Method for manufacturing a suction body

Abstract

The present invention relates to a method for producing an adsorbent comprising a structure and a polymer binder.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing an adsorbent. The adsorbent comprises one or more organic frameworks. The adsorbent also comprises an organic polymer binder.

Background Art

[0002] The present invention realizes an industrially significant production of a robust adsorbent comprising an organic framework. The organic framework is typically selected from metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) materials. For clarity, the term "framework" is always used as an inclusive term to describe MOFs and COFs. MOFs and COFs are organic frameworks. The term "industrially significant" refers to a process that has the potential to produce multiple kilograms of adsorbent per day using cost-effective and readily available equipment. Thus, laboratory-based preparation protocols and procedures that produce gram quantities of samples, using, for example, beakers and test tubes, are typically not industrially significant.

[0003] Organic frameworks, such as MOFs and COFs, are sorptive crystalline materials that can be used to adsorb and desorb gases. The terms "framework" and "organic framework" are used interchangeably to describe metal-organic frameworks (MOFs) and / or covalent organic frameworks (COFs). These materials can offer many advantages in terms of performance over current sorptive materials and are candidates for improved gas adsorption and storage systems, for example, those required for practical transportation systems. MOFs and COFs are of great interest, and many research groups and companies are actively pursuing the development of synthetic routes and manufacturing methods. Examples of MOFs are HKUST-1, UiO-66, and ZIF-8.

[0004] The need to store as much gas as possible in a given volume of storage vessel means that the bulk density of the adsorbent material is very important. The higher this density, the more material can be placed in the available working volume. However, it is desirable that the density does not reach the point of loss of porosity and sorption performance.

[0005] MOFs and COFs, and many other adsorbent structured materials, are typically synthesized in the form of fine, low-density powders. Fine powders are not suitable for many uses of organic structures, such as bulk storage or selective adsorption of components from fluids. The low bulk density of typical MOF or COF powders limits the amount of adsorbent material that can be placed in a container. In addition, the inevitable channelling and compaction of fine, low-density powders causes major problems for the uniform flow of fluids through the powder bed. For such adsorbent materials to be industrially useful, they need to be formed into larger, mechanically robust bodies with higher density that retain high volumetric efficiency. Conventional options for forming larger, robust bodies from fine powders include tableting and extrusion molding.

[0006] However, many organic structures are not robust under pressure. For example, the bonds in MOFs are based on metal coordination chemistry and are therefore relatively weak. If many MOFs and COFs are subjected to high compressive forces, their internal pores may collapse. As a result of this collapse, the MOF or COF becomes amorphous and loses surface area and, consequently, fluid storage capacity. High-pressure manufacturing processes for forming consolidated bodies of MOFs and COFs, such as tableting, can result in consolidated bodies with reduced surface area and even poorer fluid storage capacity.

[0007] The alternative process is to mix the structural powder with a plasticizer / liquid to form a paste / soft solid, then extrude the material to form an extrudate, and then remove the plasticizer / liquid to cure the extrudate. However, such extrudates often require the presence of a binder material, typically an inorganic particulate binder such as hydrated alumina, to provide a mechanically robust body, and the use of pre-dried structural powders, particularly organic structural powders, can have several disadvantages such as introducing an undesirable level of meso- and macroporosity. Extrusion is a mechanically simple and widespread process and an attractive manufacturing method.

[0008] For the extrusion process, i.e., the particle production step, to be industrially significant, the extrudate / body produced must be able to be made at an industrially significant rate using existing equipment. Most of the techniques published for the extrusion (or other particle formation steps) of MOFs or COFs describe small-scale, e.g., laboratory, results. A paste / soft solid or blend mixture containing an adsorbent powder in addition to the plasticizer / lubricant liquid is typically made into a single extrudate strand, which is left to dry and then cut into small pieces. The physical properties required for the mixture to be extruded or formed into small bodies enabling industrially significant large-scale processing are not described in the art. However, the successful handling of the formed small bodies after extrusion or general manufacturing is essential for any further large-scale manufacturing rate.

[0009] In the extrusion process, the extruded strands need to be broken or cut into even smaller lengths (the "extrudates"). This can be done by mechanical cutting of the longer extrudates or by breakage during extrusion and subsequent handling. Extrudates are often formed by mechanical cutting of the extrudate strands using a die face-cutter. The extrudates are cut by a rotating blade that moves across the surface of the die plate. This means that the extrudates can be cut to a controlled length, which can be controlled by the rotational speed of the cutting tool and the design of the die.

[0010] For the extrudate cutting process, or any body forming process based on cutting, to work well, it is desirable for the material not to stick to any of the blades used to cut the material. If a large amount of material actually sticks to the cutting tool, this results in the accumulation of material on the cutting tool and the production of large chunks of material rather than individual extrudates or bodies. It is also necessary for the bodies, such as extrudates, not to stick to each other or to the equipment side immediately after cutting or breaking. This is often a major problem with the extrusion cutting process, which is due to the concentration of extrusion in a small space leading to frequent extrudate:extrudate collisions. If the extrudates or bodies are too soft and / or too sticky, they may stick to each other after a collision. Also, if the extruded strands are too soft or too sticky, mechanical breakage of the extrudate strands, for example in processes that rely on extrusion-spheronization, will not work properly.

[0011] The problem of not sticking deformable materials to cutting blades applies to materials in other forms than extrudates, such as flakes, thick plates, tablets, or other larger bodies. Extrudates are a very convenient form, however, it is also industrially significant that other larger bodies, such as the larger "thick plates" formed by tray drying or large flat tablets, can be cut or otherwise broken into smaller bodies, for example, by the use of a flaker or other cutting tools. The formation of smaller bodies is very often followed by optional, but highly preferred, further process steps such as spheronization and / or controlled drying in a spheronizer.

[0012] Thus, it can be seen that in order to successfully carry out the large-scale production of adsorbent structure bodies by extrusion or other particle forming processes, a mixture that has been treated to have specific physical properties is required. Any mixture should not be too soft when being cut or broken, otherwise it will stick either to itself, or to the equipment side, or to the cutting tool, leading to the process becoming immediately infeasible. If the mixture is too hard, the porosity of the MOF or COF can be damaged by the high pressure required to extrude the mixture or otherwise form the body, or generally the particles can become too hard to be easily spheronized.

[0013] The use of a binder is often important to provide sufficient robustness to the organic (or other) body. Binders described in the art often comprise inorganic particles such as hydrated alumina. Such inorganic microparticle binders need to be used at relatively high levels (e.g., 30 wt%) in order to be effective and to provide robustness depending on particle:particle interlocking. Such high levels of such binders essentially dilute the volumetric performance of such adsorbents due to the binder replacing the structural material. However, such particulate binders do not block the pores of the structural material. In most of the art, a process is described in which pre-formed and dried MOF powder (often spray-dried powder) is mixed with a binder (typically an inorganic binder) and a plasticizer / lubricant and subsequently extrusion molded. The MOF powder can be spray-dried and optionally crushed prior to mixing with the binder and plasticizer and extrusion molding. Other known processes simplify the treatment by spray-drying a mixture of MOF powder and an inorganic binder and subsequently extrusion molding the spray-dried granules.

[0014] For clarity, the term "body of the structure" describes the body, e.g., the extrudate, where in this case, most of the body (i.e., >50 wt%) comprises one or more structural materials and mixtures and blends thereof.

[0015] The inventors have found that an optimized organic structure body is formed when the microcrystals of MOF or COF forming the structure body are kept in a dispersed state and typically in a small size before forming the body. For example, this is better if the organic structure microcrystals obtained from the reaction mixture do not pass through a thorough drying step that forms individual dry and robust granules before being formed into a larger body. Rather, this is better if the microcrystals formed in the reaction mixture are solvated (still having some free solvent) and kept in a dispersed state before being formed into a larger body. Typically, the smaller the organic structure microcrystals, the more tightly packed they can be in the adsorbent. However, it is possible to combine a limited amount of pre-dried structure powder with the solvated structure (as described above) without excessive loss of beneficial properties. Considering that sufficient solvent and strong stirring are provided, it is also possible to redissolve and redisperse the aggregates of the pre-dried structure powder. In the process of the present invention, a high level of solvent can be used in any of the redissolving steps.

[0016] For clarity, "undried" in the context of this application describes a concentrated mass of structural material that has sufficient solvent to be deformable under moderate, e.g., hand pressure, but is solid enough to generally retain its shape during handling if formed into a molded body. Typically, a mass of undried structure will have less than 75% free solvent, or less than 70% free solvent, or less than 60% free solvent, or even less than 50% free solvent. "Wet" refers to a mass of structural material and solvent that typically has sufficient free solvent, e.g., greater than 60%, or greater than 70%, or greater than 80% solvent, to form a high-concentration paste or slurry. "Dried" refers to a body or mass of structural material that has been sufficiently dried to form a hard and robust body. Such a physically hard structure body can still contain a significant level of solvent, perhaps due to the high adsorptivity of typical structural materials such as MOFs or COFs. A dried structure body can typically still contain up to 50% solvent.

[0017] Typically, "free" solvent refers to the proportion of solvent or solvents that can be removed from the material by drying at 25 °C for 10 hours. Free solvent is not tightly bound to the chemical species and can affect the rheology of the body. Free solvent is a portion of the total solvent. A sample size between 2 g and 10 g is generally used when measuring the free solvent level.

[0018] Therefore, it is possible to partially dry the wet material to first form an undried material and then further dry it to form a dried material. In the case of any given structural body-containing mixture, the wet material will have a higher free solvent level than the undried material, and the undried material will in turn have a higher free solvent level than the dried material. However, the absolute amount of solvent at these different (wet, undried, dried) stages can vary for different structures and binders. The dried structural body can pass through further processing steps such as solvent washing and activation at high temperature to completely remove the residual solvent.

[0019] Although not wishing to be bound by theory, any drying step (e.g., spray drying) that forms structural microcrystals in a powder comprising individual particles or granules is thought to essentially create significant levels of macro- and mesoporosity in these larger dried agglomerated particles. The rapid removal of the solvent involved in many drying processes is thought to create larger pores or regions of non-uniform hardness. These structural powders, even when passed through a size reduction step, can introduce an undesirable level of meso- and macro-porosity into any structural body formed from them, thus reducing the volumetric performance of the body. High pressure may be used in an extrusion molding step to partially "squeeze out" at least some of this undesirable porosity, but this can potentially easily collapse the internal pores of many organic structures. However, an adsorbent structural body can be made by incorporating a portion (i.e., <50%) of the structural material as a pre-dried powder to limit the amount of undesirable porosity.

[0020] The inventors have found that when a wet structural material (such as those described above) is combined with a polymer binder (preferably in solution), partially dried to form a mass of an undried structure / binder with specified properties, formed into a structure / binder body, and subsequently further dried under controlled (restricted temperature) conditions to form a dried structure adsorbent, an optimized structure body is formed. It may be preferable to pass the dried extrudate or body through subsequent steps of further solvent exchange and washing. The binder can be present in solution, preferably in aqueous solution, to improve dispersion, or can be in solid form, or can be a combination of solid and solution. Adding a binder in solid form, preferably as a fine powder, by strong mixing may be advantageous as it does not introduce additional free solvent. Suitable binders can include soluble organic polymer materials such as methylcellulose or polyvinyl alcohol.

[0021] By controlling, for example, the level of free solvent in the undried structure / binder mass, the physical properties of the undried structure / binder mass can be controlled so that industrially significant processes such as extrusion molding / spheronization can be used successfully. A preferred feature of the process is that a large proportion of the structural microcrystals do not form into individual dried powder particles before forming into a larger structure body. This can avoid introducing undesirable levels of meso- and macroporosity into the resulting structure body.

[0022] One challenge is the need to concentrate a dispersion mixture of small structured microcrystals, typically formed in a dilute reaction mixture. Preferably the microcrystals have an average particle size of less than about 900 nm, or less than about 800 nm, or less than about 600 nm, or less than about 400 nm, or even less than about 200 nm. When the size of the preferred microcrystals is small, separation steps such as filtration become more difficult, and a step of moderately aggregating the microcrystals in the reaction mixture prior to separation may be advantageous. The solvent can always be removed by evaporation, but it is preferred if at least some of the solvent present can be removed by other separation processes such as filtration, sedimentation, or centrifugation, because this will also remove dissolved materials such as unreacted raw materials in the solvent being removed. The dilute reaction mixture (typically up to 5% or up to 10% solids) is concentrated to form a wet mass of structures typically having more than 10% solids. Typically, the wet mass of structures will contain <30% solids content. Subsequently, this is then contacted with a polymeric binder (preferably in solution) to obtain a wet binder mass. The wet binder mass is then formed into an undried binder mass by reducing the amount of solvent. The wet binder mass is typically too liquid to form into individual bodies (especially when the polymeric binder is in solution). The solids level can be less than 20%. Removal of the free solvent further solidifies the binder mass. The undried binder mass is here rendered suitable for forming into extrudates or other bodies, followed optionally by spheronization and / or other process steps.

[0023] Typically, the free solvent is a solvent or a proportion of a plurality of solvents that is not strongly bound to another chemical species, such as a binder polymer, and is available to plasticize the binder and generally acts as a lubricant. The free solvent can be removed by drying at 25 °C for 10 hours under ambient conditions. Solvents that do not evaporate under these conditions are not considered to be "free". The total level of solvent in the sample is determined by measuring the weight loss of the sample heated to 100 °C under vacuum for > 10 hours. The % solids content of the material is 100% minus the total solvent level. Preferably, the free solvent to be removed consists of water. When the free solvent consists of water, the level of the free solvent is generally evaluated by water activity. All of this needs to be carried out in an industrially meaningful way. Summary of the Invention Means for Solving the Problems

[0024] The present invention provides: (a) forming a mass of a wet structure, the mass of the wet structure comprising: (i) an organic structure; and (ii) a first solvent, preferably, the organic structure comprises a metal-organic framework (MOF), a covalent organic framework (COF), or a mixture thereof; (b) contacting the mass of the wet structure with a polymer binder to form a mass of a wet binder; (c) partially drying the mass of the wet binder to form a mass of an undried binder; (d) extruding and / or cutting the mass of the undried binder to form an undried adsorbent; (e) removing at least a part of the first solvent from the undried adsorbent to form a dried adsorbent; (f) contacting the dried adsorbent with a second solvent to form a washed adsorbent; (g) Removing at least a portion of the second solvent from the washed adsorbent to form a deactivated adsorbent; (h) Activating the deactivated adsorbent by passing the deactivated adsorbent through a temperature greater than 100° C. to form an adsorbent; There is provided a method for manufacturing an adsorbent, comprising:

[0025] Typically, the mass of the undried binder is formed into an undried adsorbent, such as an extrudate of a predetermined length. They are subsequently preferably passed through a further spheronization step. The undried adsorbent is subsequently dried to form a dried adsorbent. Preferably, step (e) is carried out under controlled and restricted conditions, such as at <about 80° C., or less than about 60° C., or less than about 40° C., or even at ambient conditions such as about 20° C., so as to slowly dry the undried adsorbent. Slowly drying the undried adsorbent is considered important to avoid cracking and fragmentation of the undried adsorbent as the solvated binder material dries and shrinks. High drying temperatures can be used for less volatile solvents such as DMF, while low drying temperatures can be used for more volatile solvents such as water or ethanol or methanol. The dried adsorbent is subsequently typically passed through a washing step using a second solvent to remove unreacted material and excess binder to enhance the surface area to give a washed adsorbent. After any solvent washing step, the washed adsorbent is subsequently dried and activated at a high temperature to form an adsorbent. DETAILED DESCRIPTION OF THE INVENTION

[0026] Throughout this specification, one or more aspects of the invention may be combined with one or more of the features described herein to define distinct embodiments of the invention.

[0027] Wherever the singular form of a noun is used in this specification, unless the context otherwise indicates, this shall be taken to include the plural forms of that noun, and vice versa. For example, it is desirable that the term "adsorbent body" be understood to also refer to a plurality of adsorbent bodies, that the term "metal-organic framework (MOF)" be understood to also refer to a plurality of metal-organic frameworks (MOFs), and that the term "covalent organic framework (COF)" be understood to also refer to a plurality of covalent organic frameworks (COFs).

[0028] Throughout this specification, the term "comprise", or variations such as "comprises" or "comprising", are to be understood as implying the inclusion of a stated element, ingredient, or step, or group of elements, ingredients, or steps, but not the exclusion of any other element, ingredient, or step, or group of elements, ingredients, or steps. The term "comprising" includes within its scope the terms "consisting of" and "consisting essentially of".

[0029] The term "consisting" or variations thereof are to be understood as implying the inclusion of a stated element, ingredient, or step, or group of elements, ingredients, or steps, and the exclusion of any other element, ingredient, or step, or group of elements, ingredients, or steps.

[0030] The term "consisting essentially of" or variations thereof is understood to mean including the recited components, ingredients, or steps, or groups of components, ingredients, or steps, and that additional components may be present, but that they merely do not substantially affect the essential characteristics of the formulation, composition, or compound.

[0031] As used herein, the term "about" when used in reference to a numerical or quantitative value refers to a value within ±5% of the specified value.

[0032] A method for manufacturing an adsorbent. The method comprises: (a) forming a mass of a wet structure, wherein the mass of the wet structure: (i) an organic structure; and (ii) a first solvent, and preferably the organic structure comprises a metal-organic framework (MOF), a covalent organic framework (COF), or a mixture thereof; (b) contacting the mass of the wet structure with a polymer binder to form a mass of a wet binder; (c) partially drying the mass of the wet binder to form a mass of an undried binder; (d) extruding and / or cutting the mass of the undried binder to form an undried adsorbent; (e) removing at least a portion of the first solvent from the undried adsorbent to form a dried adsorbent; (f) contacting the dried adsorbent with a second solvent to form a washed adsorbent; (g) removing at least a portion of the second solvent from the washed adsorbent to form an unactivated adsorbent; (h) activating the unactivated adsorbent by passing the unactivated adsorbent through a temperature greater than 100°C to form an adsorbent, and comprising.

[0033] Typically, it is necessary to first wash and concentrate such materials from the dilute reaction mixtures typically used to synthesize the structured microcrystals to form a mass of wet structures. The removal of large amounts of liquid can be carried out in a number of ways. This can be carried out by spray drying, but as mentioned previously, this results in the undesirable formation of larger dried granules and can also leave undesirable residual materials. Washing of the mass of wet structures may mean that a mixture of solvents is present in the mass of wet structures.

[0034] Concentrating the structured microcrystals from the reaction mixture or wash mixture is generally carried out in the laboratory by use of a centrifuge. Centrifuging the reaction mixture is very effective in separating the solid particles from the surrounding liquid and can form a more concentrated slurry or solid layer. Centrifugation can be continuous or batch and can be integrated with other washing and separation steps. A preferred industrial solution is that the structured microcrystals in the reaction mixture are concentrated into a mass of wet structures by a filtration step. This can be carried out easily, but does, of course, leave behind a filtered mass of wet structures with a substantially high level of residual free solvent, for example, as compared to high speed centrifugation.

[0035] Adding the polymer binder solution further increases the level of solvent. Such a mass of wet binder is too liquid to be successfully extruded and / or cut. The mass of wet binder needs to be passed through a drying or free solvent reduction step to form a mass of undried binder that is solid enough to enable any extrusion and / or cutting steps to be realized.

[0036] As used herein, the term "free solvent" refers to a solvent that is available for plasticizing the binder. A solvent that is tightly held inside the pores of a structure (e.g.) or tightly bound to binder molecules or other chemical species is not "free" because that solvent is not available for plasticizing the binder. Water held inside a hydrate is not "free" and thus cannot act as a lubricant or affect the rheology of the mixture. When the solvent is water, the level of free solvent is related to the measured water activity. The water activity of a material at a given temperature is defined as the ratio of the humidity of the air in equilibrium with the sample at that temperature to the saturation humidity of the air at that temperature. If the first solvent comprises water in any possible case, this is highly preferred due to the resulting process simplification and ease of industrial use.

[0037] Typically, the level of free solvent can be reduced by controlled evaporation or by adding one or more porous fine powders at a moderate level (e.g., up to about 40 wt%) that can adsorb at least a portion of the free solvent. Such powders can include silica, activated carbon, finely divided pre-dried organic structures, zeolites, or combinations thereof. Silica, for example, can strongly adsorb a large amount of solvent inside its pores so that the solvent is no longer free. The level of free solvent in the body can be measured by measuring the weight loss of the sample at 25°C over 10 hours, since only the solvent that is not tightly bound to or held by other chemical species will be removed by this temperature.

[0038] The present invention provides a method for manufacturing a high-performance adsorbent structure body by extrusion and / or cutting processes using a multi-stage drying process, where in this case, a mass of wet structure bodies is preferably contacted with a polymer binder in solution and even more preferably in an aqueous solution to form a mass of wet binder. Preferably, the use of a high level of solvent means that the binder is well dispersed around the structure microcrystals, and the multi-stage drying process means that the level of binder in the final structure body does not need to be restricted by the requirements of intermediate processing. Thus, typically, the mass of wet binder has sufficient free solvent, which is removed to form a further solid undried mass of binder, which is formed into an undried adsorbent and can subsequently be passed through at least one further solvent reduction step. The undried adsorbent can be formed by extrusion and / or cutting processes. Preferably, the undried adsorbent is passed through a spheronization step before the further solvent reduction step to form a dried adsorbent. The dried adsorbent can be dried after undergoing a washing step using a second solvent to form a washed adsorbent.

[0039] It is highly preferred if most or all of the structure microcrystals do not undergo a thorough drying step to form individual dried granules before being incorporated into a larger body with the binder. A preferred process is where the structure is first synthesized in a dilute reaction mixture, washed and / or concentrated to form a mass of wet structure bodies. The concentration step can be carried out by any known means and can include an aggregation step, by which small individual structure microcrystals are aggregated together by either chemical or mechanical (e.g., ultrasonic) means to form larger secondary aggregates, which are more easily removed from the reaction mixture, for example by filtration or centrifugation, to form a mass of wet structure bodies. Such in-situ aggregates typically do not have sufficient robustness to maintain any undesirable porosity, etc. during further processing.

[0040] The agglomerates of the wet structure are subsequently, preferably in solution, brought into contact with a polymer binder to form agglomerates of the wet binder. It may be advantageous to further remove some of the free solvent from the agglomerates of the wet structure before contacting the organic polymer binder with the slurry. The level of free solvent in the agglomerates of the wet binder is subsequently reduced until the resulting agglomerates of the undried binder have rheological properties suitable for being extruded and / or cut without damaging the cutting tool, deforming excessively, or sticking to the surface. The agglomerates of the undried binder are subsequently cut to form small bodies and are preferably spheronized. The smaller undried adsorbents are subsequently passed through a gentle (slow) drying step to form dried adsorbents, typically followed by a solvent washing step in a second solvent.

[0041] Step (a) of forming agglomerates of the wet structure. Step (a) forms agglomerates of the wet structure.

[0042] Preferably, step (a) is: (i) (a) a structure precursor material, such as a metal organic structure precursor material and / or a covalent organic structure precursor material; (b) a reaction solvent, are brought into contact together to form a dilute reaction mixture, wherein the dilute reaction mixture: (a) metal organic structure microcrystals and / or covalent organic structure microcrystals; (b) a reaction solvent, comprises; (ii) concentrating the dilute reaction mixture by removing at least some of the reaction solvent and any other solvent to form agglomerates of the wet structure, wherein the agglomerates of the wet structure may also contain a first solvent from any washing step for removing the reaction solvent and other unwanted materials, and is carried out by. The first solvent used in any washing step may be the same as or different from the reaction solvent.

[0043] In step (i), contacting the precursor material of the structure with the reaction solvent together can be carried out by at least one of the following: a) Dissolving the precursor material of the structure typically in an alcohol solvent such as water or ethanol; and / or b) Condensing the dissolved precursor material of the structure to form structure microcrystals, such as metal-organic structure microcrystals and / or covalent organic structure microcrystals. can be executed by at least one of them.

[0044] Suitable conditions for the contacting step (i), such as the solvent, reaction temperature, and reaction time, vary depending on the precursor material and the structure microcrystals, and such conditions are within the scope of those skilled in the art.

[0045] Preferably, the precursor material of the metal-organic structure can be one or more, or a plurality of, metal ions, such as metal cations, and one or more, or a plurality of, organic ligands, such as multidentate organic ligands.

[0046] One or more, or a plurality of, metal ions can be selected from the group consisting of ions of zirconium, iron, zinc, hafnium, magnesium, and potassium. The metal ions can be provided by a salt of a metal ion, such as ZrCl4.

[0047] Multidentate organic ligands are organic ligands that can donate two or more pairs of electrons in a complex formation reaction to form two or more coordination bonds. One or more, or multiple types of, organic ligands may comprise two or more oxygen and / or nitrogen atoms suitable for donating a pair of electrons to form two or more coordination bonds. Preferably, the oxygen atoms may be present as carboxylates or nitro groups. Preferably, the nitrogen atoms may be present as amine groups. Typically, multiple types of organic ligands may be aromatic carboxylates, aromatic amines, and / or aromatic nitros. Preferably, the organic ligand is selected from the group consisting of tetrakis(4-carboxyphenyl)porphyrin (TCPP), 1,4-benzenedicarboxylic acid (BDC), 1,3,5-benzenetricarboxylic acid (H3BTC), 1,3,5,8-(p-benzoato)pyrenelinker (H4TBAPy), 4’,4’’’,4’’’’’,4’’’’’’’-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1’-biphenyl]-3-carboxylic acid)) (H4ETTC).

[0048] Preferably, the covalent organic framework precursor material may be boronic acids (e.g., phenyldiboronic acid) capable of forming boronate esters (condensation with alcohols), boroxines (self-condensation), or borazines (condensation with amines); nitriles (e.g., 1,4-dicyanobenzene) capable of forming triazines; or amines and aldehydes (e.g., anilines and benzaldehydes) capable of forming imines.

[0049] Preferably, the structural microcrystals in the dilute reaction mixture aggregate into larger secondary particles prior to partial removal of the reaction solvent.

[0050] Preferably, the aggregation step is as follows: (a) adding a poor solvent; (b) adding a polymer aggregation aid comprising a polymer used as a binder; and / or (c) applying high-frequency ultrasound. is carried out by at least one of.

[0051] Preferably, the poor solvent is miscible with the reaction solvent and has a hydrogen bonding HSP parameter dH that differs from the HSP hydrogen bonding parameter of the reaction solvent by a value greater than about 10 MPa 0.5 and has a hydrogen bonding HSP parameter dH that differs by a value greater than about 10 MPa.

[0052] As used herein, the term "poor solvent" refers to a solvent that makes a solute, i.e., a dissolved substrate (e.g., metal-organic framework microcrystals and / or covalent organic framework microcrystals), less soluble or completely insoluble compared to a solvent that makes the solute soluble. The poor solvent is miscible with the reaction solvent. By adding a poor solvent to a solvent containing a solute, separation or precipitation of the solute from the solvent occurs, i.e., the poor solvent reduces the solubility of the solute in the solvent and separates the solute from the solvent as a solid precipitate or aggregate.

[0053] Preferably, the solvent removal step (ii) is one of the following: (a) a filtration step; (b) a sedimentation step; (c) a centrifugation step; (d) an evaporation step; and (e) any combination thereof, is carried out by at least one of.

[0054] Alternatively, or in addition thereto, step (a) is: i. contacting the metal-organic framework precursor material and / or the covalent organic framework precursor material (the framework precursor materials described herein) and optionally the reaction solvent together; ii. mixing and milling the metal-organic framework precursor material and / or the covalent organic framework precursor material together to form a reaction mixture, wherein the reaction mixture comprises metal-organic framework microcrystals and / or covalent organic framework microcrystals; iii. contacting the reaction mixture with a first solvent; iv. removing some, but not all, of the first solvent to form a mass of the wet structure; can be carried out by.

[0055] The reaction solvent can be the same as the first solvent. Alternatively, the reaction solvent can be different from the first solvent.

[0056] Preferably, the mixing and milling of the metal-organic framework precursor material and / or the covalent organic framework precursor material can be carried out in a mill, such as a ball mill using balls of, for example, steel, stone, or ceramic as the milling media. The mixing and milling steps are typically carried out using the solid precursor material, but this can also be carried out in the presence of a milling solvent, which can be removed before contacting the reaction mixture with the first solvent. Such methods are suitable for batch and continuous operations and provide an energy-efficient synthesis method.

[0057] After step ii. The reaction mixture can be passed through a washing and / or purification step to remove any impurities and / or unreacted precursor material.

[0058] Suitable milling and mixing conditions, such as speed, intensity, temperature, additives, reaction time, vary depending on the precursor material and the structure microcrystals, and such conditions are within the scope of those skilled in the art.

[0059] Preferably, the structure material is in particulate form during step (a). The structure material can be dispersed in a gel or slurry. More preferably, the structure material is in particulate form having an average primary particle size of less than about 900 nm.

[0060] Preferably, the structure material is in the form of microcrystals.

[0061] Preferably, the structural material has a small primary particle size, preferably a weight average particle size of from about 5 nm to about 900 nm, or from about 10 nm to about 800 nm, or from about 12 nm to about 700 nm, or from about 15 nm to about 500 nm. Small primary particles typically increase particle packing in the adsorbent, giving a higher bulk density. The method for measuring the particle size is described in more detail below. The particle size of the structural material is preferably measured once the material has been formed in the adsorbent. However, the particle size of the structural material can also be measured prior to step (a).

[0062] Particle size control of the structural material is considered important to ensure the formation of high-quality, high-density adsorbents. If the particles are too large, this can result in an adsorbent with a poor (low) density profile and / or poor robustness.

[0063] Step (a) can also be carried out by dispersing the pre-dried structural powder in a first solvent. Preferably, the structural powder is dispersed by a high-shear step. Suitable equipment includes high-shear mixing devices such as sonicators such as the IKA Ultra Turrax T25 or the Bandelin SONOPULS HD 2000. The pre-dried structural powder can also be dispersed in the first solvent by a wet milling step. Suitable equipment includes ball mills or roller mills. Typically, a high level of solvent (e.g., > about 70 wt%) and a high level of strong agitation are required to ensure good redispersion of the structural powder and to avoid problems associated with pre-drying the structural material.

[0064] Step (b) of forming a wet binder mass. Step (b) involves contacting a polymer binder with the wet structural mass to form a wet binder mass.

[0065] The polymer binder can be present in solution, or added as a solid (preferably as a fine powder), or as a slurry. Preferably, the polymer binder is added as a solution. The polymer binder is typically mixed with the wet structure, and the mixing is for a long time to ensure uniformity.

[0066] Step (c) of forming an undried binder mass. Step (c) partially dries the wet binder mass to form an undried binder mass (which is also referred to as a further dried binder mass, or a partially dried binder mass, or an intermediate partially dried binder mass). In other words, step (c) removes (e.g., evaporates) and / or captures (e.g., adsorbs onto an adsorbent material) at least a portion, but not all, of the first solvent from the wet binder mass to form the undried binder mass.

[0067] Step (c) can be implemented in several different ways. The wet binder mass can be further dried before cutting. This can potentially be carried out, for example, in a wiped film evaporator, and the resulting undried binder mass is subsequently cut to form small bodies. The wet binder mass can be left to dry on a flat surface to form an undried binder mass, which can then potentially be cut in a cutting mill or flaker or other suitable cutting equipment. Such a method is an example of removing (e.g., evaporating) at least a portion, but not all, of the first solvent from the wet binder mass to form the undried binder mass.

[0068] Another option is to add an additional adsorbent solid material that can adsorb some of the liberated first solvent. Such materials can be selected from fine activated carbon, or silica, or zeolite, or even some pre-dried structural material (if the level is not too high), and mixtures thereof. The structural powder may or may not be the same as that which forms the mass of the structure. Preferably the additional adsorbent material is selected from activated carbon, zeolites, organic structures, silica, and mixtures thereof. The additional adsorbent solid material can even be a polymer binder if a sufficient amount thereof is added in fine powder form. Considering that there is a limit to the amount of additional adsorbent solid material added, some limited additional porosity can be tolerated. Such a method is an example of capturing at least some, but not all, of the first solvent from the wet binder mass to form an undried binder mass, i.e., some of the first solvent binds, for example, to the additional adsorbent material.

[0069] A preferred option is to form an undried binder mass from the wet binder mass by combining evaporating the free solvent from the wet binder mass and adding a limited amount of additional adsorbent solid material. This can be done following different unit operations, for example, removing some of the liberated first solvent in a wiped film evaporator followed by adding the additional adsorbent solid material in a mixer or extruder.

[0070] Silicas suitable for use as additional adsorbent materials are precipitated silicas or fumed silicas, preferably fumed silica. Suitable fumed silicas include products such as the Aerosil product group provided by Evonik. Suitable precipitated silicas include products such as the Sipernat product group provided by Evonik.

[0071] Typically, the undried binder mass formed by reducing the free solvent level is 10 s before any cutting step -1and at 25 °C, > 4.0×10 5 It has a viscosity of mPa·s. The mass of the undried binder retains sufficient free solvent and can be deformed under pressure and impact, so it can be spheroidized, for example, in a spheronizer. Typically, the viscosity of the mass of the undried binder is -1 and at 25 °C is less than 1.25×10 6 mPa·s.

[0072] Step (d) of forming an undried adsorbent. Step (d) extrudes and / or cuts the mass of the undried binder to form an undried adsorbent. Preferably, step (d) extrudes and / or cuts the mass of the undried binder to form an undried adsorbent.

[0073] Step (e) of forming a dried adsorbent. Step (e) removes at least a portion of the first solvent from the undried adsorbent to form a dried adsorbent. Preferably, step (e) is carried out gradually, for example, at a temperature of less than about 80 °C or less than about 50 °C or less than about 40 °C, or even at ambient temperature.

[0074] Step (f) of forming a washed adsorbent. Step (f) contacts the dried adsorbent with a second solvent to form a washed adsorbent.

[0075] Step (g) of forming a non-activated adsorbent. Step (g) removes at least a portion of the second solvent from the washed adsorbent to form a non-activated adsorbent.

[0076] Step (h) Activation step. Step (h) activates the non-activated adsorbent by passing the non-activated adsorbent through a temperature greater than about 100 °C to form an adsorbent.

[0077] Optionally, steps (g) and (h) can be carried out simultaneously.

[0078] A mass of wet structure. The mass of wet structure is formed in step (a). The mass of wet structure comprises: (i) an organic structure; and (ii) a first solvent. Preferably, the structure comprises an organic structure selected from a metal-organic framework (MOF) and a covalent organic framework (COF). Most preferably, the mass of wet structure comprises a metal-organic framework. Preferably, the mass of wet structure is a mass of wet organic structure.

[0079] It may be preferable to pass the mass of wet structure through one or more steps of washing and re-concentration following initial formation. The first solvent may be the same as the reaction solvent or may be different depending on the washing step.

[0080] A structure. The structure is an organic structure. Most preferably, the structure is a metal-organic framework.

[0081] An organic structure. Preferably, the organic structure comprises a metal-organic framework (MOF), a covalent organic framework (COF), or a mixture thereof. Preferably, the organic structure is a metal-organic framework (MOF), a covalent organic framework (COF), or a mixture thereof. The organic structure can be made to comprise a mixture of two or more metal-organic frameworks (MOF) and / or two or more covalent organic frameworks (COF), or a combination thereof.

[0082] Preferably, the organic structure material is: (i) Zr-containing MOFs; (ii) Zeolite imidazolate structures and Zn-containing MOFs such as Zn-containing UTSA-16 and CALF-20; (iii) MOF-74 and its derivatives; (iv) Al-based MOFs; (v) Fe-based MOFs; (vi) M(F 6-x )L x Family of MOFs; (vii) Cu-based MOFs; (viii) Co-based metal-organic frameworks (MOFs) including Co-UTSA-16; (ix) Cr-based MOFs (x) Nb-based MOFs; (xi) Ni-based MOFs; (xii) Mn-based MOFs; (xiii) Mixed-metal MOFs; and (xiv) Combinations of any of these, which are one or more metal-organic frameworks (MOFs) selected from the group consisting of

[0083] Suitable Zr-containing MOFs include UiO-66, UiO-67, UiO-68, NU-1000, PCN-222, MOF-808, and Zr-fumarate, as well as their chemically functionalized derivatives.

[0084] Suitable ZIF monoliths include ZIF-7, ZIF-8, ZIF-67, ZIF-71, and ZIF-90.

[0085] Suitable derivatives of MOF-74s include Mn, Ni, Co, Cu, and Zn deformed forms.

[0086] Suitable Al-based MOFs include Al-fumarate, MIL-53, CAU-10, MIL-160(Al), and Al-soc-MOF-1.

[0087] Suitable Cr-based MOFs include MIL-100(Cr) and MIL-101(Cr).

[0088] M(F 6-x )L x Suitable MOFs of the family include SIFSIX-3-Ni, TIFSIX-3-Ni, NbOFFIVE-1-Ni and SIFSIX-2-Cu-i.

[0089] Suitable Cu-based MOFs include HKUST-1 and ROS-17.

[0090] Suitable Co-based MOFs include cobalt-based UTSA-16 and its derivatives.

[0091] Suitable Fe-based MOFs include MIL-100(Fe) and MIL-101(Fe).

[0092] Suitable mixed-metal MOFs include MOFs of a mixture system of two or more metals selected from Fe, Ti, and Zn.

[0093] Suitable MOFs can be those comprising mixed ligands or co-crystalline MOFs. In this case, the MOF comprises at least two chemically distinct organic ligands bonded to the same metal ion. This feature can be used to adjust the chemical behavior of the MOF.

[0094] The two chemically distinct organic ligands may preferably be chemical analogs. By chemical analogs, it is contemplated that not only the structural aspects of the ligand, specifically the portions involved in binding to the metal ion, but also the backbone are the same.

[0095] A particularly preferred feature is that the chemically distinct organic ligands are chemical analogs such that they have the same backbone structure but differ from each other due to functionalization of the backbone structure. The structural similarity of the binding of different organic ligand anions to the metal ion means that specific morphological forms of the MOF can be formed. If the dissimilarity of the organic ligands is too great, the MOF can be amorphous or full of defects.

[0096] For example, many MOFs have dicarboxylic acids as their organic ligands. Each carboxylic acid group is involved in binding to the metal ion. The backbone structure refers to the structure between two carboxylic acid bonding groups.

[0097] The dimensions of the backbone structure determine the dimensions of the pores formed by the organic ligands that bind to the metal ions. The chemical differences are derived from the functional pendant groups attached to the backbone structure.

[0098] Representative examples are shown below. In these cases, the backbone structure is (deprotonated) terephthalic acid (A).

[0099]

Chem.

[0100] Further representative examples are described below. Two representative chemical analogs are terephthalic acid (CAS 100-21-0) and 2-aminoterephthalic acid (CAS 10312-55-7). Other representative analogs of terephthalic acid include 2-bromoterephthalic acid (CAS 586-35-6), 2-nitroterephthalic acid (CAS 610-29-7), trimellitic acid (CAS 528-44-9), and 2-hydroxyterephthalic acid (CAS 636-94-2), among others.

[0101] The use of such chemical analogs makes it possible to produce specific MOFs with variable chemical properties. Also, it may be preferable for two chemically distinct organic ligands to comprise different backbone structures. The use of organic ligands with different backbone structures can enable the introduction of "defects" into a monolithic body with an incomplete MOF structure or allow for more complex MOF structures. Depending on the situation, these defects can increase the porosity.

[0102] Preferably, the molar ratio of the first organic ligand to the second organic ligand is greater than about 1:2. More preferably, the molar ratio of the first organic ligand to the second organic ligand is greater than about 1:3. Such ratios are effective in improving the physical and / or chemical properties of the body produced from such co-crystals.

[0103] An adsorbent comprising a mixture of structural materials can be prepared by mixing different structural materials together prior to adding a polymer binder.

[0104] A suitable MOF adsorbent can be made to include a mixture of MOF microcrystals produced using different ligands. For example, suitable UiO-66-based MOFs can be made to include a mixture of UiO-66 BDC and UiO-66 BDC-NH2.

[0105] COFs suitable for use with the present invention include imine-bonded COFs and / or hydrazone-bonded COFs, etc. Thus, the adsorbent can comprise an imine-bonded COF and / or a hydrazone-bonded COF.

[0106] Examples of imine-linked COFs include 3D-COOH-COF, 3D-COOH-COF, 3D-CuPor-COF, 3D-CuPor-COF-0P, 3D-OH-COF, 3D-Por-COF, 3D-Por-COF-0P, 3D-Py-COF, 3D-Py-COF-2P, 4PE-1P, 4PE-1P-oxi, 4PE-2P, 4PE-3P, 4PE-TT, BF-COF-1, BF-COF-2, BW-COF-AA, BW-COF-AB, CCOF-1, CCOF-2, CC-TAPH-COF, COF-112, COF-300, COF-320, COF-366-Co, COF-366-F4-Co, COF-366-F-Co, COF-366, COF-366-(Ome)2-Co, COF-505, COF-AA-H, COFBTA-PDA, COF-DL229, COF-LZU1, COF-SDU1, COF-TpAzo, CuP-Ph COF, CuP-TFPh COF, DAAQ-TFP COF, DABQ-TFP-COF, DAQ-TFP COF, DaTP, DhaTab, 2,3-DhaTab, 2,5-DhaTab, 2,3-DhaTph, 2,5-DhaTph, 2,3-DhaTta, 2,3-DmaTph, DMTA-TPB1 / 2’, DMTA-TPB1 / 3’, DMTA-TPB1 / 4’, DMTA-TPB1 / 5’, DMTA-TPB2, DMTA-TPB3, DMTA-TPB4, EB-COF:Br, EB-COF:Cl, EB-COF:F, EB-COF:I, FL-COF-1, HAT-COF, HAT-NTBA-COF, HBC-COF, HB-COF-AA, HB-COF-AB, HCC-H2P-COF, HO2C-H2P-COF, SIOC-COF-5, SIOC-COF-6, SIOC-COF-7, TAPB-BMTTPA-COF, TAPB-PDA COF, TAPB-TFP, TAPB-TFPB, Tb-DANT-COF, TBI-COF, TDFP-1, TEMPO-COF, TFB-COF, TfBD, TfpBDH, TH-COF-1, Thio-COF, TPA-COF-1, TPA-COF-2, TpBD, TpBD-2NO2, TP-BDDA-COF, TpBDH, TPBD-ME2, TPB-DMTP-COF, TpBD-NH2, TpBD-NHCOCH3, TpBD-NO2, TpBD-(OMe)2, TpBPy, TP-COF-BZ, TP-COF-DAB, Tp-DANT-COF, TPE-COF-I, TPE-COF-II, TPE-COF-III, TPE-COF-IV, TP-EDDA-COF, TpMA, TpPa-1, TpPa-2, TpPa-F4, TpPa-NO2, TpPa-Py, TpPa-SO3H, TpPa-SO3H-Py, Tp-Stb, TPT-COF-1, TPT-COF-2, TpTD, TpTG-Br, TpTG-Cl, TpTG-I, TpPa-1-F2, Tp-Ttba, TRIPTA, TTF-COF, TTF-Py-COF, TTI-COF, TzDa, Tp-Azo, HPB-COF, ILCOF-1-AA, ILCOF-1-AB, iPrTAPB-TFP, iPrTAPB-TFPB, LZU-301, LZU-301-sol, LZU-70, LZU-72, LZU-76, N3-COF, NN-TAPH-COF, NS-COF, NUS-10, NUS-14, NUS-15, NUS-9, HO-H2P-COF, OH-TAPH-COF, PC-COF, PI-2-COF, PI-3-COF, Por-COF, Py-1P COF, Py-1PF COF, Py-2,Examples include 2’-BPyPh-COF, Py-2,3-BPyPh-COF, Py-2,3-DHPh-COF, Py-2PE COF, Py-3PEBTD COF, Py-3PE COF, Py-An COF, Py-DHPh COF, PyTTA-BFBIm-iCOF, RT-COF-1, SA-COF, Salen-COF, SB-PORPy, SIOC-COF-3-AB, and SIOC-COF-4-AB, etc.

[0107] Examples of hydrazone-bonded COFs include COF-42-bnn, COF-42-gra, COF-43-bnn, COF-43-gra, COF-ASB, COF-LZU8, CPF-1, CPF-2, and TFPT-COF, etc.

[0108] Preferably, the COF can be any of those listed herein, or any combination thereof.

[0109] The first solvent and the reaction solvent. The first solvent describes the solvent or solvent mixture present in the wet mass of the structure. The first solvent can contain the residual amount of solvent from previous steps in the process in addition to the solvent added for washing or other purposes. Typically, the first solvent is not the same as the solvent used for the synthesis of the structure (reaction solvent). Instead, the first solvent can be the same as the reaction solvent. Since the reaction solvent is often difficult to handle, it is preferable if it can be washed away and replaced with the first solvent to simplify subsequent processing. Preferred first solvents include dimethyl sulfoxide (DMSO), polar aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMS), and N-methyl-2-pyrrolidone, low molecular weight alcohols including ethanol and methanol, water, acetone, organic acids such as acetic acid, and mixtures and combinations thereof, etc. Water is particularly preferred.

[0110] Polymer binder. Preferably, the polymer binder is polyvinyl alcohol (PVA), polyvinyl acetate, polyvinyl alcohol / acetate copolymer, polyimide, polyamide, polyvinyl pyrrolidone, polyacrylates including polyacrylic acid, polycarboxylates, polyethylene glycols, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), polylactic acid and its derivatives, or biopolymer-based materials such as polysaccharide gums including xanthan gum and guar gum, alginates, chitosan, etc., cellulose-based polymers such as cellulose, cellulose acetate, hydroxypropyl methylcellulose (HPMC), methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose phthalate (HPMCP), etc., and an organic polymer binder selected from any mixtures and combinations thereof. Preferred binder mixtures comprise PVA and a cellulose-based polymer, particularly hydroxyethylcellulose or methylcellulose.

[0111] Moist binder mass. The moist binder mass is formed in step (b). It may be preferred that the moist binder mass is formed from a dried structural material suitably dispersed in a first solvent. Typically, the moist binder mass will comprise less than about 30 wt.% solids content or less than about 25% solids content or less than about 20% solids content.

[0112] Undried binder mass. The undried binder mass is formed in step (c). The undried binder mass preferably comprises less than about 75% free solvent, or less than about 70% free solvent, or less than about 60% free solvent, or even less than about 50% free solvent. For any given adsorbent structure, the undried binder mass contains less free solvent than the moist binder mass.

[0113] Typically, it is important to control the rheology of the mass of the undried binder. The rheology of the mass of the undried binder is a complex combination of factors such as the structural particle size, the amount of the first solvent present, the nature of the organic polymer binder, and the presence of other materials. Typically, the mixture being cut needs to be sufficiently "solid" if they are to be cut successfully without being damaged.

[0114] In addition, a preferred option is that the formed body is passed through a spheronization step after cutting or breaking, for example, within a spheronizer. The spheronization of the formed body is preferred as a dust reduction step. However, for the extrudates to be spheronized, they need to be sufficiently deformable for this spheronization to occur. Typically, there is an optimal operating range for the rheology value of the mixture being cut. When water is used as the solvent, this means that there is an optimal moisture activity range.

[0115] One measure of how "solid" a material is its viscosity. Typically, therefore, it is important that the viscosity of the mass of the undried binder is within a certain range of limits.

[0116] Thus, the mass of the undried binder in the preferred method of the present invention typically has a viscosity at 10 s greater than about 3.0×10 5 mPa·s, or greater than about 4.0×10 5 mPa·s, or greater than about 5.0×10 5 mPa·s, or greater than about 6.0×10 5 mPa·s, or greater than about 7.0×10 5 mPa·s, or even greater than about 1.0 mPa·s×10 6 mPa·s. The preferred viscosity can be selected based on the nature and design of the cutting, as well as the subsequent processing steps. In the preferred method of the present invention, the mass of the undried binder typically has a viscosity less than about 3.0×10 -1 mPa·s, or about 2.0×10 6 mPa·s or less,6 less than mPa·s, or about 1.25×10 6 less than mPa·s, with a viscosity at 10 s -1 thereof.

[0117] Un-dried adsorbent. The un-dried adsorbent is formed in step (d).

[0118] Dried adsorbent. The dried adsorbent is formed in step (e).

[0119] Second solvent. Preferred second solvents include water and low molecular weight alcohols including ethanol and methanol. The second solvent can be one comprising a mixture of solvents. It is possible to use two or more types of second solvents in the washing step. Typically, the second solvent is not the same as the first solvent, or the reaction solvent, or any solvent used to form the polymer binder solution.

[0120] Washed adsorbent. The washed adsorbent is formed in step (f).

[0121] Un-activated adsorbent. The un-activated adsorbent is formed in step (g).

[0122] Adsorbent. The adsorbent comprises a structural material and a polymer binder. Typically, the adsorbent has a minimum internal dimension of less than about 10 mm. This can be measured by optical means, such as microscopy. Typically, the adsorbent has a bulk density greater than about 0.7 g / cm 3 thereof.

[0123] Hansen solubility parameter. The HSP values of most solvents can be found in standard reference tables, such as the CRC Handbook of Solubility Parameters and Other Cohesion Parameters (2 nd nd Edition).

[0124] A method for measuring viscosity. A device suitable for measuring the viscosity of a lump of undried binder is the Anton Paar MCR 92 Rheometer, which has a 25 mm diameter plate, a 25-degree angle cone, and is measured at 25 °C using a 3.0 mm gap. Place about 2 g of the sample on the plate, lower the upper cone to the target gap distance, remove the excess sample from the side, and measure the rotational viscosity. Typically, the viscosity is measured over a range up to a shear rate of 50 s -1 . For the purposes of this specification, the viscosity of the material is the viscosity measured at 10 s -1 .

[0125] A method for measuring water activity. The water activity of a material is defined as the fractional relative humidity of the atmosphere in equilibrium with that material, i.e., the ratio of the partial pressure of water vapor above the material to the partial pressure of water vapor above pure water at the same temperature. The term "Relative Humidity" (or RH) is used to describe water in the atmosphere or gas phase in equilibrium with a solid and is expressed as a percentage, with the relative humidity of pure water in a closed system being 100%. Thus, for any material, the water activity value (aw) is defined as %RH / 100.

[0126] Suitable devices include, for example, the probe HC2-AW connected to the Hygrolab C1 display unit, both of which are manufactured by Rotronic Measurement Solutions. It is desirable to set up the device appropriately and operate it according to the manufacturer's instructions. The RH of the material is determined by placing a sample of the material inside the measurement chamber of the HC2-AW, ensuring that the sample fills a volume greater than 1 / 4 of the available volume, sealing the chamber, and leaving it to reach equilibrium as indicated on the display.

[0127] Unless otherwise specified, the water activity measurement is carried out at 25 °C.

[0128] A method for evaluating the particle size distribution of particles in an adsorbent by SAXS. The particle size distribution of the particle adsorbent forming the adsorbent can be evaluated by SAXS. In principle, in a SAXS experiment, light is scattered as a result of the contrast in electron density between two phases. Based on this, the size of equivalent spherical particles, or other shapes, can be calculated. The SAXS intensity at a specific angle depends on the electron density contrast. This also depends on the size of the particles. Large particles cause scattering at low angles, and small particles cause scattering at much larger angles. To generate measurement results, a piece of adsorbent material is placed on a sample holder. For SAXS, X-rays are generated by synchrotron radiation. One or more sets of data are collected over the entire range of scattering angles as the target range. Using a Kratky instrument, small-angle scattering at large scattering angles (from 1e-1 to 4e-0 degrees) can be collected. Using a Bonse Hart instrument, small-angle scattering at even smaller scattering angles (from 2.2e-3 to 5e-1 degrees) can be collected. In this case, after background removal, two data sets are combined into a single scan and the data is subsequently sharpened. These sharpened data are then converted into a volume size distribution function by a regularization method. The volume distribution function is the final output of this procedure.

[0129] Measurement of the particle size of structural microcrystals. The particle size distribution of structural microcrystals can be measured by dynamic light scattering method if in a reaction mixture. Suitable instruments include NANO-flex II manufactured by Colloid Metrix, which is operated according to the manufacturer's instructions. The sample probe can be inserted directly into the reaction mixture. Dilution of the reaction mixture is usually not necessary.

[0130] Embodiments of the present invention. The following are embodiments of the present invention.

[0131] 1. (a) A step of forming a mass of a wet structure, wherein the mass of the wet structure is: (i) an organic structure and; (ii) a first solvent between 50 wt% and 95 wt%, and comprising, preferably, an organic structure comprising a metal organic framework (MOF), a covalent organic framework (COF), or a mixture thereof; (b) contacting a mass of the moist structure with a polymer binder to form a mass of the moist binder; (c) partially drying, preferably removing, at least a part but not all of the first solvent from the mass of the moist binder to form a mass of the undried binder; (d) extruding and / or cutting the mass of the undried binder to form an undried adsorbent; (e) removing at least a part of the first solvent from the undried adsorbent to form a dried adsorbent; (f) contacting the dried adsorbent with a second solvent to form a washed adsorbent; (g) removing at least a part of the second solvent from the washed adsorbent to form an unactivated adsorbent; (h) activating the unactivated adsorbent by passing the unactivated adsorbent through a temperature greater than 100 °C to form an adsorbent, A method for manufacturing an adsorbent, comprising.

[0132] 2. Step (a) is: (i) (a) a metal organic framework precursor material and / or a covalent organic framework precursor material; and (b) a reaction solvent, contacting them together to form a dilute reaction mixture, wherein the dilute reaction mixture: (a) comprises metal organic framework microcrystals and / or covalent organic framework microcrystals; and (b) a reaction solvent; (ii) removing the reaction solvent from the dilute reaction mixture; (iii) contacting the concentrated reaction mixture with a first solvent; (iv) removing some, but not all, of the first solvent to form a mass of the wet structure; The process according to embodiment 1, carried out by.

[0133] 3. The process according to embodiment 2, wherein the metal-organic framework microcrystals and / or covalently organic framework microcrystals in the dilute reaction mixture aggregate into larger secondary particles prior to the removal of the reaction solvent.

[0134] 4. The agglomeration step is as follows: (a) adding a poor solvent; (b) adding a polymer agglomeration aid containing a polymer used as a binder; and / or (c) applying high-frequency ultrasonic waves, The process according to embodiment 3, carried out by at least one of.

[0135] 5. The poor solvent is miscible with the reaction solvent and has a hydrogen bonding HSP parameter dH that is more than 10 MPa different from the HSP hydrogen bonding parameter of the first solvent 0.5 The process according to embodiment 4.

[0136] 6. The solvent removal step (ii) is as follows: (a) a filtration step; (b) a sedimentation step; (c) a centrifugation step; (d) an evaporation step; and (e) any combination thereof, The process according to any one of embodiments 2 to 5, carried out by at least one of.

[0137] 7. The process according to any one of embodiments 1 to 6, wherein the mass of the wet structure is passed through a roller milling process.

[0138] 8. Step (a) is: i. contacting a metal-organic framework precursor material and / or a covalent organic framework precursor material (precursor materials described herein) with an optional reaction solvent; ii. mixing and milling together a metal-organic framework precursor material and / or a covalent organic framework precursor material to form a reaction mixture, wherein the reaction mixture comprises metal-organic framework microcrystals and / or covalent organic framework microcrystals; iii. contacting the reaction mixture with a first solvent; iv. removing some but not all of the first solvent to form a wet structure mass; The process according to Embodiment 1, which is carried out by the above.

[0139] 9. The process according to any one of Embodiments 1 to 8, wherein the organic polymer binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyimide (PI), polyvinylpyrrolidone, polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, chitosan, celluloses including cellulose acetate, hydroxypropylmethylcellulose (HPMC), methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose phthalate (HPMCP), and any combination thereof.

[0140] 10. The metal-organic framework (MOF) is: (i) Zr-containing MOFs; (ii) Zn-containing MOFs; (iii) MOF-74 and its derivatives; (iv) Al-based MOFs; (v) Fe-based MOFs; (vi) MOFs of the M(F 6-x )L x family. (vii) Cu-based MOFs; (viii) Co-based MOFs; (ix) Cr-based MOFs; (x) Nb-based MOFs; (xi) Ni-based MOFs; (xii) Mn-based MOFs; (xiii) Mixed-metal MOFs; and (xiv) Any combination thereof, The process according to any one of Embodiments 1 to 9, selected from.

[0141] 11. Step (c) is the following: (i) Evaporating the solvent; and / or (ii) Adding additional adsorbent powder to the wet binder material, wherein the adsorbent powder is selected from silica, zeolite, activated carbon, graphene, metal-organic frameworks, covalent organic frameworks, and combinations thereof, The process according to any one of Embodiments 1 to 10, carried out by at least one of.

[0142] 12. The mass of the undried binder formed in step (c) is between 3.0×10 5 mPa·s and 3.0×10 6 mPa·s, having a viscosity at 10 s -1 and 25 °C, the process according to any one of Embodiments 1 to 11.

[0143] 13. The first solvent is water, and the mass of the undried binder has a water activity between 0.5 and 0.9, or between 0.55 and 0.85, or even between 0.6 and 0.8, the process according to any one of Embodiments 1 to 12.

[0144] 14. The adsorbent is: (i) More than 50 wt% metal-organic framework material and / or covalent organic framework material; and (ii) Less than 20 wt% polymer binder, The process according to any one of Embodiments 1 to 13, comprising

[0145] 15. The process according to any one of Embodiments 1 to 14, wherein the metal-organic framework is selected from NbOFFIVE-1-Ni and the polymeric organic binder is selected from polyvinyl alcohol and methyl cellulose.

[0146] 16. The process according to any one of Embodiments 1 to 15, wherein the undried adsorbent is spheronized.

[0147] All references referred to herein are incorporated herein in their entirety as if each reference's entire content were set forth herein in full.

[0148] While specific examples and / or embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications within the scope of the present invention be covered by the scope of the appended claims.

Examples

[0149] A 1-liter reaction mixture comprising microcrystalline MOF (UiO-66-NH2) having an average particle size of less than 900 nm was prepared by dispersing it in a reaction solvent comprising water and a solids content of 10%.

[0150] The sample was divided into four equal aliquots, and each aliquot was centrifuged in a Jeol JR15 at 5250 g for 15 minutes.

[0151] When the supernatant was poured out and removed from each sample flask, a thick wet layer remained at the bottom of the flask. Subsequently, 250 g of methanol was added to each flask, and the sample was strongly stirred to redisperse and wash the microcrystals.

[0152] Subsequently, the flask was centrifuged again at 5250 g for 40 minutes to form a thick solid layer (a mass of the wet structure) comprising MOF, methanol, and any residual reactants / solvents from the reaction mixture. The solid layer was analyzed to have a solids content of 27.5%.

[0153] Subsequently, 280 g of the wet structure was mixed with 280 g of a 2.6 wt% aqueous solution of methyl cellulose to form a mass of the wet binder. This had a solids level of 14.9%, 10 s -1 and a viscosity of 2.54×10 4 mPa·s at 25 °C, and a water activity of 0.95.

[0154] Warm air from a hair dryer was applied to the stirred mixture, and the mass of the wet binder was stirred in a Kenwood kitchen stand mixer to reduce the level of the first solvent (in this case a mixture of water and methanol). This was carried out for 50 minutes to obtain a mass of the undried binder having a solids content of 27.9%. The material was a very thick, but still sticky, paste.

[0155] 0.5 g of Sipernat 22S silica was mixed into 150 g of the above undried binder mass. This gave a further solid material. The solids content of the material was 29.8%, 10 s -1 and a viscosity of 5.8×10 5 mPa·s at 25 °C, and a water activity of 0.81.

[0156] Subsequently, the mass of the undried binder was extruded through a hand spaghetti maker. The extrudate could be easily extruded without sticking to each other and could be easily cut. Samples of the extrudate were cut manually to a length of 5 mm, and the cut extrudates were manually spheronized to form approximately spherical beads (undried adsorbents).

[0157] Subsequently, the undried adsorbent was left to dry further for 24 hours under ambient conditions (21 °C) to form hard, robust beads (dried adsorbent) having a solids content of 77% and a water activity of 0.4.

[0158] Subsequently, 1.2 g of the beads were placed in 100 ml of methanol (second solvent) for 48 hours. Subsequently, the methanol was exchanged and the adsorbent was left for a further 48 hours. The washed beads (washed adsorbent) were removed from the methanol and left to dry under ambient conditions. The washed and dried beads (unactivated adsorbent) were subsequently activated by heating at 105 °C in a vacuum furnace for 12 hours to obtain the final adsorbent. The activated beads had a BET surface area of 1050 m 2 / g.

Claims

1. (a) A step of forming a mass of a wet structure, wherein the mass of the wet structure is: (i) an organic structure; (ii) A step comprising a first solvent between 50 wt% and 95 wt%; (b) The step of bringing the mass of the wet structure into contact with a polymer binder to form a mass of the wet binder; (c) The step of partially drying the wet mass of binder to form a mass of undried binder; (d) The step of extruding and / or cutting the undried mass of binder to form an undried adsorbent; (e) The step of removing at least a portion of the remaining first solvent from the undried adsorbent to form a dried adsorbent; (f) The step of bringing the dried adsorbent into contact with a second solvent to form a washed adsorbent; (g) The step of removing at least a portion of the second solvent from the washed adsorbent to form an inactivated adsorbent; (h) A step of activating the inactive adsorbent by passing it through a temperature greater than 100°C to form an adsorbent, A method for producing an adsorbent comprising [a certain substance].

2. Step (a) is: (i) (a) Metal-organic structural precursor material and / or covalent organic structural precursor material; (b) Reaction solvent and Bring them into contact together, To form a dilute reaction mixture, wherein the dilute reaction mixture is: (a) with metal-organic structure microcrystals and / or covalent organic structure microcrystals; (b) comprising a reaction solvent; (ii) Removing the reaction solvent from the dilute reaction mixture; (iii) Contacting the concentrated reaction mixture first with the solvent; (iv) Removing some, but not all, of the first solvent to form a mass of wet structure, The method according to claim 1, as performed by...

3. The method according to claim 2, wherein the metal-organic structure microcrystals and / or covalent organic structure microcrystals in the dilute reaction mixture aggregate into larger secondary particles prior to the removal of the reaction solvent.

4. The aforementioned aggregation step is as follows: (a) Adding a poor solvent; (b) Adding a polymer flocculant containing a polymer used as a binder; and / or (c) Applying high-frequency ultrasound, The method according to claim 3, which is carried out by at least one of the following.

5. The poor solvent is miscible with the reaction solvent, and its HSP hydrogen bonding parameter is 10 MPa compared to the first solvent. ０．５ The method according to claim 4, having a more significantly different hydrogen bond HSP parameter dH.

6. Steps (ii) and (iv), or either or both, are as follows: (a) Filtration step; (b) Settlement step; (c) Centrifugal separation step; (d) Evaporation step; and (e) Any combination of those, The method according to claim 2, which is carried out by at least one of the following.

7. The method according to claim 1, wherein the mass of the moist structure is formed by dispersing a pre-dried structural material in a first solvent.

8. Step (a) is: i. Bringing a metal-organic structure precursor material and / or a covalent organic structure precursor material into contact with a reaction solvent as desired; ii. Mixing and crushing the metal-organic structure precursor material and / or covalent organic structure precursor material together to form a reaction mixture; wherein the reaction mixture comprises the metal-organic structure microcrystals and / or covalent organic structure microcrystals; iii. Contacting the solvent of the first reaction mixture; iv. Removing some, but not all, of the first solvent to form a mass of wet structures, The method according to claim 1, as performed by...

9. The method according to any one of claims 1 to 8, wherein the polymer binder is an organic polymer binder selected from polyvinyl alcohol (PVA), polyvinyl acetate, polyvinyl alcohol / acetate copolymer, polyimide, polyamide, polyvinylpyrrolidone, polyacrylates including polyacrylic acid, polycarboxylates, polyethylene glycols, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), polylactic acid and its derivatives, or biopolymer materials such as polysaccharide gum including xanthan gum, guar gum, arginate, and chitosan, or cellulosic polymers such as cellulose, cellulose acetate, hydroxypropyl methylcellulose (HPMC), methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any mixtures and combinations thereof.

10. The aforementioned metal-organic structure (MOF) is: (i) Zr-containing MOFs; (ii) Zn-containing MOFs; (iii) MOF-74 and its derivatives; (iv) Al-based MOFs; (v) Fe-based MOFs; (vi) M(F ６－ｘ ) L ｘ MOF family; (vii) Cu-based MOFs; (viii) Co-based MOFs; (ix) Cr-based MOFs; (x) Nb-based MOFs; (xi) Ni-based MOFs; (xii) Mn-based MOFs; (xiiii) Mixed metal MOFs; and (xiv) Any combination of those, The method according to any one of claims 1 to 8, selected from the following.

11. Step (c) is as follows: (i) Evaporating the solvent; and / or (ii) Adding further adsorbent solid material to a mass of moist binder, wherein the further adsorbent solid material is selected from silica, zeolite, activated carbon, graphene, metal-organic structures, covalent organic structures, and combinations thereof. The method according to any one of claims 1 to 8, carried out by at least one of the following.

12. The undried mass of binder formed in step (c) is 3.0 × 10 ５ mPa. s and 3.0 × 10⁻⁶ ６ 10s between mPa.s －１ The method according to any one of claims 1 to 8, having a viscosity at 25°C.

13. The method according to any one of claims 1 to 8, wherein the first solvent comprises water, and the undried mass of binder has a water activity between 0.5 and 0.

9.

14. The adsorbent body: (i) more than 50 wt% of metal-organic structural material and / or covalent organic structural material; (ii) A polymer binder of less than 20 wt%, The method according to any one of claims 1 to 8, comprising:

15. The method according to any one of claims 1 to 8, wherein the undried adsorbent is subjected to a spheroidizing treatment.