0491] The composition comprises a first MOF monolithic body and a second MOF monolithic body, wherein the maximum particle size (particle length) of the first MOF monolithic body is about 4 mm to about 8 mm, and the maximum particle size of the second MOF monolithic body is 0.5 mm or less.

[0492] Comparative samples containing only the first MOF monolithic matrix were also prepared, wherein the maximum particle size (particle length) of the first MOF monolithic matrix was approximately 4 mm to 8 mm. The comparative samples were then prepared into a packed bed.

[0493] The bulk density of a composition containing at least a first MOF monolithic matrix and a second MOF monolithic matrix was compared with that of a comparative sample containing only the first MOF monolithic matrix by measuring the bulk density of the sample.

[0494] Compared with the comparative sample containing only the first MOF monolithic body, the composition containing both the first MOF monolithic body and the second MOF monolithic body showed a bulk density that was about 29% higher (Table 1).

[0495] Table 1. Filling density of compositions prepared using a first MOF monolithic matrix and a second MOF monolithic matrix, or using only the first MOF monolithic matrix.

[0496]

[0497] Example 2

[0498] HKUST-1 compositions comprising a first MOF monolithic host and a second MOF monolithic host as described herein were prepared. The MOF of the first MOF monolithic host and the second MOF monolithic host is HKUST-1, wherein the metal ion of the MOF is Cu, and the organic linker of the MOF is benzene-1,3,5-tricarboxylate.

[0499] A first monolithic MOF matrix was prepared by extrusion using HKUST-1 as the MOF and methylcellulose as the binder. HKUST-1 was synthesized according to a scheme described in the literature and supplied as a 25% water 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 3 mm orifice to form extrudate pellets. The extrudates were cut into different lengths, further dried, and then washed in a solvent to remove excess binder. The extrudates were then dried further. Testing revealed that the extrudates had a macroporosity of 11.1%, a MOF composition of 94%, and an average particle width of 2.9 mm.

[0500] The aspect ratio of the extrudate containing the first MOF monolithic body is approximately 3.5 to approximately 5 (as measured using hand calipers). The extrudate is compacted and filled into a cylinder of known volume. After compaction for 1 minute, the bulk density of the first MOF monolithic body is measured to be 0.58 g / cm³. 3 .

[0501] The second MOF monolithic body was prepared as follows: The partially dried HKUST-1 binder paste was spread on a tray and dried under ambient conditions for 2 days. Then, the solid material was milled in a Retsch mill and sieved to obtain small portions between 0.85 mm and 0.45 mm. This was used as the second MOF monolithic body.

[0502] The second MOF monolithic host particles have a particle size of less than about 0.9 mm and a particle aspect ratio of about 1.

[0503] A blend of a first MOF monolithic matrix and a second MOF monolithic matrix was prepared to provide an HKUST-1 composition comprising approximately 71.5 wt% of the first MOF monolithic matrix and approximately 28.5 wt% of the second MOF monolithic matrix. The particles were compacted into cylinders of known volume. After compaction for 1 minute, the bulk density of the HKUST-1 composition comprising the first and second MOF monolithic matrices was measured to be 0.73 g / cm³. 3 .

[0504] Compared to the comparative sample containing only the first MOF monolithic body, the composition containing both the first and second MOF monolithic bodies showed a 25.8% increase in bulk density (Table 2). This can be attributed to the increase in the usable external surface area of ​​the composition due to the increase in bulk density and the increase in external area per unit mass.

[0505] Table 2. Filling density of compositions prepared using a first MOF monolithic matrix and a second MOF monolithic matrix, or using only the first MOF monolithic matrix, wherein the MOF is HKUST-1.

[0506]

[0507] Comparison Example 1

[0508] Comparative HKUST-1 compositions were prepared from a first MOF monolithic body containing HKUST-1 as described above in Example 2 and a conventional MOF monolithic body containing HKUST-1.

[0509] The conventional MOF monolithic matrix has the same composition as the first MOF monolithic matrix containing HKUST-1, but the aspect ratio of the particles in the conventional MOF monolithic matrix ranges from approximately 1.5 to approximately 3.5 (as measured using hand calipers). The particles were compacted into a cylinder of known volume. After compaction for 1 minute, the bulk density of the conventional MOF monolithic matrix was measured to be 0.63 g / cm³. 3 This indicates that the packing density is only slightly increased compared to the first MOF monolithic body containing HKUST-1 with a particle aspect ratio of 3.5 to 5.

[0510] The comparative composition was prepared by combining a 50:50 mixture of a first MOF monolithic body containing HKUST-1 and a conventional MOF monolithic body containing HKUST-1. The comparative HKUST-1 composition had a bulk density of approximately 0.62 g / cm³. 3 .

[0511] This indicates that this combination of monolithic matrix does not result in a significant improvement in filling efficiency. Because conventional MOF monolithic matrixes have particle aspect ratios of approximately 1.5 to 3.5, they cannot efficiently fill around extrudates with larger aspect ratios (3.5 to 5).

[0512] Comparison Example 2

[0513] The HKUST-1 composition was prepared from a first MOF monolithic body containing HKUST-1 (i.e., having a diameter of about 2.9 mm) as described above in Example 2 and a narrow MOF monolithic body containing HKUST-1, but wherein the particle width of the narrow MOF monolithic body is about 0.9 mm and the particle length of the narrow MOF monolithic body is up to about 10 mm.

[0514] The narrow MOF monolithic matrix containing HKUST-1 has the same composition as the first MOF monolithic matrix containing HKUST-1. The extrudate of the narrow MOF monolithic matrix is ​​much thinner than that of the first MOF monolithic matrix. Specifically, the particle length of the narrow MOF monolithic matrix is ​​significantly longer than the particle width of the first MOF monolithic matrix.

[0515] The comparative composition was prepared by combining a 2.5:1 mixture of a first monolithic MOF matrix and a narrow monolithic MOF matrix. The particles were tapped into cylinders of known volume. After tapping for 1 minute, the bulk density of the comparative composition was measured to be 0.59 g / cm³. 3 .

[0516] This indicates that this combination of monolithic modules did not result in a significant improvement in filling efficiency or bulk density. Although narrow MOF monolithic modules have smaller particle widths compared to first MOF monolithic modules, they are not efficient at filling around extrudates with large aspect ratios (3.5 to 5).

[0517] Example 3

[0518] UTSA-16 compositions comprising a first MOF monolithic host and a second MOF monolithic host as described herein were prepared. The MOF of the first MOF monolithic host and the second MOF monolithic host is UTSA-16, wherein the metal ion of the MOF is Co, and the organic linker of the MOF is a citrate.

[0519] A first monolithic MOF matrix was prepared by extrusion using ZU-301 as the MOF and methylcellulose as the binder. UTSA-16 was synthesized according to a scheme described in the literature and supplied as a 27% water 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 3 mm orifice to form extrudate pellets. The extrudates were cut into different lengths and further dried. The extrudates were then further dried. Testing revealed that the extrudates had a macroporosity of 9.1%, a MOF composition of 95%, and an average particle width of 2.85 mm.

[0520] The aspect ratio of the extrudate containing the first MOF monolithic body is approximately 2 to approximately 3.6 (as measured using hand calipers). The extrudate is compacted and filled into a cylinder of known volume. After compaction for 1 minute, the bulk density of the first MOF monolithic body is measured to be 0.88 g / cm³. 3 .

[0521] The second MOF monolithic body was prepared as follows: Partially dried UTSA-16 and binder material were further dried under ambient conditions until no further weight loss was observed. The hardened solid material was then milled in a Retsch milling machine and sieved to obtain small portions between 0.85 mm and 0.45 mm. This was used as the second MOF monolithic body.

[0522] A blend of a first monolithic MOF matrix and a second monolithic MOF matrix was prepared to provide a first UTSA-16 composition comprising a first monolithic MOF matrix and a second monolithic MOF matrix in a 2.5:1 ratio (i.e., 71.5 wt% of the first monolithic MOF matrix and 28.5 wt% of the second monolithic MOF matrix). The particles were compacted into cylinders of known volume. After compaction for 1 minute, the bulk density of the first UTSA-16 composition comprising the first and second monolithic MOF matrices was measured to be 1.03 g / cm³. 3 .

[0523] A blend of a first MOF monolithic matrix and a second MOF monolithic matrix was prepared to provide a second UTSA-16 composition comprising a first MOF monolithic matrix and a second MOF monolithic matrix in a 1.64:1 ratio (i.e., 62 wt% of the first MOF monolithic matrix and 38 wt% of the second MOF monolithic matrix). The particles were compacted into cylinders of known volume. After compaction for 1 minute, the bulk density of the second UTSA-16 composition comprising the first MOF monolithic matrix and the second MOF monolithic matrix was measured to be 1.10 g / cm³. 3 .

[0524] A blend of a first monolithic MOF matrix and a second monolithic MOF matrix was prepared to provide a third UTSA-16 composition comprising a first monolithic MOF matrix and a second monolithic MOF matrix in a 1.23:1 ratio (i.e., 55 wt% of the first monolithic MOF matrix and 45 wt% of the second monolithic MOF matrix). The particles were compacted into cylinders of known volume. After compaction for 1 minute, the bulk density of the third UTSA-16 composition comprising the first and second monolithic MOF matrices was measured to be 1.08 g / cm³. 3 .

[0525] This indicates that improvements in packing density were achieved for a range of different ratios of first MOF monolithic body to second MOF monolithic body (Table 3).

[0526] Table 3. Filling densities of compositions prepared using a first MOF monolithic matrix and a second MOF monolithic matrix with different ratios of a first matrix and a second matrix, or using only the first MOF monolithic matrix, wherein the MOF is UTSA-16.

[0527]

[0528] Example 4

[0529] ZU-301 compositions comprising a first MOF monolithic host and a second MOF monolithic host as described herein were prepared. The MOF of the first MOF monolithic host and the second MOF monolithic host is ZU-301, wherein the metal of the MOF is Zn, and the organic linker of the MOF is oxalate and 3-methyl-1H-1,2,4-triazole.

[0530] A first monolithic MOF matrix was prepared by extrusion using ZU-301 as the MOF and PVA as the binder. ZU-301 was synthesized according to the scheme described in the literature and supplied as a 25% water slurry after washing and concentration steps. It was then added as a powder mixture to a 50:50 mixture of PVA and methylcellulose binder and blended by stirring. The resulting mixture was partially dried under ambient conditions to form a deformable solid in a manner similar to other samples. The partially dried material was then extruded through a Caleva extruder with a template having 3 mm orifices to form extrudate pellets. The extrudates were cut into different lengths and further dried, followed by solvent washing in methanol and further drying. Testing revealed that the extrudates had a macroporosity of 12.9%, a MOF composition of 92%, and an average particle width of 2.88 mm.

[0531] The aspect ratio of the extrudate containing the first MOF monolithic body is approximately 2.5 to approximately 4.8 (as measured using hand calipers). The extrudate is compacted and filled into a cylinder of known volume. After compaction for 1 minute, the bulk density of the first MOF monolithic body is measured to be 0.76 g / cm³. 3 .

[0532] The second MOF monolithic body was prepared as follows. The ZU-301 extrudate prepared above was milled in a Retsch cutting mill and sieved to obtain small portions between 0.85 mm and 0.45 mm. This was used as the second MOF monolithic body.

[0533] A blend of a first MOF monolithic matrix and a second MOF monolithic matrix was prepared to provide a ZU-301 composition comprising a first MOF monolithic matrix and a second MOF monolithic matrix in a 3.5:1 ratio (i.e., 77.5 wt% of the first MOF monolithic matrix and 22.5 wt% of the second MOF monolithic matrix). The particles were compacted into cylinders of known volume. After compaction for 1 minute, the bulk density of the ZU-301 composition comprising the first and second MOF monolithic matrices was measured to be 0.89 g / cm³. 3 .

[0534] Compared with the comparative sample containing only the first MOF monolithic body, the bulk density of the composition containing both the first MOF monolithic body and the second MOF monolithic body showed an increase (Table 4).

[0535] Table 2. Filling density of compositions prepared using a first MOF monolithic matrix and a second MOF monolithic matrix, or using only the first MOF monolithic matrix, wherein the MOF is ZU-301.

[0536]

[0537] Example 5

[0538] CO2 and N2 adsorption isotherms were performed on the selected MOF at 20℃, and the results were... Figures 1 to 6 As shown in the figure. This demonstrates the excellent performance of these MOFs as CO2 trapping materials.

[0539] Example 6

[0540] The kinetics of gas adsorption into the MOF monolithic host and the composition were investigated. The gas adsorption kinetics vary depending on the external surface area of ​​the MOF monolithic host and the diffusion coefficient of the gas through the MOF monolithic host.

[0541] While larger MOF extrudates can be produced on a large scale, they may reduce adsorption kinetics compared to smaller MOF extrudates. However, as described in this paper, the industrial-scale production of small MOF extrudates is impractical.

[0542] The initial gas adsorption rate is particularly important for practical adsorption systems because real industrial systems typically do not operate under equilibrium conditions, as this would require a considerable amount of time.

[0543] Therefore, in order to characterize the adsorption kinetics of MOF monolithic hosts with different sizes, DVS tests (at 20 °C) were performed using CO2 adsorption isotherms at CO2 levels of 5% (i.e., 50,000 ppm CO2), 10%, 20%, 30%, and 40%, and the time required for the samples to reach 5% CO2 absorption was measured.

[0544] A first MOF monolithic body (referred to as the long extruder) containing ZU-301 was prepared, similar to the body of Example 4 (with a particle width of 2.9 mm, a particle length of 7.2 mm, and a particle aspect ratio of 2.5).

[0545] A relatively monolithic body containing ZU-301 (referred to as the short extrudate) was prepared, which is similar to the long extrudate but has a particle width of 2.9 mm, a particle length of 2.4 mm, and a particle aspect ratio of 0.83. Due to the short particle length and low aspect ratio, this monolithic body is impractical.

[0546] Figure 7 The adsorption kinetics of CO2 absorption for long and short extrudates are shown. This indicates that the short extrudate takes 150 minutes to reach 5% CO2 absorption, in contrast to the long extrudate which takes 237 minutes.

[0547] A second MOF monolithic body containing ZU-301 was prepared by grinding and sieving the first MOF monolithic body extrusion to obtain a small portion between 1 mm and 1.5 mm.

[0548] These second MOF monolithic modules reached a 5% CO2 load in just 28 minutes. Furthermore, the smaller second MOF monolithic module of Example 4 (i.e., a small fraction sieved to between 0.85 mm and 0.45 mm) was tested, reaching 5% CO2 absorption in just 7 minutes and rapidly reaching a 6.1% load during the first cycle. Despite their advantageous gas absorption properties, compositions containing only these second MOF monolithic modules are impractical and expensive for large-scale production due to the high levels of grinding and sieving required, and the amount of fine particles generated and necessitated for recycling.

[0549] This indicates that the composition of Example 4 (i.e., having 77.5 wt% of the first MOF monolithic body and 22.5 wt% of the second MOF monolithic body) will have an increased volumetric capacity, not only due to the higher packing density, but also due to a further and complementary increase in the initial adsorption rate.

[0550] For example, based on the data above, it is estimated that the composition of Example 4 reaches a CO2 loading of 5% by weight in approximately 188 minutes, which is significantly faster than the time required for the first MOF monolithic body alone (i.e., 237 minutes). This reduces the cycle time by approximately 20%, while increasing the capacity per cycle by between 10% and 20% due to the increased packing density. Since these capacity improvements are cumulative, it is reasonable to expect a total daily capacity increase of approximately 30% for such compositions of the present invention compared to the comparative sample.

[0551] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0552] The enumeration or discussion of obviously previously disclosed documents in this specification is not necessarily an admission that such documents are part of the prior art or common general knowledge.

[0553] Without departing from the disclosure of this invention, all embodiments of the invention and specific features mentioned herein may be separated from or combined with any other embodiments and / or specific features mentioned herein (and thus more specific embodiments and specific features as disclosed herein are described).

[0554] As used herein, the term "comprising" will take its usual meaning in the art, indicating that a component includes, but is not limited to, the relevant features (i.e., including, among other things). Thus, the term "comprising" will include references to components that are substantially composed of the relevant substances.

[0555] As used herein, unless otherwise stated, the terms "consistses substantially of" and "consisting essentially of" will refer to the relevant component that, according to relevant measurements (e.g., by weight), constitutes at least 80% (e.g., at least 85%, at least 90%, or at least 95%, such as at least 99%) of the specified substance. The terms "consistses substantially of" and "consisting essentially of" may be replaced by "consists of" and "consisting of," respectively.

[0556] To avoid any doubt, the term "comprising" will also include references to components that are "substantially composed of the relevant substance" (and in particular "composed of the relevant substance").

[0557] Wherever the word 'about' is used in the context of the amount (e.g., absolute amount, weight, volume, size, diameter, etc.) or relative amount (e.g., percentage) (including concentration and ratio), time range, and parameters (such as temperature) of an individual component or a component of a composition, it should be understood that such variables are approximate and therefore can vary from the actual figures specified herein by ±10%, for example ±5%, and preferably ±2% (e.g., ±1%). This is true even if such figures are first presented as percentages (e.g., 'about 10%' can mean ±10% of the number 10, i.e., any value between 9% and 11%).

[0558] The following numbered paragraphs summarize certain aspects of the invention.

[0559] 1. A composition comprising at least two MOF monolithic bodies,

[0560] The composition comprises at least about 50% by weight of a first MOF monolithic body based on the total weight of the composition;

[0561] The first MOF monolithic body comprises:

[0562] Organic adhesives; and

[0563] Based on the total weight of the first MOF monolithic body, at least approximately 80% by weight of MOF;

[0564] The first MOF monolithic host has a macropore volume of 15% or less of the encapsulation volume of the first MOF monolithic host and a particle aspect ratio of about 2 or greater, and

[0565] The second MOF monolithic body includes:

[0566] Adhesives; and

[0567] MOF;

[0568] The second MOF monolithic body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first MOF monolithic body.

[0569] 2. The composition according to paragraph 1, wherein the binder of the second MOF monolithic body is an organic binder.

[0570] 3. The composition according to paragraph 1, wherein the second MOF monolithic body comprises at least about 50% by weight of MOF based on the total weight of the second MOF monolithic body.

[0571] 4. The composition according to paragraph 1, wherein the second MOF monolithic body comprises, based on the total weight of the second MOF monolithic body, at least about 80% by weight of MOF and up to about 20% by weight of binder.

[0572] 5. The composition according to paragraph 1, wherein the second MOF monolithic body has a macropore volume of about 15% or less of the encapsulation volume of the second MOF monolithic body.

[0573] 6. The composition according to paragraph 1, wherein the composition comprises at least about 70% by weight of the first MOF monolithic body and / or up to about 30% by weight of the second MOF monolithic body based on the total weight of the composition.

[0574] 7. The composition according to paragraph 1, wherein the first MOF monolithic body has a macropore volume of about 12% or less of the encapsulation volume of the first MOF monolithic body, and / or wherein the second MOF monolithic body has a macropore volume of about 12% or less of the encapsulation volume of the second MOF monolithic body.

[0575] 8. The composition according to paragraph 1, wherein the aspect ratio of the particles of the first MOF monolithic body is about 3 or greater.

[0576] 9. The composition according to paragraph 1, wherein the first MOF monolithic body has a maximum particle size greater than or equal to about 1 mm and / or a minimum particle size greater than or equal to about 500 μm.

[0577] 10. The composition according to paragraph 1, wherein the maximum particle size of the second MOF monolithic body is less than or equal to about 5 mm.

[0578] 11. The composition according to paragraph 1, comprising about 10% by weight or less of MOF material having a particle size of about 50 μm or less, based on the total weight of the composition.

[0579] 12. The composition according to paragraph 1, having a content of about 0.3 g / cm³. 3 Or a higher packing density.

[0580] 13. The composition according to paragraph 1, wherein the first MOF monolithic body and / or the second MOF monolithic body has a content of about 0.3 g / cm³. 3 Or a higher encapsulation density.

[0581] 14. The composition according to paragraph 1, wherein the first MOF monolithic body and / or the second MOF monolithic body has a relative density of about 0.3 or greater.

[0582] 15. The composition according to paragraph 1, wherein the first MOF monolithic body and / or the second MOF monolithic body has a microporosity of about 40% or greater based on the total pore volume.

[0583] 16. The composition according to paragraph 1, wherein the first MOF monolithic body and / or the second MOF monolithic body has a thickness of about 10 μm. 2 / g or larger BET surface area.

[0584] 17. The composition according to paragraph 1, wherein the composition further comprises a gas selected from hydrogen, carbon dioxide, methane, krypton, and mixtures thereof.

[0585] 18. The composition according to paragraph 1, wherein the first MOF monolithic body and the second MOF monolithic body comprise the same MOF and / or the same binder.

[0586] 19. The composition according to paragraph 1, wherein the MOF of the first monolithic body and / or the second MOF monolithic body 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.

[0587] 20. The composition according to paragraph 17, wherein the composition is selected from compositions in which,

[0588] The gas contains hydrogen and the first monolithic MOF body contains a MOF selected from HKUST-1, ZIF-8, MOF-808, UiO-66 and mixtures thereof;

[0589] The gas contains carbon dioxide and the first MOF monolithic body contains a MOF selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof;

[0590] The gas contains krypton, and the first monolithic MOF body contains an MOF, which is MOF-74; and

[0591] The gas contains methane and the first MOF monolithic body contains an MOF, which is HKUST-1.

[0592] 21. A method for preparing the composition according to paragraph 1, comprising the following steps:

[0593] a. Providing a wettable adhesive MOF block, the wettable adhesive MOF block comprising:

[0594] i.MOF;

[0595] ii. Based on the total weight of the wetted binder MOF bulk, about 50% to about 95% by weight of a first solvent; and

[0596] iii. An organic binder, wherein the binder can be added as a solution, dispersion, powder, or mixture thereof;

[0597] b. Optionally, reduce the proportion of the first solvent in the wetted adhesive MOF block to provide an undried adhesive MOF block;

[0598] c. Extruding and cutting the wet binder MOF block or the undried binder MOF block to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or greater;

[0599] d. Remove at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body;

[0600] e. Optionally, a second solvent is added to the first dried MOF monolithic body to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic body to provide an optional MOF monolithic body with reduced first binder;

[0601] f. Optionally, at least some of the second solvent is removed from the MOF monolithic body reduced by the optional first binder to provide an optional first unactivated MOF monolithic body;

[0602] g. Activating the first dried MOF monolithic body or the optional first unactivated MOF monolithic body by subjecting it to a temperature of about 100°C or greater to provide a first MOF monolithic body; and

[0603] h. Combining the first MOF monolithic body with the second MOF monolithic body to provide a composition, wherein the second MOF monolithic body is as defined in paragraph 1.

[0604] 22. The method according to paragraph 21, wherein the method further comprises one or more steps to provide a second MOF monolithic body used in step (h), wherein the steps include:

[0605] Some of the first dried MOF monolithic body is ground to provide a second dried MOF monolithic body, wherein the second dried MOF monolithic body has a maximum particle size that is approximately equal to or smaller than the minimum particle size of the first dried MOF monolithic body.

[0606] and / or

[0607] Grinding some of the optional first binder-reduced MOF monolithic body to provide an optional second binder-reduced MOF.

[0608] The monolithic body, wherein the optional second binder-reduced MOF monolithic body has a maximum particle size that is approximately less than or equal to the minimum particle size of the optional second binder-reduced MOF monolithic body.

[0609] 23. A gas storage container comprising the composition according to paragraph 1.

[0610] 24. The gas storage container according to paragraph 23, comprising one or more of the following:

[0611] a. Thermal insulation material of the external wall;

[0612] b. Apparatus for heating and cooling the composition;

[0613] c. Internal baffle;

[0614] d. A device for securing the composition in place;

[0615] e. A shape in which the composition is at a distance of about 10 cm from the outer wall;

[0616] f. Devices for monitoring pressure and / or temperature; and / or

[0617] g. A valve that controls the input and output flow of gas.

[0618] 25. A method for filling, storing, and / or releasing gas into a gas storage container as described in paragraph 23 and / or from a gas storage container as described in paragraph 23.

[0619] 26. The method according to paragraph 25, wherein the gas comprises hydrogen, carbon dioxide, methane, krypton, or a mixture thereof.

[0620] 27. The method described in paragraph 25, wherein the method is part of a gas purification process.

[0621] 28. The method according to paragraph 25, wherein the gas comprises hydrogen and the first monolithic MOF body comprises a MOF selected from HKUST-1, ZIF-8, MOF-808, UiO-66 and mixtures thereof.

[0622] 29. The method according to paragraph 28, wherein the composition comprises about 0.6 to about 0.8 g / cm³ at 77 K and 10 atm. 3 MOF and approximately 0.04 to approximately 0.065 g / cm³ 3 The volume composition of hydrogen gas.

[0623] 30. The method according to paragraph 25, wherein the gas comprises carbon dioxide and the first monolithic MOF body comprises a MOF selected from UTSA-16, CALF-20, ZU-301, TIFSIX-3-Ni, NbOFFIVE-1-Ni, UiO-66-NH2 and mixtures thereof.

[0624] 31. The method according to paragraph 30, wherein the composition comprises about 0.6 to about 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to approximately 0.1 g / cm³ 3 The volume composition of carbon dioxide.

[0625] 32. The method according to paragraph 25, wherein the gas comprises krypton and the first MOF monolithic body comprises MOF-74.

[0626] 33. The method according to paragraph 32, wherein the composition comprises about 0.6 to about 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to approximately 0.1 g / cm³ 3 The volume composition of kryptonite.

[0627] 34. The method according to paragraph 25, wherein the gas comprises methane and the first MOF monolithic body comprises HKUST-1.

[0628] 35. The method according to paragraph 34, wherein the composition comprises about 0.6 to about 0.8 g / cm³ at 293 K and 5 atm. 3 MOF and approximately 0.05 to approximately 0.1 g / cm³ 3 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 wt.%, based on the total weight of the solid composition, of a first MOF monolithic body; wherein the first MOF monolithic body comprises: an organic binder; and at least about 80 wt.%, based on the total weight of the solid first MOF monolithic body, of a MOF; wherein the first MOF monolithic body has a macropore volume of about 15% or less of the enclosed volume of the first MOF monolithic body, a particle aspect ratio of about 2 or greater, and a minimum particle diameter of greater than or equal to about 1 mm, and wherein the second MOF monolithic body comprises: a binder; and a MOF; wherein the second MOF monolithic body has a maximum particle diameter that is about equal to or less than the minimum particle diameter of the first MOF monolithic body.

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

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

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

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

6. The composition of 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 of 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 wherein the first MOF monolithic body has a minimum particle diameter of about 1 to about 5 mm, and / or wherein the maximum particle diameter of the second MOF monolithic body is about 20 pm to about 3 mm.

10. The composition of 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. ​ ​ ​ ​ ​ ​ 8. The composition of any one of claims 1-7, having a bulk density of about 0.3 to about 1.5 g / cm 3 and / or wherein the first MOF monolith body and / or the second MOF monolith body has an envelope density of about 0.4 to about 2 g / cm 3 and / or wherein the first MOF monolith body and / or the second MOF monolith body has a relative density of about 0.3 to about 1.

3.

9. The composition according to any one of claims 1 to 8, wherein the first MOF monolithic body and / or the second MOF monolithic body has a microporosity of about 40% to about 75% based on the total pore volume, and / or wherein the first MOF monolithic body and / or the second MOF monolithic body has a microporosity of about 0 to about 2,500 m³ / s. 2 / g of BET surface area. ​ 11. The composition of any one of claims 1 to 10, wherein the composition further comprises a gas selected from the group consisting of hydrogen, carbon dioxide, methane, krypton, water, and mixtures thereof.

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

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

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

15. The composition of any one of claims 1 to 14, wherein the MOF of the first MOF monolithic body and / or the second MOF monolithic body is independently selected from the group consisting of 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.

16. The composition of any one of claims 12 to 15, selected from the group of compositions wherein: the gas comprises hydrogen and the first MOF monolithic body and / or the second MOF monolithic body comprises a suitable MOF; the gas comprises carbon dioxide and the first MOF monolithic body and / or the second MOF monolithic body comprises a suitable MOF; the gas comprises krypton and the first MOF monolithic body and / or the second MOF monolithic body comprises a suitable MOF; and the gas comprises methane and the first MOF monolithic body and / or the second MOF monolithic body comprises a suitable MOF.

17. A method of making the composition of any one of claims 1 to 16, comprising the steps of: a. providing a wet binder MOF bulk comprising: i. a MOF; ii. about 50 wt% to about 95 wt% of a first solvent based on the total weight of the wet binder MOF bulk; and iii. an organic binder, wherein the binder can be added as a solution, dispersion, powder, or mixtures thereof; b. optionally reducing the proportion of the first solvent in the wet binder MOF bulk to provide a non-dried binder MOF bulk; c. extruding and cutting the wet binder MOF block or the undried binder MOF block to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or greater; d. removing at least some of the remaining first solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body; e. optionally adding a second solvent to the first dried MOF monolithic body to remove at least a portion of any residual first solvent, at least a portion of any unreacted reactants, and at least a portion of the organic binder from the first dried MOF monolithic body to provide an optional first binder-reduced MOF monolithic body; f. optionally removing at least some of the second solvent from the optional first binder-reduced MOF monolithic body, to provide an optional first unactivated MOF monolithic body; g. activating the first dried MOF monolithic body or the optional first unactivated MOF monolithic body by subjecting the first dried MOF monolithic body or the optional first unactivated MOF monolithic body to a temperature of about 100°C or greater to provide a first MOF monolithic body; and h. 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 of making a composition according to any one of claims 1 to 16, comprising the steps of: I. forming a wet MOF reaction block, wherein the wet MOF reaction block comprises: i. about 20% to about 70%, or about 30% to about 60% by weight, or about 40% to about 50% of MOF, based on the total weight of the wet MOF reaction block; ii. about 3% to about 50%, about 8% to about 40%, or about 10% to about 30% of unreacted MOF precursors, by weight of MOF in the wet MOF reaction block; and iii. about 10% to about 70% by weight, preferably about 10% to about 60%, preferably about 10% to less than about 50% of reaction solvent, by weight of the wet MOF reaction block; II. contacting the wet MOF reaction block with an organic binder to provide a wet binder MOF block; III. optionally reducing the proportion of the reaction solvent in the wet binder MOF block to provide an undried binder MOF block; IV. extruding and cutting the wet binder MOF block or the undried binder MOF block to provide a first undried MOF monolithic body having a particle aspect ratio of about 2 or greater; V. removing at least some of the remaining solvent from the first undried MOF monolithic body to provide a first dried MOF monolithic body; VI. optionally contacting the first dry MOF monolith body with a washing solvent to remove at least a portion of residual reaction solvent, at least a portion of any unreacted reactants, and / or at least a portion of the organic binder from the first dry MOF monolith body to provide an optional first binder-reduced MOF monolith body; VII. optionally removing at least some of the second solvent from the optional first binder-reduced MOF monolith body, to provide an optional first unactivated MOF monolith body; VIII. activating the first dry MOF monolith body or the optional first unactivated MOF monolith body by subjecting the first dry MOF monolith body or the optional first unactivated MOF monolith body to a temperature of about 100 °C or greater to provide a first MOF monolith body; and IX. combining the first MOF monolith body with a second MOF monolith body to provide a composition, wherein the second MOF monolith body has a maximum particle diameter that is about less than or equal to a minimum particle diameter of the first MOF monolith body.

19. The method of claim 17 or 18, wherein the method further comprises one or more steps to provide a second MOF monolith body for use in step (h) or step (IX), wherein the steps comprise: grinding some of the first dry MOF monolith body to provide a second dry MOF monolith body, wherein the second dry MOF monolith body has a maximum particle diameter that is about equal to or less than a minimum particle diameter of the first dry MOF monolith body; and / or grinding some of the optional first binder-reduced MOF monolith body to provide an optional second binder-reduced MOF monolith body, wherein the optional second binder-reduced MOF monolith body has a maximum particle diameter that is about less than or equal to a minimum particle diameter of the optional first binder-reduced MOF monolith body.

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

21. The gas storage vessel of claim 20, comprising one or more of: a. insulation of the outer wall; b. a device to heat and cool the composition; c. internal baffles; d. a device to constrain the composition in place; e. a shape such that the composition is greater than or equal to about 10 cm from the outer wall; f. a device to monitor pressure and / or temperature; and / or g. a valve to control the flow of gas in and out.

22. Use of the gas storage vessel of claim 20 or claim 21 for the uptake, storage, and / or release of a gas.

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

24. The use of 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 use of any one of claims 22-25, wherein the gas comprises hydrogen and the first MOF monolithic body and / or the second MOF monolithic body comprises a suitable MOF, optionally wherein the composition comprises a bulk volume composition of about 0.4 to about 1.1 g / cm 3 of MOF and about 0.025 to about 0.09 g / cm 3 of hydrogen at 77 K and 10 atm.

27. The use of any one of claims 22 to 25, wherein the gas comprises carbon dioxide and the first MOF monolith body and / or the second MOF monolith body comprises a suitable MOF, optionally wherein the composition comprises a packing volume composition of about 0.4 to about 1.1 g / cm3 of MOF and about 0.03 to about 0.14 g / cm3 of carbon dioxide at 293 K and 5 atm. 3 3 MOF and about 0.03 to about 0.14 g / cm3 of carbon dioxide.​ 28. The use of any one of claims 22-25, wherein the gas comprises krypton and the first MOF monolith body and / or the second MOF monolith body comprises a suitable MOF, optionally wherein the composition comprises a packing volume composition of about 0.4 to about 1.1 g / cm3 of MOF and about 0.03 to about 0.14 g / cm3 of krypton at 293 K and 5 atm. 3 3 MOF and about 0.03 to about 0.14 g / cm3 of krypton at 293 K and 5 atm.​ 29. The use of any one of claims 22-25, wherein the gas comprises methane and the first MOF monolith body and / or the second MOF monolith body comprises a suitable MOF, optionally wherein the composition comprises a packing volume composition of about 0.4 to about 1.1 g / cm3 of MOF and about 0.03 to about 0.14 g / cm3 of methane at 293 K and 5 atm. 3 3 of methane.​ 30. The use of any one of claims 22-25, wherein the gas comprises water and the first MOF monolith body and / or the second MOF monolith body comprises a suitable MOF, optionally wherein the composition comprises a packing volume composition of about 0.4 to about 1.1 g / cm 3 of MOF and about 0.03 to about 0.14 g / cm 3 of water at 293 K and 5 atm.

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