A process for the production of an adsorbent body

Abstract

The present invention relates to a process for the production of an adsorbent body(ies) comprising a framework and a binder.

Description

A process for the production of an adsorbent bodyField of the invention

[0001] The present invention relates to industrially relevant processes for making an adsorbent body, said adsorbent body per se, and uses for said adsorbent body. The adsorbent body comprises metal-organic framework or frameworks and is suitable for use in gas storage and purification systems, particularly industrial systems. The inventive process simplifies the production of high performance adsorbent body(ies).Background of the invention

[0002] The present invention provides industrially relevant production of robust adsorbent bodies comprising metal-organic frameworks (MOFs). The term “industrially relevant” refers to processes that may be capable of producing large (for example, multi-kilo) quantities of adsorbent bodies per day using equipment which is cost-effective and readily available. Labbased making protocols and procedures using e.g., beakers and test tubes making gram quantity samples are typically not industrially relevant, even if they produce materials of very high quality.

[0003] Metal-organic frameworks (MOFs) are a relatively new class of porous, crystalline materials formed by the reaction of metal ion species with organic ligand molecules by coordination chemistry. MOFs typically have exceptionally high surface areas. The ability to adapt or change the pore sizes and chemistry of the MOF means that many MOFs can be modified to be selective to adsorption of specific species. MOFs are typically made by sol-gel synthesis techniques resulting in fine powders. The MOFs are typically separated from the reaction mix, usually by centrifugation or sometimes filtering, followed by washing, recentrifugation or filtering and finally drying. This typically forms a powder. To be useful in industrial processes, the resulting MOF powders typically need to be formed into a larger body(ies) to avoid problems such as compaction and channelling, which may reduce fluid flow and performance. These larger bodies typically need to be mechanically robust and attrition and abrasion resistant to be industrially useful.

[0004] Many industrial processes exist to form fine powders into larger bodies, such as tablets, extrudates, granules and coating layers, that is a coating layered onto a substrate. For example, extrudates are typically formed by mixing MOF with a binder and plasticiser and extruding the plasticised mix through an orifice. However, these processes may very oftenreduce the sorbent properties of the adsorbent material. The application of high pressures, e.g., as often used in tabletting processes, can destroy the internal pores of the adsorbent material. This is especially relevant for MOFs that have coordination chemistry bonds and are typically less robust. Achieving a high-density MOF adsorbent body using high mechanical pressure may be counterproductive if doing so causes significant collapse of the internal pores of the adsorbent material.

[0005] An alternative process to tabletting, extrusion or granulation for forming a MOF body is preparing a coating layer comprising MOF and binder on a substrate. However, the use of a binder can cause other problems and is not straightforward. High levels of particulate binder(s), such as alumina, may impair the performance of the adsorbent body by reducing the amount of adsorbent material in the body. Additionally or alternatively, high levels of binder(s) applied as solutions or liquids may block the pores of the adsorbent material and reduce sorbent performance. However, the mechanical robustness of adsorbent bodies, such as their resistance to attrition and abrasion, is typically insufficient if very low levels of binder are used.

[0006] An ideal adsorbent body may be one that combines high sorbent properties (usually measured by BET area and N2adsorption isotherms) and physical robustness, such as resistance to attrition or abrasion. It may also be industrially preferable if the adsorbent body combines high density with high surface area and good sorbent performance. High density means allow for a lower volume of adsorbent body to be needed for a given process requirement, as compared to a low-density body. This can have very significant industrial advantages such as smaller and lighter (hence cheaper) equipment. These product requirements are typically regarded as being mutually contradictory. High surface area adsorbent bodies are typically associated with lower densities.

[0007] Whether or not the internal pores of a MOF in an adsorbent body have been collapsed during processing is typically indicated by the relative density of the resultant MOF body. The relative density is defined as the envelope density of the MOF body divided by the crystal density of the MOF. The crystal density of the MOF is the theoretical density of a single MOF crystal. Crystal densities have been calculated for many MOFs and are available from the Cambridge Structural Database at the Cambridge Crystallographic Data Centre.

[0008] Each MOF has a specific crystal density depending on their structure. If the envelope density of an adsorbent body is greater than the crystal density (i.e., the relative density is > 1), then this is likely due to the collapse of internal pores. The greater the relative density isabove 1 , the more the internal pores will have been collapsed and the lower the sorption capacity. Limiting high relative density is necessary to avoid inefficient internal pore collapse. However, the relative density of an adsorbent body should typically not be much less than 1 as this would be volumetrically inefficient. Very low relative densities typically indicate excessive levels of undesirable larger macro-pores.

[0009] Throughout this application, the IUPAC definitions of micropores (diameter of < 2 nm), meso-pores (diameter of 2 nm - 50 nm) and macropores (diameter of > 50 nm) are used.

[0010] The envelope density of a body can be measured by dividing the weight of a body (in grams) by its envelope volume (in cm3). The envelope volume is defined in ASTM D3766 as “the ratio of the mass of a particle to the sum of the volumes of the solid in each piece and the voids within each piece, that is, within close-fitting imaginary envelopes completely surrounding each piece". The envelope density of a body can be measured as described later.

[0011] The ideal adsorbent body may be one that simultaneously meets what can appear to be contradictory requirements. The ideal adsorbent body should preferably be robust and attrition or abrasion resistant. It should preferably have a high surface area to have a good sorption capability. The adsorbent body ideally needs to have a high density to minimise the volume of material required for a given process whether for tablets, extrudates, granules or coating on a substrate. These requirements can often seem incompatible.

[0012] The adsorbent bodies preferably also need to be simple and environmentally friendly to make. A major factor in whether a process is industrially relevant or not is the amount and nature of solvents used in the synthesis of MOFs. Many of the synthesis routes published in the art are sol-gel processes and use high levels of reaction solvents such as DMF. This is highly problematic on a larger scale. Such solvents can be handled in a lab environment but would be very difficult to handle in the quantities need for large-scale production. As mentioned previously, MOFs reaction mixes are typically centrifuged to separate the MOF from the reaction solvent and then washed further with a washing solvent in combination with further centrifugation steps resulting in a complex process. A further problem comes from the use of solvents when adding binders. Many binders, such as organic polymers, are more effective when added as solutions or dispersions but this introduces additional solvent into the process.

[0013] Processes that enable the production of high-performance adsorbent bodies without requiring high levels of solvent are highly advantageous. It is also highly preferable if thesolvents are less environmentally harmful or easy to recycle. Water and low chain length (C1 to C4) alcohols are preferred with water being especially preferred.

[0014] Typically, MOFs are synthesised by mixing and contacting MOF precursor species in high levels of solvents. Reducing the amount of solvent in a typical MOF reaction mix almost invariably reduces the yield of the reaction. This is typically due to the reduced contact between the reactants e.g., by one of the precursors being present in non-solubilised solid form. This typically results in unreacted materials in the reaction that need to be removed from the MOF mix, e.g., by washing. Not doing so results in reduced sorbent performance. Typically this washing is done by re-dispersing the MOF in washing solvent and centrifuging the dispersion to separate solid from liquid, often repeated multiple times. Separating the solid MOF from the suspension, for example by centrifuging or filtering etc., is usually complex, expensive and time consuming, especially on a large scale. Hence processes that enable an easier washing and purification of MOF are of industrial benefit. Processes that reduce the amount of solvents used in synthesising MOFs bodies are also of interest.

[0015] The inventors have also observed that removal of high levels of solvent from adsorbent bodies or gels during processing can introduce unwanted levels of macro-porosity into the resulting bodies or can result in the bodies cracking or even forming powders. Without wishing to be bound by theory, this is believed to be due to the reduction in volume of solvated polymeric binders that can happen during drying. This is especially true with polymeric organic binders which are often added as solutions. As they dry, such binders form progressively thicker gels. During the drying, the volume of these gels decreases as solvent evaporates. The reduction in volume of the binder can leave voids in the body, especially if faster drying rates are used, such as at higher temperatures. Removal of solvents is typically best done at lower temperatures, such as less than about 50 °C or less than about 40 °C or even at ambient temperature.Process Routes for Forming Adsorbent Bodies

[0016] For clarity, the term “adsorbent body” or “adsorbent bodies” used herein describes a body or bodies, such as an extrudate, tablet, granule or coating layer (the coating layer may be present as a coating layer on a substrate), wherein the majority of the body (i.e., > about 70 wt%) comprises one or more MOF. One approach described in the art to prepare adsorbent bodies is to mix MOF with a binder and / or plasticiser / liquid to form a paste / soft solid and then to extrude the material to form an extrudate, followed by removal of the plasticiser / liquid to harden the extrudate or coating, for example. The use of pre-dried MOF powder can havesome disadvantages such as the introduction of unwanted levels of meso- and macroporosity. Extrusion is a mechanically simple and widespread process and is an attractive production method. Coating, for example by spraying, spreading, painting or dip-coating is also a simple and robust production method for forming MOF bodies in the form of thin layers or coatings on a substrate(s).

[0017] For an extrusion, coating or any MOF body-making, process to be industrially relevant, it preferably has to be able to make handleable bodies at industrially relevant rates using extant equipment. Most of the published art on the extrusion (or other body formation steps) of MOFs describes work that has been done on a small scale, for example in a laboratory.. Mixes of pastes / soft solids or blends containing adsorbent powder plus a plasticiser / lubricant liquid are typically made into single extrudate strands which are allowed to dry and are then cut up. The required physical properties of the mix being extruded or otherwise formed into small bodies to enable industrially relevant processing at scale are not described in the art. However, successful post-extrusion or general post-production handling of the formed small bodies is crucial to any larger-scale production rate.

[0018] For extrusion processes, the extruded strands typically need to be broken or cut into smaller lengths (“extrudates”) for use in industrially relevant processes. This can be done by mechanical cutting or by relying on the breakage of longer extrudates during extrusion and subsequent handling. Extrudates are often formed by the mechanical cutting of the extrudate strands using a die face-cutter. The extrudates can be cut by a rotating blade moving across the surface of the die-plate. This means that the extrudates can be cut to controlled lengths, which can be controlled by the rotational speed of the cutter tool and design of the die.

[0019] For an extrudate-cutting process, or any body-forming process based on cutting, to work, the material preferably should not stick to any blade used to cut the material. If significant amounts of material do stick to the cutting tool, this will rapidly result in the build-up of material on the cutting tool resulting in the production of large masses of material rather than discrete extrudates or bodies.

[0020] The inventors have now developed a simplified process for the production of adsorbent bodies (MOF bodies). The inventive process includes significant reductions in the amounts of solvent used in the synthesis of the MOF. If required, the optional washing step to remove unreacted materials and other by-products from the MOF is made much simpler. This optional washing step typically makes it easier to remove unreacted materials from the MOF mix and means it is practical to synthesize MOF using lower levels of reaction solvent even if thisresults in a lower reaction yield. The unreacted reactants are typically recycled. Virtually any MOF-forming reaction will inherently result in some residual unreacted material. The easier removal of residual unreacted material facilitated by the inventive process makes the levels of unreacted precursors of less practical concern.

[0021] The inventors have developed the inventive process disclosed herein which removes unreacted materials and other contaminants from the absorbent body preparation process in a much simpler manner.

[0022] Typically, MOF bodies are formed, in a known method, by a sequential process of (i) synthesising MOF in a reaction mix, (ii) concentrating the MOF by centrifuging / filtration, (iii) washing the MOF, (iv) concentrating the MOF, (v) adding binder to the MOF, (vi) forming a MOF body, and (vii) drying the MOF body.

[0023] Typically step (iv) includes drying the MOF to form a powder prior to subsequent processing steps. Note that some processes described in the art describe forming MOF bodies from pre-formed MOF powder, meaning that steps (i) to (iv) have been carried out separately to steps (v) to (vii).

[0024] The inventors have now found that the washing step (iii) can be done after forming and drying the MOF body. Binder can be added directly to the MOF reaction mix and the mixture then formed and dried to form a dried MOF body. Without wishing to be bound by theory, it is believed that washing a dried MOF body may be much simpler than washing a concentrated MOF gel or slurry prior to forming a MOF body due to the much larger size of the MOF body compared to the MOF particles. The MOF body can simply be immersed in washing solvent and easily removed - e.g., by lifting / scooping, decanting or filtration. It is believed that this is typically much more viable - especially on a large scale - than, for example, dispersing a centrifuged MOF mix in washing solvent and re-centrifuging the suspension. It is surprising that dried MOF bodies can still be successfully washed of contaminants and unreacted materials despite the reduced contact between the MOF body and washing solvent (compared to the contact between MOF and washing solvent in a gel or slurry) and the compact, dense packing of MOF crystallites and binder within the MOF body. The inventors have seen that extended contact with washing solvent- for example greater than 1 day or 2 days or even a week - may be required. The binder system typically needs to be highly robust to withstand this extended washing. Limiting the dimensions of the MOF body to limit the maximum distance between any internal point of the MOF body and an external surface may be beneficial. If the MOF body is a coating layer, the limited depth of such an adsorbent body inthe form of a coating layer makes washing easier as dissolved materials have less distance to migrate through the MOF body.

[0025] Ideally, the washing step should leave sufficient binder that the MOF body and ultimately the adsorbent body is robust and retains high attrition and abrasion resistance. A particularly preferred approach may be to use a thermally activated cross-linking binder. The MOF reaction mix and binder is dried, typically for at least one hour or even much longer, at a low temperature to gradually remove the solvent without causing excessive porosity. The initially dried MOF body is then dried at a higher temperature for an extended period such greater than one hour to cause the binder to cross-link and form a more coherent and robust binder material. The MOF body is then washed in washing solvent and the cross-linked MOF material maintains its robustness during the washing process.

[0026] The inventors have observed that optimised MOF bodies may be formed when the MOF crystallites are kept dispersed, and preferably of small size, before forming the body. This may be achieved by forming the adsorbent bodies directly from the MOF reaction mix.

[0027] Without wishing to be bound by theory, any pre-drying step (such as spray-drying) which forms the MOF crystallites into powders comprising discrete particles or granules may inherently create significant levels of macro and meso-porosity in the larger dried aggregated particles of the powder. For example, it is believed that the rapid removal of solvent involved in many drying processes may create larger pores or in-homogeneously hard regions. These MOF powders, even when subjected to a size reduction step, may then introduce unwanted levels of meso and macro-porosity into MOF adsorbent bodies formed from them, thus reducing the volumetric performance of the MOF adsorbent body. High pressures may be used in an extrusion step to partially “squeeze out” at least part of this unwanted porosity but this can then collapse the internal pores of many MOFs.

[0028] Instead, without wishing to be bound by theory, it may be better if the MOF crystallites are kept in the reaction mix (reaction mass) before being mixed with binder and formed into larger bodies. However, this may make the issue of processing the mixes more challenging if the level of solvent is high. It may be especially beneficial for industrially relevant processing for the level of solvent in the reaction mix to be as low as possible whilst still ensuring acceptable % yields. The inventors have observed that acceptable yields may require a certain amount of solvent and that the % yield of the MOF in the reaction mix (MOF reaction mass) can drop significantly with very low levels of solvent, such as less than about 10wt%. Thus itmay be necessary to optimise the contradictory requirements of minimising solvent level for process simplification and maximising the resulting % yield.

[0029] The inventors have discovered that an optimised process may be achieved by forming MOF crystallites in a reaction mass which may be at least partially based on solid precursors rather than solutions but having enough solvent to obtain adequate yields, adding binder to the reaction mass, forming it into bodies either by coating or extrusion, optionally with partial drying, followed by optionally washing to remove unreacted materials. This combines process simplicity and viability with MOF quality and performance.

[0030] The bodies, e.g., extrudates or granules formed by cutting, should not stick to each other or equipment sides immediately after cutting or breaking. This is often a major problem with extrusion cutting processes due to the concentration of extrudes in a small space leading to frequent extrudate:extrudate impacts. If the extrudates or bodies are too soft and / or sticky, they can stick to each other after extrudate:extrudate impact or processes which rely on mechanical breakage of the extrudate strands, such as extrusion-spheronisation, just do not work.

[0031] The issue of not having deformable material sticking to a cutting blade applies to material in other forms apart from extrudates, such as flakes, slabs, tablets or other larger bodies. Extrudates are a convenient form of body but being able to cut or otherwise break other larger bodies, such as larger “slabs” formed by tray-drying or large flat tablets, into smaller bodies by the use of e.g., a flaker or other cutting tool is also of industrial relevance. The formation of smaller bodies can be followed by further process steps such as rounding in a spheroniser and / or further controlled drying.

[0032] Thus, it can be seen that successful, large-scale production of adsorbent bodies by extrusion, or other particle-forming process, requires the mix being processed to have specific physical properties. Any mix cannot be too soft when being cut or broken else it will stick either to itself or to the sides of equipment or to the cutting tools, rapidly leading to the process not being viable. If the mix is too hard, then the high pressures required to extrude the mixture, or otherwise form the bodies, may damage the porosity of the MOF and / or generally make particles too hard to easily spheronise or generate excessive amounts of fines in any milling step.

[0033] The use of a binder is typically required to provide sufficient robustness to an adsorbent body comprising MOF. Binders described in the art often comprise inorganic particles - suchas hydrated alumina. Such inorganic particulate binders need to be used at relatively high levels (such as 30 wt %) to be effective and rely on particle:particle interlocking to provide robustness. The high levels of such binders inherently dilute the volumetric performance of such adsorbent bodies due to the replacement of framework material by binder. However, such particulate binders do not block the pores of the framework material.

[0034] Most of the art describes processes wherein pre-formed and dried MOF powder (often a spray-dried powder) is mixed with a binder and a plasticiser / lubricant and then extruded. The MOF powder can also be optionally milled prior to being mixed with the binder and plasticiser and extruded. Other known processes spray-dry a mixture of MOF powder and inorganic binder and then extrude the spray-dried granules to simplify processing. This however is likely to introduce unwanted porosity.

[0035] The inventors have found that optimised MOF adsorbent bodies can be formed in an industrially relevant process, as described herein, when a wet MOF reaction mass or wet MOF mass (such as described above) is combined with a binder to form a wet MOF binder mass, partially dried to form an undried MOF binder mass (undried binder mass or partially dried MOF binder mass), formed into undried adsorbent bodies or shaped MOF bodies and then further dried to form dried MOF adsorbent bodies or dried MOF bodies.Summary of the invention

[0036] The present invention provides, in a first aspect, a process for the production of an adsorbent body, wherein the process comprises the steps of:(a) forming a wet metal-organic framework (MOF) reaction mass (wet MOF mass), wherein the wet metal-organic framework reaction mass comprises MOF, unreacted MOF precursors, and reaction solvent;(b) contacting the wet MOF reaction mass with a binder to form a wet binder mass;(c) partially drying the wet binder mass to form an undried binder mass;(d) forming the undried binder mass into an undried adsorbent body;(e) removing at least some of the remaining solvent from the undried adsorbent body to form a dried adsorbent body;(f) activating the dried adsorbent body by subjecting the dried adsorbent body to a temperature of greater than about 100 °C to form an adsorbent body.

[0037] After forming the undried adsorbent bodies or the dried adsorbent bodies, the undried adsorbent bodies or dried adsorbent bodies can optionally be washed and dried by contacting the bodies with a washing solvent so as to remove unreacted materials and / or residual reactant solvent. Step (e) is preferably done as an individual low temperature step but can be carried out as part of the higher temperature activation step (f).

[0038] Typically, the undried binder mass is formed into undried adsorbent bodies, such as extrudates of pre-determined length or distribution of lengths. They can then preferably be subjected to a further rounding step. Alternatively, the undried binder mass can be formed by other processes, such as spreading the wet binder mass into a layer or sheet followed by drying to form the undried binder mass and then milling or cutting to form the undried adsorbent body / bodies. The undried adsorbent bodies can then be further dried to form dried adsorbent bodies. Preferably, step (e) is at least initially carried out under controlled and limited conditions, such as less than 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, preferably so as to slowly further dry the undried adsorbent bodies.

[0039] Slowly drying the undried adsorbent bodies is believed to be important to avoid cracking and fragmentation of the undried adsorbent bodies as solvated binder material dries and shrinks. Reducing the amounts of solvent to be removed, such as by using a wet MOF reaction mass as described herein, helps reduce the scale of this problem since the binder is not as solvated and has less volume to start with. This makes it easier and more industrially practical to make high-density bodies. Higher drying temperatures can be used for low- volatility solvents such as dimethylformamide (DMF) whereas lower drying temperatures are used for more volatile solvents such as water, or ethanol, or methanol, or mixtures thereof. Prior to step (f), the dried adsorbent bodies may optionally be subjected to a washing step with washing solvent to remove unreacted materials to enhance the surface area to give washed adsorbent bodies. Following any solvent washing steps, if used, the dried adsorbent bodies are then activated at high temperature to remove residual solvent and form adsorbent bodies.

[0040] The present invention provides, in a second aspect, a process for the production of an adsorbent body, wherein the process comprises the steps of:(a) providing a wet metal-organic framework (MOF) mass, wherein the wet metalorganic framework mass comprises MOF, unreacted MOF precursors, and reaction solvent;(b) contacting the wet MOF mass with a binder to form a wet MOF binder mass;(c) partially drying the wet MOF binder mass to form a partially dried MOF binder mass;(d) shaping the partially dried MOF binder mass into a partially dried MOF body;(e) removing at least some of the remaining solvent from the partially dried MOF body to form a dried MOF body;(f) activating the dried adsorbent body by subjecting the dried MOF body to a temperature of greater than about 100 °C to form an adsorbent body.

[0041] After forming the partially dried MOF bodies and dried MOF bodies, the partially dried MOF bodies and dried MOF bodies can optionally be washed and dried by contacting the bodies with a washing solvent so as to remove unreacted materials and / or residual reactant solvent. Step (e) is preferably done as an individual low temperature step but can be carried out as the initial stage of a higher temperature activation step (f).

[0042] Typically, the partially dried MOF binder mass is shaped into a partially dried MOF body(ies), such as extrudate(s) of pre-determined length or distribution of lengths. They can then preferably be subjected to a further rounding step. Alternatively, the partially dried MOF binder mass can be dried by other processes, such as spreading the wet MOF binder mass into a layer or sheet followed by drying to form the partially dried MOF binder mass and then milling or cutting to form (shape) the partially dried MOF body / bodies. The partially dried MOF body(ies) can then be further dried to form a dried MOF body(ies). Preferably, step (e) is carried out under controlled and limited conditions, such as less than 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, preferably so as to slowly further dry the partially dried MOF bodies.

[0043] Slowly drying the partially dried MOF body(ies) is believed to be important to avoid cracking and fragmentation of the partially dried MOF body(ies) as solvated binder material dries and shrinks. Reducing the amounts of solvent to be removed, such as by using a wet MOF mass as described herein, helps reduce the scale of this problem since the binder is not as solvated and has less volume to start with. This makes it easier and more industrially practical to make high-density bodies. Higher drying temperatures can be used for low- volatility solvents such as dimethylformamide (DMF) whereas lower drying temperatures are used for more volatile solvents such as water, or ethanol, or methanol, or mixtures thereof.

[0044] The drying step (e) is preferably done as an individual low temperature (less than about 100 °C) step but can also be combined with a subsequent high temperature (greater than about 100 °C) step, preferably for sufficient time to cross-link binder if an appropriate binder is used. The low temperature step may be for a period of for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater. The high temperature step may be for a period of for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater.

[0045] Prior to step (f), the dried MOF body(ies) may optionally be subjected to a washing step with washing solvent to remove unreacted materials to enhance the surface area to give washed MOF body(ies). Following any solvent washing steps, if used, the dried MOF body(ies) / washed MOF body(ies) may then be activated at high temperature to remove residual solvent and form adsorbent bodies. Prior to this activation step and following the washing step, the washed MOF bodies may be dried preferably via an individual low temperature (less than about 100 °C) step but can also be combined with a subsequent high temperature (greater than about 100 °C) step to cross-link the binder if an appropriate binder is used. The low temperature step may be for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater. The high temperature step may be for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater.

[0046] The present invention provides, in a third aspect, a process for the production of an adsorbent body, wherein the process comprises the steps of:(a) providing a wet metal-organic framework (MOF) mass, wherein the wet metalorganic framework mass comprises MOF, unreacted MOF precursors, and reaction solvent, preferably by contacting together MOF precursors and reaction solvent;(b) contacting the wet MOF mass with binder to form a wet MOF binder mass;(c) shaping the wet MOF binder mass into a shaped MOF body;(d) drying the wet MOF body to form a dried MOF body;(e) optionally contacting the dried MOF body with washing solvent to form a washed MOF body;(f) optionally removing at least some of the remaining solvent from the washed MOF body to form a second dried MOF body;(g) activating the first dried MOF body, the second dried MOF body, or the washed MOF body by subjecting the first dried MOF body, the second dried MOF body, or the washed MOF body to a temperature of greater than about 100 °C to form an adsorbent body.

[0047] After step (b) and before step (c), the process may comprise partially drying the wet MOF binder mass to form a partially dried MOF binder mass. The partially dried MOF binder mass may be used in shaping step (c).

[0048] Step (c) is preferably carried out by coating a non-MOF substrate with the wet MOF binder mass to form a MOF body on the surface of the substrate and ultimately an adsorbent body on the surface of the substrate. In this preferred embodiment, the adsorbent body typically forms a coating or coating layer on the surface of the substrate. The external surface of the substrate(s) is typically at least partially coated with adsorbent body, preferably, the external surface of the substrate(s) is coated with adsorbent body. The wet MOF binder mass may be partially dried prior to coating. During steps (d) and (e), the shaped MOF bodies are dried and washed. In step (e) the dried MOF body(ies) are contacted with a washing solvent so as to remove unreacted materials and / or residual reactant solvent. After (b) and before step (c), the process may comprise the step of partially drying the wet MOF binder mass to form a partially dried binder mass.

[0049] Additionally or alternatively, step (c) may comprise one or more drying steps. For example, partially dried MOF binder mass(es) can be formed by partially drying the wet MOF binder mass to make the partially dried MOF binder mass which is solid enough to beprocessed and handled and, for example, formed into extrudates in step (c). The drying step (d) is preferably done as an individual low temperature (less than about 100 °C) step but can also be combined with a subsequent high temperature (greater than about 100 °C ) step to cross-link the binder if an appropriate binder is used. The low temperature step may be for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater. The high temperature step may be for about 1 hour or greater, preferably for about 2 hours or greater, preferably about 5 hours of greater.

[0050] In the foregoing aspects, the wet MOF reaction mass (wet MOF mass) may be formed by contacting MOF precursors, such as metal salts, buffers, modulators and organic ligands, with reaction solvent, in a reaction mixture typically such that at least some of the precursors remain in solid form in the mass. This reaction mixture can be reacted for at least about 30 minutes, or at least about 1 hour, or at least about 2 hours, or at least about 3 hours, or at least about 4 hours at a controlled temperature of less than about 100 °C, or less than about 90 °C, or less than about 80 °C, or less than about 70 °C, or less than about 60 °C, or less than about 50 °C. Preferably, the reaction is carried out at about 60 °C. The wet MOF reaction mass (wet MOF mass) may comprise or may consist of MOF crystallites, unreacted MOF precursors (including metal salts, organic ligands, buffers and modulators) and reaction solvent. The reactants may be stirred together and reacted to have the form of a very thick paste or gel. This process may be applicable to a wide range of different MOFs by varying the reaction temperature, reaction time and level of reaction solvent. The reactant mix is typically sheared or stirred during this period. This can improve the yield of the reaction as well as reduce the MOF particle size. Equipment such as a high-torque Z-blade mixer or helical-screw mixer can be used as the reaction vessel. Typically, the wet MOF reaction mass (wet MOF mass) is in the form of a very thick paste or gel. The wet MOF reaction mass (wet MOF mass) then may be blended with the binder.

[0051] For the purpose of clarity, “unreacted MOF precursors” typically comprise the precursors used to prepare the MOF, i.e. the materials which the MOF comprised in the adsorbent body is made from. This term is typically used to describe generally the solids proportion of the wet MOF reaction mass (wet MOF mass) that is not the MOF, however there may be unreacted MOF precursors in solution.

[0052] Typically, the wet MOF binder mass is formed (shaped) into a shaped MOF body(ies), such as thin layers (e.g. coatings), granules, tablets or extrudates of pre-determined length or distribution of lengths. Extrudates can then preferably be subjected to a further rounding step, for example. As an alternative to extrusion, the shaped MOF body(ies) can be formed (shaped)by other processes, such as coating the wet MOF binder mass onto a substrate or spreading the wet MOF binder mass into a layer or sheet followed by drying to form the shaped MOF body(ies). The shaped MOF body(ies) may then optionally be subjected to further processing steps, such as milling or cutting. Preferably, step (d) is carried out, at least initially, under controlled and limited conditions, such as less than 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, preferably so as to slowly further dry the shaped MOF bodies.

[0053] Slowly drying the shaped MOF body(ies) is believed to be important to avoid cracking and fragmentation of the shaped MOF body(ies) as solvated binder material dries and shrinks. Reducing the amounts of solvent to be removed, such as by using a wet MOF mass as described herein, helps reduce the scale of this problem since the binder is not as solvated and has less volume to start with. This makes it easier and more industrially practical to make high-density bodies. Higher drying temperatures can be used for low-volatility solvents such as dimethylformamide (DMF) whereas lower drying temperatures are used for more volatile solvents such as water, or ethanol, or methanol, or mixtures thereof. In step (e), the dried MOF body(ies) are then subjected to a washing step with washing solvent to remove unreacted materials to enhance the surface area to give washed MOF body(ies). Following the solvent washing steps, the washed MOF body(ies) are then activated at high temperature to remove residual solvent and form adsorbent bodies.

[0054] In a fourth aspect, the present invention provides an adsorbent body or bodies made according to the process of the first to third aspect, preferably wherein the bodies have an envelope density of greater than about 0.3 g / cm3and less than about 1.5 g / cm3.

[0055] In a fifth aspect, the present invention provides the use of an adsorbent body or bodies produced according to the first to third aspect or an adsorbent body according to the fourth aspect for gas storage and / or purification, preferably hydrogen storage and carbon dioxide capture.

[0056] In a sixth aspect, the present invention provides the use of an adsorbent body or bodies produced according to the first to third aspect or an adsorbent body according to the fourth aspect for: (i) a gas separation process, preferably the gas separation process may be selected from the group consisting of carbon dioxide capture, krypton recovery, krypton purification, and combinations thereof; (ii) carbon dioxide adsorption; (iii) removing CO2directly from the flue gas of an industrial process and / or directly from the air; (iv) separation of Kr from a mixture of Kr / CF4 / N2, to obtain pure Kr from a mixture of Kr, CF4and N2; (v) wateradsorption, preferably water harvesting or heating, ventilation, and air conditioning (HVAC); (vi) gas storage, preferably hydrogen storage; (vii) field catalysis; and / or (viii) hydrocarbon separation and / or purification.

[0057] The optimised process of the invention described herein may include that the wet MOF binder mass is used to (i) form a coating layer on a substrate and dried to form the shaped MOF body, or (ii) is first partially dried, formed into shaped MOF bodies such as extrudates, granules or layers (e.g. coatings). The shaped MOF bodies are then further dried to form dried MOF bodies and ultimately adsorbent bodies. It may be preferred that the dried MOF adsorbent bodies are then subjected to an additional solvent exchange and washing step. The binder can be in solution, preferably aqueous solution, to improve dispersion, or can be in solid form. Preferably the binder is a partially solvated powder or slurry as this can provide an optimum balance between minimising the additional solvents added and ensuring that the binder is sufficiently solvated to be able to act well as a binder.

[0058] For the avoidance of doubt, embodiments related to each aspect of the invention apply mutatis mutandis to the other aspects of the invention. Further aspects and embodiments of the present invention will be evident from the discussion herein.

[0059] In the context of this application, “undried” may describe concentrated masses of MOF, binder and solvent which have enough solvent to be deformable under moderate - e.g., manual, pressure but which are solid enough to retain their shape when handled, if formed into a shaped body or plurality of shaped bodies or coating layer(s). Typically, undried masses will have less than about 60wt% solvent, or less than about 50wt% solvent or less than about 40wt% solvent or even less than about 30wt% solvent. “Undried” means that the undried binder mass contains less solvent by wt% than the wet binder mass (wet MOF binder mass) or wet MOF reaction mass (wet MOF mass).

[0060] “Partially dried” typically describes concentrated masses of MOF, binder and solvent which have enough solvent to be deformable under moderate - e.g., manual, pressure but which are solid enough to retain their shape when handled, if formed into a shaped body or plurality of shaped bodies or coating layer(s). Typically, partially dried masses will have less than about 60wt% solvent, or less than about 50wt% solvent or less than about 40wt% solvent or even less than about 30wt% solvent. “Partially dried” means that the partially dried MOF binder mass contains less solvent by wt% than the wet binder mass (wet MOF binder mass) or the wet MOF reaction mass (wet MOF mass). The wet MOF binder mass can contain up to 90wt% total solvent including reaction solvent, solvent provided with the binder (for exampleY1 if the binder comprises an emulsion or solution) and any solvent added as a process aid, for example to assist with the substrate coating process e.g. as a diluent.

[0061] “Wet” typically refers to masses of MOF, binder and solvent which typically have enough solvent, for example over about 60wt% or over about 70wt%, or up to about 90 wt% to form dispersions, thick pastes or deformable mixes and which cannot be handled easily as discrete bodies, especially as a plurality of bodies. However, such wet masses are typically suitable for providing an adsorbent body as a coating on a substrate(s). “Dry” typically refers to a mass of MOF / binder / solvent which has been sufficiently dried to form hard, robust bodies. This can include bodies which have been heated sufficiently to cross-link appropriate binders.

[0062] Hence, a wet material can be partially dried to first form an undried or partially dried material and then dried further to form dry or dried material. For any given MOF-containing mix, the wet mass will have a higher solvent level, for example greater than 10wt% of the total mass, than the undried material, which in turn will have a higher solvent level than the dried material. For any given MOF-containing mix, the wet mass will have a higher solvent level, for example greater than 10wt% of the total mass, than the partially dried material, which in turn will have a higher solvent level than the dried material. However, the absolute amounts of solvent in these different stages (wet, undried or partially dried, dry) may be different for different frameworks and binders. The dry MOF bodies may be subjected to further processing steps such as solvent washing and activation at elevated temperatures to completely remove residual solvent and / or unreacted materials.Detailed description of the invention

[0063] Throughout this specification, one or more aspects of the invention may be combined with one or more features described in the specification to define distinct embodiments of the invention.

[0064] References herein to a singular of a noun encompass the plural of the noun, and vice- versa, unless the context implies otherwise. For example, the term adsorbent body should be understood to also refer to adsorbent bodies, the term a metal-organic framework (MOF) should be understood to also refer to metal-organic frameworks (MOFs).

[0065] Throughout this specification the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer orstep, or group of elements, integers or steps. The term ‘comprising’ includes within its ambit the term ‘consisting’ or ‘consisting essentially of’.

[0066] The term ‘consisting’ or variants thereof is to be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and the exclusion of any other element, integer or step or group of elements, integers or steps.

[0067] The term ‘consisting essentially of’ or variants thereof is to be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, and that further components may be present, but only those not materially affecting the essential characteristics of the formulation, composition, or compound.

[0068] The term ‘about’ as used herein, when qualifying a number or value, is used to refer to values that lie within ± 5% of the value specified.Process for the production of an adsorbent body.

[0069] The process of the first aspect preferably comprises the steps of:(a) forming a wet MOF reaction mass, preferably wherein the wet MOF reaction mass comprises:(i) from about 10% to about 70%, or from about 20% to about 70%, or from about 30% to 60%, or from about 40% to about 50%, of MOF by weight of the wet MOF reaction mass;(ii) from about 10% to about 85%, preferably from about 10% to about 80%, from about 10% to about 70%, preferably from about 10% to about 60%, preferably from about 10% to less than about 50%, reaction solvent by weight of the wet MOF reaction mass; and(iii) from about 3% to about 50%, from about 8% to about 40%, from about 10% to about 30% unreacted MOF precursors by weight of the MOF in the wet MOF reaction mass;(b) contacting the wet MOF reaction mass with a binder to form a wet binder mass;(c) partially drying the wet binder mass to form an undried binder mass;(d) forming the undried binder mass into an undried adsorbent body;(e) removing at least some of the remaining solvent from the undried adsorbent body to form a dried adsorbent body;(f) optionally contacting the dried adsorbent body with a washing solvent to form a washed adsorbent body and removing at least some of the washing solvent from the washed adsorbent body to form a washed adsorbent body; and(g) activating the washed or dried adsorbent body by subjecting the dried or washed adsorbent body to a temperature of greater than about 100°C to form an adsorbent body.

[0070] It is especially preferred if steps (a) and (b) and optionally (c) can all be carried out in the same reaction vessel.

[0071] The process of the second aspect preferably comprises the steps of:(a) providing a wet MOF mass, preferably wherein the wet MOF mass comprises:(i) from about 10% to about 70%, or from about 20% to about 70%, or from about 30% to 60%, or from about 40% to about 50%, of MOF by weight of the wet MOF mass;(ii) from about 10% to about 85%, preferably from about 10% to about 80%, from about 10% to about 70%, preferably from about 10% to about 60%, preferably from about 10% to less than about 50%, reaction solvent by weight of the wet MOF mass; and(iii) from about 3% to about 50%, from about 8% to about 40%, from about 10% to about 30% unreacted MOF precursors by weight of the MOF in the wet MOF mass, preferably the wet MOF mass is formed by contacting together MOF precursors and reaction solvent;(b) contacting the wet MOF mass with a binder to form a wet MOF binder mass;(c) partially drying the wet MOF binder mass to form a partially dried MOF binder mass;(d) shaping the partially dried binder mass into a shaped MOF body;(e) removing at least some of the remaining solvent from the partially dried MOF body to form a dried MOF body;(f) optionally contacting the dried MOF body with a washing solvent and removing at least some of the washing solvent to form a washed MOF body; and(g) activating the washed or dried MOF body by subjecting the dried or washed MOF body to a temperature of greater than about 100°C to form an adsorbent body.

[0072] It is especially preferred if steps (a) and (b) and optionally (c) can all be carried out in the same reaction vessel.

[0073] The process of the third aspect preferably comprises the steps of:(a) providing a wet MOF mass, preferably wherein the wet MOF mass comprises:(i) from about 10% to about 70%, or from about 20% to about 70%, or from about 30% to 60%, or from about 40% to about 50%, of MOF by weight of the wet MOF mass;(ii) from about 10% to about 85%, preferably from about 10% to about 80%, from about 10% to about 70%, preferably from about 10% to about 60%, preferably from about 10% to less than about 50%, reaction solvent by weight of the wet MOF mass; and(iii) from about 3% to about 50%, from about 8% to about 40%, from about 10% to about 30% unreacted MOF precursors by weight of the MOF in the wet MOF mass, preferably the wet MOF mass is formed by contacting together MOF precursors and reaction solvent;(b) contacting the wet MOF mass with a binder to form a wet MOF binder mass;(c) shaping the wet MOF binder mass into a shaped MOF body, preferably the wet MOF binder mass is shaped into a shaped MOF body by either(I) partially drying the wet MOF binder mass to form a partially dried MOF binder mass and then shaping the partially dried MOF binder mass into the shaped MOF body; or(II) coating a substrate with wet MOF binder mass, optionally wherein the wet MOF binder mass is partially dried prior to the coating step, to form the shaped MOF body;(d) drying the shaped MOF body to form a dried MOF body, preferably by removing at least some of the remaining solvent from the shaped MOF body to form a dried MOF body;(e) optionally contacting the dried MOF body with a washing solvent and removing at least some of the washing solvent to form a washed MOF body; and(f) activating the washed or dried MOF body by subjecting the dried or washed MOF body to a temperature of greater than about 100°C to form an adsorbent body.

[0074] It is especially preferred if steps (a) and (b) and optionally at least part of (c) can all be carried out in the same reaction vessel.

[0075] The inventors have found that adding binder as a solution or slurry may further increase the level of solvent. Such wet MOF binder masses are typically too soft to be easily extruded and / or cut. The wet MOF binder mass typically needs to be subjected to a drying or partial drying step to form an undried binder mass (or partially dried MOF binder mass) which is sufficiently solid-like for any extrusion and / or cutting step to be viable.

[0076] Typically, the wt% level of solvent in the wet binder mass (wet MOF binder mass) can be reduced by controlled evaporation or by the addition of low levels (for example up to about 40 wt%) levels of one or more porous fine powders which can adsorb at least some of the solvent. Such powders can include silica, activated carbons, fine, pre-dried organic frameworks, zeolites or combinations thereof. Silica, for example, is able to strongly adsorb many solvents within its pores.

[0077] The present invention provides an improved process for the production of high performing adsorbent MOF bodies, optionally by a multi-stage drying process, wherein a wet MOF reaction mass (wet MOF mass) is contacted with a binder, typically an organic polymeric binder, typically in solution / slurry or as a partially solvated powder, to form a wet binder mass (wet MOF binder mass). Preferably, the wet binder mass (wet MOF binder mass) then hasenough solvent removed to form a more solid-like undried binder mass (partially dried MOF binder mass) which can be more easily formed (or shaped) into undried adsorbent bodies (or partially dried MOF bodies or shaped MOF bodies) and then subjected to at least one further solvent reduction step. Typically, such undried adsorbent bodies (or partially dried MOF bodies or shaped MOF bodies) can be formed by an extrusion and / or cutting process or even a coating process. Preferably, in the shaping step, the wet MOF binder mass can be directly used to coat a substrate and then dried to form the dried MOF body and ultimately the adsorbent body (on the surface of the substrate(s)). The undried (partially dried) or dried MOF bodies can preferably undergo a washing step using a washing solvent followed by high temperature drying to form activated adsorbent bodies.Step (a) - providing (and / or forming) a wet MOF reaction mass (wet MOF mass).

[0078] Step (a) forms a wet MOF reaction mass (wet MOF mass).

[0079] Preferably, step (a) is carried out by contacting together:(a) metal-organic framework precursor materials, preferably two or more metal-organic framework precursor materials,(b) reaction solvent, to form the wet MOF reaction mass (wet MOF mass). Preferably at least some of the precursor materials are in solid form. Preferably, no further reaction steps are carried out following the contacting together. Preferably, the wet MOF reaction mass (wet MOF mass) is not subject to any washing or concentrating steps. Preferably, the wet MOF reaction mass (wet MOF mass) is not subject to any solvent exchange processes. Preferably, the wet MOF reaction mass (wet MOF mass) is used directly following preparation.

[0080] Step (a) provides a wet MOF mass, preferably step (a) is carried out by contacting together:(a) metal-organic framework precursor materials, preferably two or more metal-organic framework precursor materials,(b) reaction solvent, to form the wet MOF reaction mass (wet MOF mass). Preferably at least some of the precursor materials are in solid form. Preferably, no further reaction steps are carried outfollowing the contacting together. Preferably, the wet MOF reaction mass (wet MOF mass) is not subject to any washing or concentrating steps. Preferably, the wet MOF reaction mass (wet MOF mass) is not subject to any solvent exchange processes. Preferably, the wet MOF reaction mass (wet MOF mass) is used directly following preparation.

[0081] Suitable conditions for this contacting reaction are well within the ambit of the skilled person. For example, this contacting reaction may be carried out at temperatures of less than about 100 °C, for example from about 20 °C to about 100 °C, or from about 50 °C to about 90 °C, for periods of time greater than about 30 mins, or greater than about 1 hour, or greater than about 2 hours, or greater than about 4 hours, or less than about 2 days, or less than about 1 day, or less than about 18 hours, with optional shearing during the reaction period so as to form a wet metal-organic framework reaction mass (wet MOF mass).

[0082] Suitable equipment includes a Sigma or Z-blade type high torque mixer or a helicalscrew type mixer. Intense shearing can help the homogeneity of the mix and reduce the resulting particle size. Alternatively, equipment such as the Cyclomixer from Hosokawa Micron could be used.

[0083] The conditions of the reaction mixture to form the wet MOF reaction mass (wet MOF mass), such as type and concentration of solvent, temperature, reaction time etc can be varied such that a very wide range of different MOFs can be formed at acceptable yield. Equipment such as twin-screw extruders are not preferred due to the short residence time which limits the flexibility of the process and range of MOFs that can be made. It is preferred if steps (a) and (b) and preferably (c) of the first aspect can all be carried out in the same reaction vessel. It is preferred if steps (a), (b) and preferably (c) of the second aspect can all be carried out in the same reaction vessel. It is preferred if steps (a) and (b) of the third aspect can be carried out in the same reaction vessel.

[0084] One option is to mix the different precursors with part of the reaction solvent before adding the separate precursors together with stirring. For example, ZU-301 can be prepared by (i) preparing a dispersion / slurry of zinc carbonate basic in water with heating and agitation and (ii) dissolving oxalic acid and 3-methyl-1 ,2,4-triazole in a water / ethanol mix and (iii) adding the ligand solution to the zinc carbonate dispersion / slurry with lots of stirring and at elevated temperature for several hours.

[0085] Preferably, the metal-organic framework precursor material may be one or more, or a plurality of, metal ions, e.g. metal cations, and one or more, or a plurality of, organic ligands, e.g. multidentate organic ligands.

[0086] The metal ions may be selected from the group consisting of: Zn2+, Zr2+, Cu2+, Al3+, Mn2+, Mg2+, Nb2+, Fe2+, Fe3+, Ti2+, Ti3+, Ti4+, Co2+, Cr2+, Nb2+, Ni2+, Ca2+and mixtures and combinations thereof. More preferably, the MOF contains metal ions selected from one or more of Zn2+, Zr2+or Al3+. The metal ions may be provided by the salt of the metal ion, such as ZrCI4.

[0087] Preferably, the metal-organic framework is a Zn-containing MOF, an Al-containing MOF, or a Zr-containing MOF. For example, the metal-organic framework is a Zr-containing metal-organic framework and the metal-organic framework precursor materials comprise a Zr metal salt that has been pre-reacted to form Zre oxo-metal clusters

[0088] A multidentate organic ligand is an organic ligand capable of donating two or more pairs of electrons in a complexation reaction to form two or more coordinate bonds. The one or more, or plurality of, organic ligands may comprise two or more oxygen and / or nitrogen atoms suitable for donating a pair of electrons to form the two or more coordinate bonds. Preferably, the oxygen atoms may be present as carboxylate or nitro groups. Preferably, the nitrogen atoms may be present as amine groups. Typically, the plurality of organic ligands may be an aromatic carboxylate, an aromatic amine and / or an aromatic nitro.

[0089] Typically, the MOF formed and / or provided in step (a) comprises or is in the form of MOF crystallites. Preferably, the crystallites have a small primary particle size, preferably having a mean 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, or from about 20 nm and 400 nm. Preferably, the crystallites may have a mean particle size of from about 30 nm to about 100 nm. Small primary particles typically increase particle packing in the adsorbent bodies to give higher body densities. The method of measuring particle size is described in more detail below. The particle size of the MOF is preferably measured in a diluted mix of wet MOF reaction mass (wet MOF mass) by DLS, but can be measured once the material has been formed into the adsorbent body using small angle X-ray scattering (SAXS). Optical image analysis techniques (microscopic analysis) are also suitable for analysis of crystallites in the solid adsorbent body formed in the process of the invention.

[0090] The wet MOF reaction mass (wet MOF mass) may have a solids content of from about 20 wt% to about 75 wt%, or from about 25 wt% to about 60 wt%, or from about 30 wt% to about 50 wt%. Conventional adsorbent body synthesis via a dilute sol-gel may only achieve a solids content of 8 wt% or less, whereas the process of the present invention can achieve high solids content without the need for centrifugation. The wet MOF reaction mass (wet MOF mass) is kept under reaction conditions for long enough to ensure that the majority of the precursors have reacted.Step (b) - forming a wet binder mass (wet MOF binder mass).

[0091] Step (b) contacts the wet MOF reaction mass (wet MOF mass) with a binder, preferably a polymeric organic binder, to form a wet binder mass (wet MOF binder mass).

[0092] The binder can be in solution (if soluble in a suitable solvent) or it can be added as a solid (preferably as 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. The partial pre-solvation of the binder increases the interaction and efficacy of the binder with the wet MOF reaction mass (wet MOF mass) compared to addition as a pure powder whilst limiting the amount of extra solvent required. Adding a soluble organic polymeric binder as a solution or emulsion can be very effective for the dispersion and subsequent performance of the binder (thus limiting the amount needed) but significantly increases the amount of solvent that subsequently need to be removed. The binder is typically mixed with the wet MOF reaction mass (wet MOF mass) with extended mixing to ensure homogeneity.

[0093] The binder, preferably polymeric organic binder, may be partially solvated, preferably by pre-mixing with one or more solvents selected from the group consisting of: water, DMSO, short-chain length 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.

[0094] The binder may be added to the wet MOF reaction mass (wet MOF mass) in an amount of from about 0.5% to about 50 wt%, or from about 0.5% to about 40 wt%, or from about 0.5% to about 30%, or about 1% to about 25%, or about 5% to about 20% or about 10% to about 15%, by weight of the MOF in the wet MOF reaction mass (wet MOF mass).

[0095] The binder may be provided as a solution, emulsion or dispersion. Optionally, the binder may be provided as from about 4wt% to about 70wt% binder solution or dispersion, orfrom about 10wt% to about 50wt% binder solution or dispersion, or from about 30wt% to about 40wt% binder solution or dispersion. Typically, adsorbent body formation processes utilise dilute binder solutions, such as about 4wt% binder solution. Using more concentrated binder solutions or dispersions may improve the efficiency of the adsorbent body formation process as a solvent reduction steps can be minimised but can introduce other problems such as mixing. The binder may be provided as a fine powder with no added solvent. The binder may be added as a partially solvated powder, for example having a solvent level of less than about 30wt%, or less than about 20wt%, or less than about 10wt%, or less than about 5wt%.

[0096] The binder is contacted with the wet MOF reaction mass (wet MOF mass) 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, or about 1 :2 or about 1 :1.

[0097] Preferably, step (b) immediately follows step (a).Forming an undried binder mass or a partially dried MOF binder mass.

[0098] This step partially dries the wet binder mass (wet MOF binder mass) to form an undried binder mass or partially dried MOF binder mass. This step removes at least some (but not all) of the reaction solvent from the wet binder mass (wet MOF binder mass) to form an undried binder mass or a partially dried MOF binder mass.

[0099] This step can be achieved in several different ways. The wet binder mass (wet MOF binder mass) can be dried before cutting. This could be done in, e.g., a wiped film evaporator or heated high-torque mixer and the resulting undried binder mass or partially dried MOF binder mass is then cut and / or formed into smaller bodies, such as extrudates, granules or substrate coating layers. The wet binder mass (wet MOF binder mass) could be spread out and allowed to dry on flat surfaces, such as trays, to form an undried binder mass or a partially dried MOF binder mass followed by being cut in a cutting mill or flaker or other suitable cutting equipment. Such methods are examples of removing (e.g. evaporating) at least some but not all of the reaction solvent from the wet binder mass (wet MOF binder mass) to form an undried binder mass or a partially dried MOF binder mass.

[0100] Another option is to add an additional adsorbent solid material that is able to adsorb some of the reaction solvent, thus providing an undried binder mass or a partially dried MOF binder mass containing less solvent by wt% than the wet binder mass (wet MOF binder mass). Such material can be selected from fine activated carbon or silica or zeolite or even some pre-dried framework material or pre-dried MOF material (if levels are not too high) and mixtures thereof. The MOF powder could be the same as that forming the wet binder mass (wet MOF binder mass) or it could be different. Preferably the additional adsorbent powder is selected from activated carbons, zeolites, metal-organic frameworks, silica and mixtures. The additional adsorbent solid material can even be polymeric organic binder if sufficient quantity it is added in fine powder form. Provided quantities of additional adsorbent solid material added are limited, some limited extra porosity could be acceptable. Such methods are examples of trapping at least some but not all of the reaction solvent from the wet binder mass (wet MOF binder mass) to form an undried binder mass or a partially dried MOF binder mass, i.e. some of the reaction solvent is bound to, for example, an additional adsorbent material.

[0101] Suitable silicas for use as the additional adsorbent material are precipitated or fumed silicas, preferably fumed silica. Suitable fumed silica includes the Aerosil range from Evonik. Suitable precipitated silicas include the Sipernat range from Evonik.

[0102] Thus, this step may be carried out by (i) evaporation of solvent; and / or (ii) addition of an adsorbent material having a lower solvent level than the wet binder mass (wet MOF binder mas), to the wet binder mass (wet MOF binder mass), wherein the adsorbent material is selected from one or more of silica, zeolite, activated carbon, graphene, metal-organic frameworks or combinations thereof.

[0103] This step may also be carried out by coating the wet binder mass or wet MOF binder mass directly onto a substrate. The coating step may be carried out by spreading or spraying the wet binder mass or wet MOF binder mass onto a substrate or dip-coating the substrate in the wet MOF binder mass. In some embodiments, the wet binder mass or wet MOF binder mass may be diluted in a spraying solvent. The spraying solvent may be selected from the list of reaction solvents disclosed herein. The spraying solvent may be the same as the reaction solvent or may be different.

[0104] Preferably, this step is carried out at from about 20 °C to about 80 °C, or from 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.

[0105] Typically, the undried binder mass or partially dried MOF binder mass formed by the reduction in reaction solvent level in step (c) has a viscosity at 10s-1and 25 °C of from about 3.0 x 105mPa.s to about 3.0 x 106mPa.s. For example, the undried binder mass or partially dried MOF binder mass may have a viscosity of > about 4.0 x 105mPa.s at 10 s-1and 25 °Cbefore any cutting step. The undried binder mass or partially dried MOF binder mass retains enough solvent as to be deformable under pressure and impact so it can be rounded, eg in a spheroniser. Typically, the viscosity of the undried binder mass or partially dried MOF binder mass is less than about 1 .25 x 106mPa.s at 10 s-1and 25 °C.

[0106] Optionally, step (b) and this step may be carried out simultaneously or sequentially.Forming and / or shaping an undried adsorbent body or shaped MOF body.

[0107] The forming and / or shaping step forms the undried binder mass or partially dried MOF binder mass or wet MOF binder mass into an undried adsorbent body or shaped MOF body. The forming or shaping step may be carried out by an extrusion or injection moulding process, or by a cutting or milled process or a coating process. Preferably, the forming or shaping step extrudes and / or cuts and / or otherwise forms the undried binder mass or partially dried MOF binder mass or wet MOF binder mass to form an undried adsorbent body or shaped MOF body. Optionally, the undried adsorbent body or shaped MOF body may be subjected to a spheronisation treatment. The undried adsorbent body or shaped MOF body typically has the same composition as the undried binder mass or partially dried MOF binder mass or wet MOF binder mass.

[0108] Optionally, this step forms and / or shapes the wet MOF binder mass into shaped MOF body, preferably either by (i) partially drying the wet MOF binder mass to form a partially dried MOF binder mass and then shaping the partially dried MOF binder mass into the shaped MOF body, or (ii) coating a substrate with wet MOF binder mass, optionally wherein the wet MOF binder mass is partially dried prior to the coating step, to form the shaped MOF body. Following this step, the shaped MOF body may typically be subject to some initial drying.

[0109] In the process of the third aspect, the partial drying step described herein is optional and may be carried out prior to the shaping and / or forming step, but is not essential. Typically, the partial drying step is carried out in the process of the first and second aspect and optionally in the process of the third aspect.

[0110] At least some of the reaction solvent may be removed from the undried adsorbent body or partially dried MOF body to form a dried adsorbent body or dried MOF body. If done, preferably, this step is done gradually, such as at temperatures of less than about 80 °C or less than about 50 °C or less than about 40 °C or even at ambient temperatures.

[0111] Optionally, the dried adsorbent body or dried MOF body may be contacted with washing solvent so as to remove unreacted materials and / or reaction byproducts and to form a washed adsorbent body. This washing step may be carried out once or more than once. The washing solvent may be the same as the reaction solvent or it may be different to the reaction solvent.Forming a dried adsorbent body or dried MOF body.

[0112] This step removes at least some of the remaining solvent from the undried adsorbent body or shaped MOF body (optionally washed MOF body) to form a dried adsorbent body or dried MOF body. This step may be carried out by gradual drying at temperatures of less than about 100 °C or less than about 60 °C or even at ambient temperatures.

[0113] This step preferably carried out by a low temperature drying process. This step may also be carried out by a two stage drying process wherein a first, lower temperature stage is used to remove solvent without damaging the structure of the MOF adsorbent body. A second, higher temperature stage, may be used to react and cross-link binders. For example, drying to remove solvent can happen at temperatures less than about 80 °C or less than about 50 °C or less than about 40 °C or even at ambient temperatures, whilst temperatures of greater than about 100 °C can then be used to initiate cross-linking reactions.Washing the dried MOF body

[0114] During this step, the (first) dried MOF body is contacted with washing solvent so as to remove unreacted materials and / or reaction byproducts and to form a washed MOF body. This washing step may be carried out once or more than once, for example twice or three times. The washing solvent may be the same as the reaction solvent or it may be different to the reaction solvent. The washing may be carried out by submerging the dried MOF body in the washing solvent and then removing the washed MOF body by filtration, decantation or scooping. The washing may be carried out for from about 1 hour to about 7 days, or from about 5 hours to about 5 day, or from about 12 hours to about 3 days, or from about 1 day to about 3 days.

[0115] After this step, optionally, at least some of the remaining solvent is removed from the washed MOF body to form a (second) dried MOF body.Activation step.

[0116] This step activates the dried adsorbent body or the dried MOF body by subjecting the unactivated adsorbent body or (first or second) dried MOF body to a temperature of greater than about 100 °C, preferably under vacuum, to form an adsorbent body. Preferably, this step immediately follows the formation of the dried adsorbent body or (first or second) dried MOF body.. The formation of the dried adsorbent body or (first or second) dried MOF body can optionally be integrated as an initial part of the step.

[0117] Typically, the adsorbent body has an envelope density of greater than about 0.3 g / cm3, or greater than about 0.5 g / cm3, or greater than about 0.7 g / cm3. The adsorbent body may have an envelope density of less than about 1.5 g / cm3, or less than about 1.2 g / cm3, or less than about 1.0 g / cm3.

[0118] The adsorbent body may have a BET area of from about 300 m2 / g to about 1700 m2 / g, or from about 500 m2 / g to about 1650 m2 / g, or from about 700 m2 / g to about 1600 m2 / g, or from about 800 m2 / g to about 1550 m2 / g.

[0119] Typically, the adsorbent body may have a mean body size of greater than about 0.25 mm, preferably greater than about 0.4 mm or even larger bodies having a monolithic form. The adsorbent bodies can be incorporated into other forms, such as sheets or membranes.

[0120] Typically, the adsorbent body comprises: (i) more than about 75%, or more than about 80%, or more than about 85%, metal-organic framework material by weight of the adsorbent body; and (ii) less than about 20%, or less than about 15%, or less than about 10%, or less than about 5% binder by weight of the adsorbent body.

[0121] Optionally, the formation of a dried adsorbent body or (first or second) dried MOF body and the activation step can happen simultaneously or sequentially, preferably simultaneously.Wet MOF reaction mass / wet MOF mass.

[0122] The wet MOF reaction mass (wet MOF mass) is provided and / or formed in step (a) and is a mixture of MOF material, residual unreacted MOF precursors and reaction solvent, plus any reaction by-products. The term “unreacted MOF precursors” is typically used herein to describe generally the solid material in the wet MOF reaction mass (wet MOF mass) that is not MOF, however there may be unreacted MOF precursors in solution. “Unreacted MOFprecursors” typically comprise the precursors used to prepare the MOF, i.e. the materials which the MOF comprised in the adsorbent body is made from, these may be solid or may be in solution.

[0123] The wet MOF reaction mass (wet MOF mass) comprises: (i) from about 20% to about 70% of a metal-organic framework by weight of the wet metal-organic framework reaction mass (wet MOF mass); (ii) from about 3% to about 50% unreacted MOF precursors by weight of the MOF in the wet metal-organic framework reaction mass (wet MOF mass); and (iii) from about 10 % to about 70 % of reaction solvent by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0124] Preferably, the wet metal organic framework reaction mass (wet MOF mass) comprises from about 10% to about 70%, or from about 20% to about 70%, or from about 40% to about 60%, of a metal-organic framework by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0125] Preferably, the wet MOF reaction mass (wet MOF mass) comprises from about 3% to about 50%, from about 10% to about 25%, unreacted MOF precursors by weight of the MOF in the wet MOF reaction mass (wet MOF mass).

[0126] Preferably, the wet MOF reaction mass (wet MOF mass) comprises from about 10% to about 85%, preferably from about 10% to about 80%, from about 10 % to about 70 %, or from about 20% to about 66%, or from about 30% to about 60%, of reaction solvent by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0127] Preferably, the wet framework reaction mass (wet MOF mass) comprises from about 10 % to about 50 %, or from about 20% to less than about 50%, of reaction solvent by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0128] Preferably, the wet metal organic framework reaction mass (wet MOF mass) comprises: (i) from about 20% to about 70% of a metal-organic framework by weight of the wet metal-organic framework reaction mass (wet MOF mass); (ii) from about 3% to about 50%, from about 10% to about 25%, unreacted MOF precursors by weight of the MOF in the wet MOF reaction mass (wet MOF mass); and (iii) from about 10 % to about 50 % of reaction solvent by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0129] Preferably, the wet metal organic framework reaction mass (wet MOF mass) comprises: (i) from about 20% to about 70% of a metal-organic framework by weight of thewet metal-organic framework reaction mass (wet MOF mass); (ii) from about 3% to about 50% unreacted MOF precursors by weight of the MOF in the wet MOF reaction mass (wet MOF mass); and (iii) from about 10 % to less than about 50 % of reaction solvent by weight of the wet metal-organic framework reaction mass (wet MOF mass).

[0130] Preferably, the wet reaction metal-organic framework mass (wet MOF mass) is not subjected to one or more washing and re-concentration steps subsequent to initial formation.Metal-Organic Framework

[0131] Preferably, the MOF contains metal ions selected from one or more of : Zn2+, Zr2+, Cu2+, Al3+, Mn2+, Mg2+, Nb2+, Fe2+, Fe3+, Ti2+, Ti3+, Ti4+, Co2+, Cr2+, Ni2+and Ca2+and mixtures thereof. More preferably, the MOF contains metal ions selected from one or more of Zn2+, Zr2+or Al3+. Suitable MOFs include, but are not limited to, the MOFs listed or mentioned below.

[0132] For the purpose of clarity, references to a MOF include derivatives of that MOF with the same structure, including derivatives of the ligands and changes to the metal ions used as well as combinations and mixtures thereof. For example, a reference to CPO-27 / MOF-74 would include CPO-27-Ni, CPO-27-Mg, CPO-27-Mn, CPO-27-Zn and CPO-27-Cu as well as ligand functionalised variations thereof, such as CPO-27-Mg-NH2, and other variants unless specified otherwise.

[0133] Suitable Zr-containing MOFs include UiO-66, UiO-67, UiO-68, NU-1000, PCN-222, MOF-808 and Zr-fumarate.

[0134] Suitable Zn-containing MOFs include ZIF-7, ZIF-8, ZIF-67, ZIF-71 , ZIF-90. and Zn- containing UTSA-16, CALF-20, ZU-301 , and MOF comprising a. a plurality of metal ions, each of the plurality of metal ions having a valency selected from the group consisting of +2 and +3; and b. a plurality of organic ligands, the plurality of organic ligands comprising i. organic ligand derived from a compound of Formula I; andI ii. one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III, preferably the one or each further organic ligands is derived from a compound of Formula II;wherein each Ri is independently selected from the group consisting of I, Cl, Br, F, NH2, R4, and OR4; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, Ci to C4alkyl, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4alkyl or substituted Ci to C4alkyl, preferably R4is Ci to C4alkyl, preferably CH3or CH2CH3; wherein m = 0, 1 , 2, 3 or 4; wherein n = 1 , 2 or 3; wherein p = 0, 1 or 2; and wherein q = 0, 1 or 2, preferably a MOF comprising a plurality of zinc ions, a plurality of organic ligands derived from 3,4-dihydroxybenzoic acid and a plurality of further organic ligands derived from 1 ,2,4-triazole.

[0135] Suitable Al-containing MOFs include MIL-53, CAU-10, MIL-160(AI), Al-formate, Al- fumarate and AI-soc-MOF-1.

[0136] Suitable MOFs of the M(F6-x)Lxfamily include SIFSIX-3-Ni, TIFSIX-3-Ni, NbOFFIVE-1- Ni and SIFSIX-2-Cu-i.

[0137] Suitable Cr-based MOFs include MIL-100(Cr), and MIL-101(Cr).

[0138] Suitable Cu-based MOFs include HKUST-1 and ROS-17.

[0139] Suitable Co-based MOFs include cobalt-based UTSA-16 and derivatives thereof.

[0140] Suitable Fe-based MOFs include MIL-100(Fe) and MIL-101 (Fe).

[0141] Suitable mixed metal MOFs include MOFs based on mixtures of two or more metals selected from Fe, Ti and Zn.

[0142] Suitable MOFs can comprise mixed ligand or co-crystallite MOFs wherein the MOF comprises at least two chemically distinct organic ligands bonded to the same metal ion. This feature can help adjust the chemical behaviour of the MOF.

[0143] It may be preferred that the two chemically distinct organic ligands are chemical analogues. By chemical analogue, it is meant that the structural aspects of the ligand, specifically the backbone as well as the moieties that are involved in the bonding to metal ions, are the same.

[0144] An especially preferred feature is for the chemical distinct organic ligands to be chemical analogues, such that the organic ligands have the same backbone structure but differ from each other due to the functionalisation of the backbone structure. The structural similarity of how the different organic ligand anions bond to the metal ions means that variants of a specific MOF can be formed. If the organic ligands are too dissimilar then the MOF may be amorphous or full of defects.

[0145] For example, many MOFs have dicarboxylic acids as their organic ligands. Each carboxylic acid group is involved in bonding to a metal ion. The backbone structure refers to the structure between the two carboxylic acid binding groups. The dimensions of the backbone structure determine the dimensions of the pores formed by the organic ligands connecting with the metal ions. The chemical differences come from functional pendant groups attached to the backbone structure.

[0146] Exemplary examples are shown below. In these cases, the backbone structure is (deprotonated) terephthalic acid (A).

[0147] Additional exemplary examples are discussed below. Two exemplary chemical analogues are terephthalic acid (CAS 100-21-0) and 2-aminoterepthalic acid (CAS 10312-55- 7). Other exemplary analogues 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).

[0148] A further example is the use of blends of 1 ,2,4-triazole and 3-methyl 1 ,2,4-triazole with oxalic acid when forming variants of CALF-20. For example, mixes of about 1 :3, about 1 : 1 and about 3:1 of 1 ,2,4-triazole and 3-methyl 1 ,2,4-triazole can be used with oxalic acid. Mixtures of 1 ,2,4-triazole and oxalic acid or 3-methyl 1 ,2,4-triazole and oxalic acid may be used as ligand.

[0149] A further example is the use of mixtures of organic ligand derived from a compound of Formula I, and one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III, preferably the or each further organic ligand is derived from a compound of Formula II:Iwherein each Ri is independently selected from the group consisting of I, Cl, Br, F, NH2, R4, and OR4; wherein each R2and each R3is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4alkyl or substituted Ci to C4alkyl; wherein m = 0, 1 , 2, 3 or 4; wherein n = 1 , 2 or 3; wherein p = 0, 1 or 2; and wherein q = 0, 1 or 2.

[0150] Preferred compounds of Formula I include the group consisting of 3,4- dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, and combinations thereof. The most preferred compound of Formula I is 3,4-dihydroxybenzoic acid. Preferred compounds of Formula II include the group consisting of 1 ,2,4-triazole, 3-methyl-1 H-1 ,2,4-triazole, 3-amino- 1 H-1 ,2,4-triazole, and combinations thereof.

[0151] Particularly preferred mixtures of organic ligand derived from a compound of Formula I, and one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula II or a compound of Formula III include those comprising: (i) 3,4- dihydroxybenzoic acid and 1 ,2,4-triazole, (ii) 3,4-dihydroxybenzoic acid, 1 ,2,4-triazole and 3- methyl-1 H-1 ,2,4-triazole, (iii) 3,4-dihydroxybenzoic acid and 3-methyl-1 ,2,4-triazole, (iv) 3,4- dihydroxybenzoic acid and 3-amino-1 ,2,4-triazole, (v) 3,4-dihydroxybenzoic acid, 1 ,2,4- triazole and 3-amino-1H-1 ,2,4-triazole, (vi) 3,4-dihydroxybenzoic acid, 1 ,2,4-triazole, 3- methyl-1 H- 1 ,2,4-triazole and 3-amino-1 ,2,4-triazole, (vii) 3,4,5-trihydroxybenzoic acid and 1 ,2,4-triazole, (viii) 3,4,5-trihydroxybenzoic acid, 1 ,2,4-triazole and 3-methyl-1 H-1 ,2,4-triazole, (ix) 3,4,5-trihydroxybenzoic acid and 3-methyl-1 ,2,4-triazole, (x) 3,4,5-trihydroxybenzoic acid and 3-amino-1 ,2,4-triazole, (xi) 3,4,5-trihydroxybenzoic acid, 1 ,2,4-triazole and 3-amino-1H- 1 ,2,4-triazole, and (xii) 3,4,5-trihydroxybenzoic acid, 1 ,2,4-triazole, 3-methyl-1 H- 1 ,2,4-triazole and 3-amino-1 ,2,4-triazole.

[0152] A still further example is the use of mixtures of organic ligand derived from a compound of Formula IV, one or more further organic ligands, the or each further organic ligand being derived from a compound of Formula V or a compound of Formula VI, preferably the or each further organic ligand is derived from a compound of Formula V, and optionally organic ligand derived from the group consisting of 1H-1 ,2,4-triazole, 2H-1 ,2,3-trizaole, 1 H-1 ,2,3-triazole, and combinations thereof:wherein each Ri is independently selected from the group consisting of Cl, Br, I, F, CF3, CHF2, R4, NH2, substituted amino, Cl, Br, I, NO2, C(O)R4, OH, aryl, substituted aryl; wherein each R2and each R3 is independently selected from the group consisting of Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R4, CO2R4, CO2H, CONH2, SH, and CN; wherein R4is Ci to C4alkyl or substituted Ci to C4alkyl; wherein m = 0, 1 or 2 wherein n = 1 or 2; and wherein p = 1 or 2.

[0153] Another example is the use of mixtures of organic ligand derived from a compound of Formula VII and organic ligand derived from a compound of Formula VII:wherein each Ri is independently selected from the group consisting of: OH, NH2, substituted amino, CO2H, CONH2, CONHR6, CONR6, CO2R6, C(O)R6, OR6, CN, Cl, Br, I, F, NO2, and SH; wherein R2, R3, R4and R5are independently selected from the group consisting of H, Ci to C4alkyl, OH, NH2, substituted amino, CO2H, CONH2, CONHR6, CONR6, CO2R6, C(O)R6, OR6, CN, Cl, Br, I, F, NO2, and SH, or R2and R3are linked to form a fused benzene ring and R4and R5are independently selected from the group consisting of H, Ci to C4alkyl, OH, NH2, substituted amino, CO2H, CONH2, CONHR6, CONR6, CO2R6, C(O)R6, OR6, CN, Cl, Br, I, F, NO2, and SH;R6is selected from the group consisting of Ci to C4alkyl and substituted Ci to C4alkyl; and n is 0, 1 , 2, or 3.

[0154] A further example is the use of mixtures of organic ligand derived from oxalic acid and two of more further organic ligands, each further organic ligand being derived from a compound of Formula IX or a compound of Formula X, preferably each further organic ligand is derived from a compound of Formula IX:wherein each Ri and each R2is independently selected from the group consisting of H, Br, Cl, I, F, CF3, CHF2, NH2, substituted amino, NO2, R3, CO2R3, CO2H, CONH2, SH, and CN; wherein R3is Ci to C4alkyl or substituted Ci to C4alkyl;wherein each n is independently selected from the group consisting of 1 and 2; and wherein each m is independently selected from the group consisting of 1 and 2.

[0155] The use of such chemical analogues allows specific MOFs to be made having variable chemical properties. It may also be preferred that the two chemically distinct organic ligands comprise different backbone structures. The use of organic ligands having different backbone structures can allow for “defects” to be introduced in the monolith body, where the structure of the MOF is incomplete, or allow for more complex MOF structures. These defects can increase porosity in some situations.

[0156] Adsorbent bodies comprising mixtures of MOFs can be prepared by mixing different wet MOF reaction mixes (wet MOF masses) together prior to the addition of the binder. Suitable MOF adsorbent bodies can comprise mixtures of MOF crystallites made with different ligands. For example, a suitable UiO-66 MOF adsorbent body can comprise mixtures of UiO- 66 BDC and UiO-66 BDC-NH2.Reaction Solvent.

[0157] The reaction solvent describes the solvent or solvent mix which is present in the reaction mixture to form wet MOF reaction mass / wet MOF mass and / or in the provided wet MOF reaction mass / wet MOF mass) where MOF precursors are contacted together to form the wet MOF reaction mass (wet MOF mass). The presence of reaction solvent typically increases the yield of the reaction forming the MOF. Preferred reaction solvent include dimethyl sulfoxide (DMSO), polar, aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMS) and N-methyl-2-pyrolidone, lower molecular weight (short chain length, C1 to C4) alcohols including ethanol and methanol, glycols, water, C1 - C4 organic acids such as acetic acid and mixtures and combinations thereof. Preferably, the reaction solvent comprises one or more of: water, acetone, DMSO, short-chain length alcohols, glycols and mixtures thereof. Water and ethanol:water blends are especially preferred. Preferably, the reaction solvent comprises more than 50 wt% water.Binder.

[0158] Herein, binder may refer to one binder or one or more binders. The binder may comprise a single species of binder. The binder may comprise one or more species of binder. The binder may comprise a combination of binders.

[0159] The binder can comprise an inorganic binder or an organic polymeric binder. Preferably the binder is an organic polymeric binder. The binder may comprise one or more binders, for example a first organic polymeric binder and a second organic polymeric binder, or an organic polymeric binder and an inorganic binder.Inorganic binders.

[0160] Inorganic binders may include materials such as silica including colloidal silica suspension, alumina including hydrated alumina, aluminosilicate, Zeolite, magnesium silicate, sodium silicate, calcium silicate, titanium dioxide (TiO2), magnesium oxide (MgO), calcium carbonate (CaCO3), boron nitride (BN), kaolin (hydrated aluminium silicate), clay (e.g., bentonite, montmorillonite), calcium phosphate, zirconium oxide (ZrO2), wollastonite (CaSiO3) or combinations thereof.Organic polymeric binder.

[0161] The terms “organic polymeric binder” and “polymeric organic binder” are used interchangeably herein. Preferably, the polymeric binder is an organic polymeric binder selected from one or more of the following; polyvinyl alcohol (PVA), polyvinyl formal, polyimide, polyetherimide, polyamide, polyvinyl pyrrolidone, polyacrylates including polyacrylic acid derived materials including copolymers of methyl and ethyl methacrylate, polycarboxylate, polyethylene glycol, polysulfone, polyether sulfone including poly(1 ,4- phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), polyvinylidene fluoride, graphite, graphene, graphene oxide, fluorinated graphene, polyvinyl epoxies, polyethylene, polystyrene, polyvinylchloride, polytetrafluorethylene, silane including tetraethoxysilane (TEOS) and methyltriethoxysilane, polymers having silane moieties, polysiloxanes including polydimethylsiloxane, tetraisopropyl orthosilicate, poly-ethylene oxide polymer including block co-polymers such as PEO-PPO block co-polymers, polyolefin, epoxide and epoxy resin, polyester, polylactic acid and derivatives thereof, polybenzimidazole (PBI), polyetherimide, polyacrylamide (PAM), polyurethane including polyurethane dispersions (PUDs), polyvinyl butyral (PVB), polyethyleneimine (PEI), polyaniline (PANI), polypyrrole (PPy), polyhydroxyalkanoate (PHA), polyoxymethylene (POM), thermoplastic polyurethane (TPU), polyfurfuryl alcohol (PFA), biopolymer-based material such as sesbania powder, polysaccharide gums including xantham gum and guar gum, alginate, chitosan, cellulose-based polymer including cellulose, cellulose acetate, cellulose acetate ester, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP),carboxymethyl cellulose (CMC), carboxymethyl starch (CMS), gum arabic, or any mixtures and combinations thereof. The polymeric binder can comprise biopolymer-based materials such as polysaccharide gums including xantham gum, guar gum, alginates, chitosan, cellulose-based polymers such as cellulose, cellulose acetate, cellulose acetate esters, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), or any mixtures and combinations thereof. A particularly preferred binder mix is a blend of a cellulose-based polymer, especially hydroxyethyl cellulose or methyl cellulose, and polyvinyl alcohol.

[0162] For the avoidance of doubt, the polymeric organic binder species, such as polyacrylate, polyurethane and epoxide, may comprise moieties with cross-linking functionality and be capable of acting as cross-linking binders. References to polymeric organic binder includes references to that polymeric organic binder having cross-linking functionality.

[0163] More preferably, the organic polymeric binder may be selected from one or more of the following: polyvinyl alcohol (PVA), polyimide, polyamide, polyvinyl pyrrolidone, polyacrylates including polyacrylic acid derived materials, polycarboxylates, polyethylene glycols, poly(1 ,4- phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), hydrophobic organic polymers including polyvinylidene fluoride, graphene, graphene oxide, fluorinated graphene, polyvinyl epoxies, polyethylene, polystyrene, polyvinylchloride, polytetrafluorethylene, polymers have silane moieties, polydimethylsiloxane, polyesters, polyurethanes, polylactic acid and derivatives thereof, or biopolymer-based materials such as polysaccharide gums including xantham gum and guar gum, alginates, chitosan, cellulose- based polymers including cellulose, cellulose acetate, cellulose acetate esters, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), carboxymethyl cellulose (CMC), Polybenzimidazole (PBI), polyetherimide (PEI), polyacrylamide (PAM), polyurethane dispersions (PUDs), polyvinyl butyral (PVB), polyethyleneimine (PEI), polyaniline (PANI), polypyrrole (PPy), polyhydroxyalkanoate (PHA), polyoxymethylene (POM), thermoplastic polyurethane (TPU), polyfurfuryl alcohol (PFA), carboxymethyl starch (CMS), gum arabic or any mixtures and combinations thereof.

[0164] The polymeric organic binder may be a blend of two or more of cellulose-based polymer, polyvinyl alcohol, polyurethane, polyacrylate and epoxide, preferably the cellulose- based polymer is hydroxyethyl cellulose or methyl cellulose and the blend contains one or more components having cross-linking functionality.

[0165] The Inventors have found that the use of hydrophilic binders, such as PVA and polysaccharides, may improve air stability of the adsorbent bodies.Substrate

[0166] Preferably, the substrate(s) is a non-MOF substrate(s). The substrate(s) may be an inert material and / or a material having chemical activity. Preferably the substrate(s) is thermally conductive. Preferably the substrate(s) is electrically conductive. For example, the substrate(s) may be selected from the group consisting of: alumina, cordierite, stainless steel, aluminium, carbon, conductive ceramics (such as indium tin oxide), Yttria-stabilized zirconia (YSZ), carbon fibre, organic polymers such as polyethylene, polypropylene and combinations thereof. The substrate(s) may be porous or non-porous. The substrate(s) may be a parallel channel contactor.

[0167] The substrate(s) may be flexible or the substrate(s) may be rigid. The substrate(s) may be planar, such as a planar sheet. Thus, the adsorbent body may be coated onto one or both of the two planar surfaces of the planar sheet. The planar substrate may comprise apertures. The planar substrate may comprise a mesh. The planar substrates may be stacked together to form larger adsorbent substrate assemblies, in this embodiment the term substrate includes substrate assembly.

[0168] The substrate(s) may comprise a series of substantially parallel or parallel channels. The substantially parallel or parallel channels may have a cross-sectional channel diameter of from about 0.1 mm to about 5 mm, preferably from about 0.5 mm to about 4 mm, preferably from about 1 mm to about 3 mm. The shape of the substantially parallel or parallel channels may be square, hexagonal or circular. The substantially parallel or parallel channels may be formed from corrugation of the substrate, for example, corrugation of planar sheets of the substrate to provide e.g. sinusoidal channels. Alternatively they may be formed by extrusion of substrate material(s) through suitable die-plates followed by cutting and drying to form monoliths comprising the substantially parallel or parallel channels. It is well within the remit of the skilled person to identify an appropriate method of preparing substrates having substantially parallel or parallel channels. The substrate(s) comprising the substantially parallel or parallel channels may have a cross-sectional diameter of from about 1 cm to about 3 cm. The substantially parallel or parallel channels may have a consistent cross-sectional shape. ‘Parallel channel’ used herein means channels which are side by side, having the same distance continuously between them. By “substantially parallel channel” is meant that thechannel deviates from ‘true’ parallel by less than about 1 °, preferably less than about 0.5°, preferably less than about 0.1°.

[0169] The adsorbent body may be coated onto the substrate body, including on the surface of the substrate body in the parallel channels.

[0170] When the adsorbent body is coated on a substrate. The adsorbent body coating around the substrate(s) may be present at a depth of from about 10 microns (pm) to about 200 microns (pm), preferably from about 10 microns (pm) to about 100 microns (pm). The depth of the adsorbent body coating around the substrate(s) is measured by scanning electron microscopy (SEM) as described herein.

[0171] The depth of the adsorbent body coating around the substrate(s) may be uniform or irregular. Preferably, the depth of the adsorbent body coating around the substrate(s) is uniform.Wet MOF binder mass.

[0172] The wet binder mass or wet MOF binder mass is formed in step (b). Typically, the wet binder mass or wet MOF binder mass will comprise from about 20 wt.% solids to about 60 wt% solids content. Typically the wet binder mass or wet MOF binder mass will comprise from about 3% to about 40%, or from about 30% or to about 20% binder by weight of the theoretical mass of MOF in the wet binder mass or wet MOF binder mass.

[0173] The wet binder mass or wet MOF binder mass may comprise less than about 20%, less than about 15%, or less than about 10%, or less than about 5%, or less than about 3% binder by weight of the wet binder mass or wet MOF binder mass.

[0174] The wet MOF binder mass (wet binder mass) may comprise from about 10 % to about 90% total solvent (including reaction solvent) by weight of the wet MOF binder mass (wet binder mass) depending on the solvent level of the wet MOF reaction mass (wet MOF mass), the level of any solvent provided with the binder and any solvent, such as water, used as a diluent, for example to lower the viscosity of the wet MOF binder mass (wet binder mass) for spraying onto a substrate. Each of these solvents may be the same or may be different, for example the reaction solvent may be different from solvent used a diluent. Preferably, the solvent(s) are water or substantially aqueous.Undried binder mass or partially dried MOF binder mass.

[0175] The undried binder mass or partially dried MOF binder mass is formed the partial drying step. It may be preferred for the undried binder mass or partially dried MOF binder mass to comprise less than about 75% solvent, or less than about 70% solvent or less than about 60% solvent or even less than about 50% solvent by weight of the undried binder mass or partially dried MOF binder mass. For any given adsorbent framework, the undried binder mass or partially dried MOF binder mass contains less solvent than the wet binder mass or wet MOF binder mass.

[0176] The undried binder mass or partially dried MOF binder mass may comprise less than about 20%, or less than about 15%, or less than about 10%, or less than about 5%, binder by weight of the undried binder mass or partially dried MOF binder mass.

[0177] Typically, it is important to control the rheology of the undried binder mass or partially dried MOF binder mass. The rheology of the undried binder mass or partially dried MOF binder mass is a complex combination of factors such as framework particle (MOF crystallite) size, amount of reaction solvent present, amount of unreacted MOF precursors remaining, nature of the binder, and presence of other materials. Typically, it is necessary for mixes being cut to be sufficiently “solid-like” if they are to be successfully cut without smearing. One measure of how “solid-like” a material is its viscosity. Typically, it is therefore important for the viscosity of the undried binder mass or partially dried MOF binder mass to be within certain limits.

[0178] Thus, the undried binder mass or partially dried MOF binder mass in preferred methods of the present invention, typically has a viscosity at 10 s-1and 25 °C of greater than about 3.0 x 105mPa.s or greater than about 4.0 x 105mPa.s or greater than about 5.0 x 105mPa.s or greater than about 6.0 x 105mPa.s or greater than about 7.0 x 105mPa.s or even greater than about 1.0 mPa.s x 106mPa.s. The preferred viscosity may be chosen based on the nature and design of the cutting and subsequent processing steps. In preferred methods of the present invention, the undried binder mass or partially dried MOF binder mass typically has a viscosity at 10 s-1and 25 °C of less than about 3.0 x 106mPa.s or less than about 2.0 x 106mPa.s or less than about 1 .25 x 106mPa.s.Undried adsorbent body or shaped MOF body.

[0179] The undried adsorbent body or shaped MOF body is formed in the shaping step. This may be formed by extrusion and / or cutting or other forming processes described hereinincluding injection molding, spreading, spraying or painting. The undried adsorbent body or shaped MOF body may comprise less than about 50wt% solvent.Dried adsorbent body or (first or second) dried MOF body.

[0180] The dried adsorbent body or (first or second) dried MOF body is formed by removing at least some of the remaining solvent from the undried adsorbent body, shaped MOF body or washed MOF body.Washing solvent.

[0181] The washing solvent may be selected from one or more of the following: water (preferably, water heated to greater than about 90 °C, or greater than about 100 °C), acetone, DMSO, short-chain length alcohols (C1 to C4), glycols and mixtures thereof. Preferred washing solvents include water (preferably, water heated to greater than about 90 °C, or greater than about 100 °C) and lower molecular weight alcohols (short-chain length alcohols, C1 to C4) including ethanol and methanol, or combinations thereof. The washing solvent can comprise a mix of solvents. More than one washing solvent could be used in the washing step. Typically, the washing solvent is not the same as the reaction solvent.Washed adsorbent body.

[0182] The washed adsorbent body may be optionally formed in the optional step in which the dried adsorbent body or dried MOF body may be contacted with washing solvent to form a washed adsorbent body or washed MOF body.Unactivated adsorbent body.

[0183] The unactivated adsorbent body may describe the dried adsorbent body or (first or second) dried MOF body prior to the activation step.Adsorbent body.

[0184] The adsorbent body comprises metal-organic framework material and binder, preferably organic polymeric binder. Typically, the adsorbent body has an envelope density of greater than about 0.3 g / cm3, or greater than about 0.7 g / cm3. The adsorbent body may havean envelope density of less than about 1.5 g / cm3, or less than about 1.2 g / cm3, or less than about 1.0 g / cm3.

[0185] The adsorbent body may have a BET area of from about 300 m2 / g to about 1800 m2 / g, or from about 500 m2 / g to about 1700 m2 / g, or from about 600 m2 / g to about 1600 m2 / g, or from about 700 m2 / g to about 1500 m2 / g.

[0186] Typically, the adsorbent body may have a mean particle diameter of greater than about 0.25 mm, preferably greater than about 0.4 mm.

[0187] Typically, the adsorbent body comprises: (i) more than about 70%, or more than about 75%, or more than about 80%, or more than about 85%, metal-organic framework material by weight of the adsorbent body; and (ii) less than about 30%, or less than about 20%, or less than about 15%, or less than about 10%, binder by weight of the adsorbent body.

[0188] Each and every reference referred to herein is hereby incorporated by reference in its entirety, as if the entire content of each reference was set forth herein in its entirety.

[0189] While particular examples and / or embodiments of the present invention have been illustrated and described, it would be obvious 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. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

[0190] Aspects of the invention are further described with reference to the following numbered paragraphs:1 . A process for the production of an adsorbent body, wherein the process comprises the steps of a) forming a wet metal-organic framework reaction mass, wherein the wet metal-organic framework reaction mass comprises: (i) from about 20% to about 70% of a metalorganic framework by weight of the wet metal-organic framework reaction mass; (ii) from about 3% to about 50% unreacted MOF precursors by weight of the MOF in the wet MOF reaction mass; (iii) from about 10 % to about 70 % of reaction solvent by weight of the wet metal-organic framework reaction mass; b) contacting the wet framework reaction mass with a binder to form a wet binder mass; c) partially drying the wet binder mass to form an undried binder mass;d) forming the undried binder mass into an undried adsorbent body; e) removing at least some of the remaining solvent from the undried adsorbent body to form a dried adsorbent body; f) activating the dried adsorbent body by subjecting the dried adsorbent body to a temperature of greater than about 100 °C to form an adsorbent body. A process according to paragraph 1 wherein the wet metal-organic framework reaction mass comprises from about 30% to about 70% of a metal-organic framework by weight of wet metal-organic framework reaction mass and from about 10 % to about 50 % of reaction solvent by weight of the wet metal-organic framework reaction mass. A process according to paragraph 1 or paragraph 2 wherein(i) after step (d) and before step (e), the process comprises at least one washing step (d1) contacting the undried adsorbent body with a washing solvent so as to remove unreacted materials and / or reaction by-products, and / or(ii) step (a) is carried out by contacting together metal-organic framework precursor materials at least partially in solid form and reaction solvent at temperatures from about 20 °C to about 100 °C, so as to form a wet metal-organic framework reaction mass, and / or(iii) step (c) is carried out by (1) evaporation of solvent; and / or (2) addition of an adsorbent material having a lower solvent level than the wet binder mass, to the wet binder mass, wherein the adsorbent material is selected from one or more of silica, zeolite, activated carbon, graphene, metal-organic frameworks or combinations thereof, and / or(iv) step (e) is carried out at temperatures less than about 150 °C, preferably less than about 100 °C, preferably less than about 60 °C, and / or(v) step (b) and step (c) are carried out simultaneously, and / or(vi) the wet metal-organic framework reaction mass is not subject to a solvent exchange process. A process according to any of paragraphs 1 to 3 wherein step (d) is carried out by (i) an extrusion process, (ii) an injection moulding process, (iii) a cutting process, or (iv) a milling process. A process according to any of paragraphs 1 to 4 wherein the binder in step (b) is in the form of (i) a solution, (ii) dispersion, (iii) a partially solvated powder or (iv) a finely dispersed powder. A process according to any preceding paragraph wherein the binder is(i) a polymeric organic binder selected from one or more of the following: polyvinyl alcohol (P A), polyvinyl acetate, polyvinyl alcohol / acetate copolymers, polyimide, polyamide, polyvinyl pyrrolidone, polyacrylates include polyacrylic acid, polycarboxylates, polyethylene glycols, poly(1 ,4- phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), hydrophobic organic polymers including polyvinylidene fluoride, graphene, graphene oxide, fluorinated graphene, polyvinyl epoxies, polyethylene, polystyrene, polyvinylchloride, polytetrafluorethylene, polydimethylsiloxane, polyesters, polyurethanes, polylactic acid and derivatives thereof, or biopolymer-based materials such as polysaccharide gums including xantham gum and guar gum, alginates, chitosan, cellulose-based polymers including cellulose, cellulose acetate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), carboxymethyl cellulose (CMC) or any mixtures and combinations thereof, preferably wherein the polymeric organic binder a blend of a cellulose-based polymer and polyvinyl alcohol, preferably the cellulose-based polymer is hydroxyethyl cellulose or methyl cellulose, or(ii) an inorganic binder selected from one or more of the following: silicas including colloidal silica suspensions, aluminas including hydrated aluminas and aluminosilicates. A process according to any preceding paragraph, wherein the metal-organic framework (MOF) comprises metal ions selected from the group consisting of: Zn2+, Zr2+, Cu2+, Al3+, Mn2+, Mg2+, Nb2+, Fe2+, Fe3+, Ti2+, Ti3+, Ti4+, Co2+, Cr2+, Ni2+, Ca2+and mixtures and combinations thereof, preferably wherein the metal-organic framework is a Zr-containing metal-organic framework and the metal-organic framework precursor materials comprise a Zr metal salt that has been pre-reacted to form Zr6metal clusters. A process according to any preceding paragraph, wherein the undried binder mass formed in step (c) has a viscosity at 10s-1and 25 °C of from about 3.0 x 105mPa.s to about 3.0 x 106mPa.s. A process according to any preceding paragraph, wherein(i) the reaction solvent comprises one or more of the following: water, acetone, DMSO, C1-C4 short-chain length alcohols, C1-C4 short-chain organic acids, glycols and mixtures thereof, preferably wherein the reaction solvent comprises more than 50 wt% water, and / or(ii) the washing solvent is selected from one or more of the following: water, acetone, DMSO, C1-C4 short-chain length alcohols, glycols, C1-C4 organic acids and mixtures thereof.10. A process according to any preceding paragraph wherein the binder is partially solvated by pre-mixing with one or more solvents selected from the group consisting of: water, acetone, DMSO, short-chain length alcohols, short-chain organic acids, glycols and mixtures thereof.11 . A process according to any preceding paragraph, wherein the adsorbent body comprises: (i) more than about 75% metal-organic framework material by weight of the adsorbent body; and (ii) less than about 20% binder by weight of the adsorbent body.12. A process according to any preceding paragraph, wherein the undried adsorbent body is subjected to a spheronisation treatment.13. A process according to any preceding paragraph, wherein the metal-organic framework comprises MOF crystallites, preferably wherein the MOF crystallites have a mean particle size of from about 30 nm to about 100 nm.14. An adsorbent body or bodies made according to the process of any preceding paragraph wherein the bodies have an envelope density of greater than about 0.3 g / cm3and less than about 1.5 g / cm3.15. The use of an adsorbent body or bodies according paragraph 14 for gas storage and / or purification, preferably hydrogen storage and carbon dioxide capture.MethodsMethod of measuring viscosity.

[0192] Suitable equipment for measuring the viscosity of undried binder mass or partially dried MOF binder mass is an Anton Paar MCR 92 Rheometer with a 25 mm diameter plate, a 25 degree angle cone with a gap of 3.0 mm and measured at 25 °C. A sample of ~ 2g is placed on the plate, the upper cone lowered to the target gap distance, excess sample removed from the sides and the rotational viscosity measured. Typically the viscosity is measured over a range up to a shear rate of 50 s 1. For the purpose of this document, the viscosity of a material is the viscosity measured at 10 s-1and 25 °C.Measurement of crystallite sizes by microscopic analysis.

[0193] A preferred way to measure the dimensions of the MOF crystallites especially after formation into a larger MOF body, is to use microscopic examination using SEM or TEM equipment. Suitable TEM equipment includes the JEOL JEM 2100. Suitable SEM equipment includes the FEI Quanta 3D.

[0194] Typically, the particle size distribution of the MOF crystallites comprising the MOF body is measured by breaking the MOF body into smaller fragments to expose internal surfaces, sieving the fragments to between 500 microns and 250 microns, and mounting the fragments onto the microscope stub. The MOF crystallites making up the MOF body retain discernible individual dimensions, and these can be seen forming the various exposed surfaces. The diameter of a crystallite of MOF can be measured by visual examination by drawing the longest possible line between diametrically opposing internal surfaces. Alternatively and preferably, software such as Imaged can be used. Typically, at least 50 observations of separate particles will need to be made to give statistically valid results for the particle size distribution. Typically, multiple (e.g., at least five) different surfaces need to be examined from at least ten randomly selected particles within the field of view of each surface. Statistical analysis can then be used determine the mean particle size and other parameters of the size distribution.Method for measuring the BET area of an adsorbent body.

[0195] The BET surface area of an adsorbent body can be measured by use of ASTM method D3663-03 “Standard test method for surface area of catalysts and catalyst carriers”. The BET surface area is determined by measuring the volume of nitrogen gas adsorbed at various low- pressure levels by the monolith sample. Pressure differentials caused by introducing the monolith surface area to a fixed volume of nitrogen in the test apparatus are measured and used to calculate BET surface area. Suitable equipment for measuring BET surface area include the 3Flex from Micromeritics Corporation, used according to the manufacturer’s guidelines.Determination of the composition of the wet MOF reaction mass of MOF.1 . The amount of MOF in a reaction mass is determined as follows. A measured sample of the wet MOF reaction mass, typically ~1g of mix, is subjected to a series of washing steps followed by drying at 100 °C under vacuum. The sample is dispersed in washingsolvent, typically ethanol, methanol or an aqueous mix of these, and then centrifuged at high speed to separate the solid. Suitable conditions are centrifuging for 25min at 5250rpm using the Beckman-Coulter J-15R. The liquid is then decanted and a fresh batch of washing solvent added and the procedure repeated three times. The sample is then dried at 100 °C under vacuum to remove all solvent and the residual mass carefully weighed. The residual mass is the mass of MOF in the wet MOF reaction mass. The % of MOF in the wet reaction mass can be calculated by dividing the mass of residual MOF by the mass of the original wet MOF reaction mass. The mass of MOF can also be used to calculate the % yield from the known quantities of MOF precursors added to form the mix and the mass of MOF that would be formed at 100% yield.2. Determination of solvent level in a sample. The wt% of solvent in a wet MOF reaction mass is calculated by drying a carefully weighed 1g reaction mass at 100 °C under vacuum until there is no further weight loss, carefully measuring the weight of the residual mass and calculating the % wt loss compared to the original mass of the wet MOF reaction mass. The % wt loss is the wt % of solvent in the sample.3. The wt % of unreacted MOF precursors can be directly determined by subtracting the % values calculated in (1) and (2) from 100%. This also allows the amount of unreacted MOF precursors as a % of the amount of MOF present to be directly calculated.Method for determining the level of organic polymeric binder in a MOF body.

[0196] The level of organic polymeric binder in MOF body can be determined by thermo- gravimetric methods based on weight loss at elevated temperatures. The high temperatures used (600°C) will burn off the organic species leaving metal oxide species etc behind. The difference in % weight loss between a sample of MOF and a sample of MOF plus binder shows the level of binder. The MOF body is crushed and a sample of the MOF body material is heated up to 600 °C and the weight loss when at steady state is measured and normalised. A sample of the MOF itself is then heated under identical conditions and the weight loss normalised. The difference between the % wt losses is the % of binder present in the adsorbent body.Method for measuring envelope density of an adsorbent body

[0197] The envelope density of a body is measured by dividing the weight of a body (in grams) by its envelope volume (in cm3). The envelope volume is defined in ASTM D3766 as “the ratio of the mass of a particle to the sum of the volumes of the solid in each piece and the voids within each piece, that is, within close-fitting imaginary envelopes completely surrounding each piece".

[0198] The envelope density of a body can be measured using any technique that can used to measure the volume of the MOF material, provided that the measurement technique to measure the external dimensions of the MOF body or material is accurate. Measurement of a distance such as a cross sectional diameter using optical means should give the same results as a micrometer.

[0199] Suitable methods depend on the nature of the MOF body being measured. Techniques suitable for measuring a MOF body as an extrudate will not work for a coated substrate. Suitable methods for each are described below.

[0200] For example, the envelope density can be measured by mercury porosimetry. At atmospheric pressure, mercury does not intrude into internal pores. Therefore, the volume of mercury displaced by a body at atmospheric pressure is the envelope volume of the body. Dividing the weight of the sample by this volume gives the envelope density. The use of mercury porosimetry is described below.

[0201] One suitable technique for larger bodies such as an extrudate, such as those with a diameter > 1.5 mm, is to use accurate 3-D scanners to measure the volume of individual bodies. Suitable equipment includes the Leica BLK360. By weighing the body prior to scanning, the envelope density of the body can be calculated as described above.

[0202] The volume of larger, uniform bodies such as extrudates, can also be measured using micrometers to measure diameters and lengths of an extrudate and hence the volume provided the cross-sectional area is known.

[0203] A suitable technique for smaller MOF bodies, such as milled monoliths or granules, is to use powder pycnometers. Powder pycnometers use the volume displacement of a very fine, free-flowing test powder. Suitable equipment includes the GeoPyc Model 1360 from Micrometrics Instrument Corp. Powder pycnometers, when operated as per manufacturersinstructions are used to measure the envelope volume of a known mass of sample, this allows the envelope density to be calculated as described above. Other techniques based on the Archimedes principle of volume displacement can also be used, for example mercury porosimetry. At atmospheric pressure, mercury does not intrude into internal pores. Therefore, the volume of mercury displaced by a body at atmospheric pressure is the envelope volume of the body. Dividing the weight of the sample by this volume gives the envelope density.

[0204] The envelope volume of MOF material coating a non-MOF substrate, such as an extrudate having a non-uniform cross-sectional shape such as a trilobe, or a flat, planar substrate can be measured by optical means. The weight per unit of uncoated non-MOF substrate is measured. The weight and length of a MOF-coated non-MOF substrate is measured and the mass of MOF material per unit can be calculated by subtracting the mass per unit of uncoated non-MOF substrate from the mass / unit length of the coated substrate. The MOF-coated non-MOF substrate id then be cross-sectioned and a cross-sectioned piece placed on a SEM mount to allow examination of the cross-section. The dimensions of the thicknesses of the MOF material coating can be calculated by taking repeated measurements of the thickness at regular points around the perimeter of the substrate using software such as Imaged. Then an average thickness of the coating layer can be calculated by averaging results. This then will give a MOF material coating volume per unit of substrate. This will then allow the envelope density to be calculated as described herein.Method for Measuring Relative Density

[0205] Relative Density refers to the ratio of the envelope density of a crystalline adsorbent body compared to the single crystal density of the adsorbent material.

[0206] The single crystal density of a MOF is the density of a single crystal and is calculated theoretically from the structure. Structural and other information for MOFs, such as single crystal density, is theoretically calculated. Crystal density data for MOFs and other crystalline materials is available from the Cambridge Structural Database at the Cambridge Crystallographic Data Centre.

[0207] Relative densities of much less than 1 , such as less than 0.4, mean that there is excess porosity, mostly in the form of larger (hence less useful) pores in the body. Relative densities significantly greater than 1 , such as 1.4, imply a wasteful loss of porosity as such high values can only be achieved by destroying some of the useful pores.Method of measuring coating depth

[0208] Measured by SEM as described in relation to envelope density.Method of Measuring Parallel Channel Diameters

[0209] This can also be measured by image analysis of cross-sectional samples using SEM as described herein.Examples.

[0210] Aspects of the invention will now be demonstrated by reference to the following nonlimiting examples.

[0211] Unless otherwise mentioned, room temperature and pressure are 20 °C (293.15 K, 68 °F) and 1 atm (14.696 psi, 101.325 kPa), respectively. All reagents unless otherwise stated were obtained from commercial sources and were used without further purification.

[0212] Unless otherwise stated, all measurements herein are taken at room temperature and pressure.Bodies of HKUST-1 using different bindersolvent levels.

[0213] 1.83 g (9.2 mmol) of copper acetate monohydrate and 1.23 g (6.1 mmol) of 1 ,2,4- benzene tricarboxylic acid were mixed in a glass vial with 1.2 ml of ethanol and 4.87 ml of water. This gave a reaction mix of having a solids content of 37.6 wt% and a solvent level of 62.4 wt%.

[0214] The mixture was heated at 60 °C for 2 hours with constant stirring using the stirrer bar. The reaction mixture formed a thick gel.

[0215] After finishing the desired reaction, 0.36 g of methylcellulose (MC) binder was added as a powder. The mixture suddenly formed a very thick paste which was stirred well to mix the binder uniformly. The paste was too sticky and soft to be formed into handleable bodies. The paste was then left to dry at 60 °C for three days. After two hours the paste could be formedinto non- sticky individual bodies. After the further drying, the solid bodies were very hard and robust. They were then solvent exchanged with ethanol for 4 days, and then dried at room temperature followed by activating by heating to 150 °C under vacuum for 8h.HKUST-1 Synthesis and binder addition dissolved / dispersed in different amounts of solvents.

[0216] Three batches of 1.83 g (9.2 mmol) of copper acetate monohydrate and 1.23 g (6.1 mmol) of 1 ,2,4-benzene tricarboxylic acid were mixed in glass vials and 1 .2 ml of ethanol and 4.87 ml of water were added to each batch and the mixtures heated at 60 °C for 2 hours with constant stirring using the stirrer bar. The reaction mixtures formed thick gels.

[0217] After finishing the desired reaction, 0.36 g of Methylcellulose binder dissolved / dispersed in different amounts of solvents was added to each vial, forming very thick pastes. a. 0.36g of MC mixed with 0.9ml of ethanol b. 0.36g of MC mixed with 3.6ml of ethanol c. 0.36g of MC mixed with 9.0 ml of ethanol

[0218] The thick pastes were stirred well to mix the binder uniformly and then left to dry at 60 °C for three days. All of the mixes could be formed into bodies by manual manipulation after drying for 2 to 4 hours. After the rest of the drying, the solid bodies were then solvent exchanged with ethanol for 4 days, and then dried at room temperature. They were then activated by heating to 150 °C under vacuum for 8h.MOF-808 synthesis and binder addition.

[0219] 30 g of Zr6O8zirconium oxo-clusters and 7.5 g of 1 ,2,4-benzene tricarboxylic acid were mixed in a glass vial with 19.6 ml of water and 17.5 ml of acetic acid. The reaction mixture was stirred well and heated at 90 °C for 18 hours. The gel formed was mixed with 5.58 g of MC pre-dissolved in 140 ml of a 1 :1 mix of water / ethanol. The mixture was mixed well and then dried at 60 °C to form into solid bodies by extrusion through a syringe followed by further drying. Dried bodies were solvent exchanged with ethanol for 4 days, dried at 40-50°C, and activated at 150 °C under vacuum for 8 hrs.ZU-301 synthesis and binder addition.

[0220] Zinc carbonate, basic, (250 mg, 0.45 mmol) was dissolved / dispersed in water (0.47 mL) and heated at 90 °C. Oxalic acid (102.5 mg, 1.14 mmol) and 3-methyl-1 ,2,4-triazole (189 mg, 2.28 mmol) were dissolved in water / ethanol (0.24 / 0.24 ml). This solution was then added to the zinc carbonate solution / dispersion with stirring followed by further stirring for 18 h at 60 °C. The gel formed was then mixed with 0.386 g of MC pre-dissolved in 1 .93 ml of water. The mixture was mixed well and then partially dried at 40 °C for 4 hours to form an undried mass that could be formed into bodies. These were further dried at 40 °C for 2 days and the dried bodies were solvent exchanged with ethanol for 4 days, dried, and activated under vacuum at 150 °C for 8 hours.CALF-20 Synthesis and binder addition.

[0221] Zinc carbonate basic (250 mg, 0.45 mmol) was dissolved / dispersed in water (0.47 mL) and heated at 90 °C. Oxalic acid (102.5 mg, 1.14 mmol) and 1 ,2,4-triazole (157 mg, 2.28 mmol) were dissolved in water / ethanol (0.24 / 0.24 ml). This solution was then added to the zinc carbonate solution / dispersion with stirring followed by further stirring for 18 h at 60 °C. The gel formed was then mixed with 0.386 g of MC pre-dissolved in 1.93 ml of water. The mixture was mixed well and then partially dried at 40 °C for 4 hours to form an undried mass that could be formed into bodies. These were further dried at 40 °C for 2 days and the dried bodies were solvent exchanged with ethanol for 4 days, dried, and activated under vacuum at 150 °C for 8 hours.MOF-coated non-MOF substrate body synthesis

[0222] 3.750g of zinc carbonate basic was mixed in water (5.69 mL) and heated at 90 °C with stirring. 2.640g of 3,4-dihydroxy benzoic acid and 2.359g of 1 ,2,4-triazole was dissolved in a mixture of 2.85 mL ethanol and 2.85 mL water. The solution was then added to the zinc carbonate solution with stirring. The resultant mixture was stirred at 90 °C for 18 h. The final yield was 6 g.Binder addition procedure

[0223] The amount of binder was calculated based on the final mass of the IMM-31. 20% of MC solution and 20% acrylic solution was added to the above prepared MOF and stirred for 30 minutes.Coating procedure

[0224] 1.036 g of trilobe (cordierite) was dipped into the above MOF-binder solution. The solution was mixed well with trilobes inside and kept undisturbed for 30 minutes. After that, the trilobes were removed and dried at room temperature overnight. The trilobes were then heated at 150 °C overnight to cross-link the binder. The MOF-coated trilobes were then solvent exchanged with boiling water at 90 °C for 2-3 days. The MOF-coated trilobes were subsequently dried and activated at 150 °C. Final weight was 1.3 gram.

Claims

Claims1. A process for the production of an adsorbent body, wherein the process comprises the steps of(a) providing a wet metal-organic framework (MOF) mass, wherein the wet metal-organic framework mass comprises metal-organic framework, unreacted MOF precursors, and from about 10 % to about 85 % of reaction solvent by weight of the wet metal-organic framework mass;(b) contacting the wet metal-organic framework mass with a binder to form a wet MOF binder mass;(c) shaping the wet MOF binder mass into a shaped MOF body;(d) drying the MOF body to form a first dried MOF body;(e) optionally, contacting the first dried MOF body with a washing solvent so as to remove unreacted materials and / or reaction by-products and form a washed MOF body;(f) optionally, removing at least some of the remaining solvent from the washed MOF body to form a second dried MOF body;(g) activating the first dried MOF body, the second dried MOF body, or the washed MOF body by subjecting the first dried MOF body, the second dried MOF body orthe washed MOF body to a temperature of greater than about 100 °C to form an adsorbent body.

2. A process according to claim 1 , where the wet MOF mass comprises from about 10 % to about 70 % of reaction solvent by weight of the wet metal-organic framework mass.

3. A process according to claim 1 or claim 2 wherein the wet MOF mass comprises from about 20% to about 70% of a metal-organic framework by weight of the wet metal-organic framework mass.

4. A process according to any preceding claim wherein the wet MOF mass comprises from about 3% to about 50% unreacted MOF precursors by weight of the wet metal-organic framework mass.

5. A process according to any preceding claim wherein the wet MOF mass comprises from about 30% to about 70% of a metal-organic framework by weight of wet metal-organic framework mass and from about 10 % to about 50 % of reaction solvent by weight of the wet metal-organic framework mass.

6. A process according to any preceding claim wherein the wet MOF binder mass comprises from about 10% to about 90% total solvent by weight of the wet MOF binder mass.

7. A process according to any preceding claim wherein(i) after step (d) and before step (g), the process comprises at least one washing step (e) contacting the dried MOF body with a washing solvent so as to remove unreacted materials and / or reaction by-products and form a washed MOF body,(ii) when the process comprises step (e), the process comprises after step (e) and before step (g), removing at least some of the remaining solvent from the washed MOF body to form a second dried MOF body (step (f)); and / or(iii) step (a) is carried out by contacting together metal-organic framework precursor materials at least partially in solid form and reaction solvent at temperatures from about 20 °C to about 100 °C, so as to form a wet metal-organic framework mass, and / or(iv) step (c) is carried out by(1) partial evaporation of solvent from the wet MOF mass followed by one or more of extrusion, cutting and coating of a substrate; or(2) addition of an adsorbent material having a lower solvent level than the wet MOF binder mass, to the wet MOF binder mass, wherein the adsorbent material is selected from one or more of silica, zeolite, activated carbon, graphene, metal-organic frameworks or combinations thereof, followed by one or more of extrusion, cutting and coating of a substrate and / or(3) coating a substrate with the wet MOF binder mass;(v) step (d) is carried out at least initially at temperatures less than about 100 °C, preferably less than about 60 °C, and / or(vi) the wet MOF mass is not subject to a solvent exchange or washing process.

8. A process according to any of claims 1 to 7 wherein step (c) is carried out by (i) an extrusion process, (ii) an injection moulding process, (iii) a cutting process, (iv) a milling process, or (v) a coating process.

9. A process according to any of claims 1 to 8 wherein step (d) is carried out in two stages: (i) at less than about 100 °C, preferably for about 1 hour or greater, followed by (ii) greater than about 100 °C, preferably for about 1 hour or greater.

10. A process according to any of claims 1 to 9 wherein the binder in step (b) is in the form of (i) a solution, (ii) dispersion, (iii) a partially solvated powder or (iv) a finely dispersed powder.11 . A process according to any preceding claim wherein the binder is(i) a polymeric organic binder selected from one or more of the following: polyvinyl alcohol (PVA), polyvinyl formal, polyimide, polyetherimide, polyamide, polyvinyl pyrrolidone, polyacrylate including polyacrylic acid derived materials including copolymers of methyl and ethyl methacrylate, polycarboxylate, polyethylene glycol, polysulfone, polyethersulfone including poly(1 ,4- phenylene-ether-ether-sulfone) (PFEES), poly(tetrahydrofuran) (PTHF), polyvinylidene fluoride, graphite, graphene, graphene oxide, fluorinated graphene, polyvinyl epoxies, polyethylene, polystyrene, polyvinylchloride, polytetrafluorethylene, silane including tetraethoxysilane (TEOS) and methyltriethoxysilane, polymers having silane moieties, polysiloxanes including polydimethylsiloxane, polysulfone, tetraisopropyl orthosilicate, poly-ethylene oxide polymer including block co-polymers such as PEO-PPO block co-polymers, polyolefin, epoxide and epoxy resin, polyesters, polylactic acid and derivatives thereof, polybenzimidazole (PBI), polyetherimide, polyacrylamide (PAM), polyurethane including polyurethane dispersions (PUDs), polyvinyl butyral (PVB), polyethyleneimine (PEI), polyaniline (PANI), polypyrrole (PPy), polyhydroxyalkanoate (PHA), polyoxymethylene (POM), thermoplastic polyurethane (TPU), polyfurfuryl alcohol (PFA), biopolymer-based material such as sesbania powder, polysaccharide gums including xantham gum and guar gum, alginate, chitosan, cellulose-based polymer including cellulose, cellulose acetate, cellulose acetate ester, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), carboxymethyl cellulose (CMC), carboxymethyl starch (CMS), gum arabic, or any mixtures and combinations thereof, preferably wherein the polymeric organic binder is a blend of two or more of cellulose-based polymer, polyvinyl alcohol, polyurethane, polyacrylate and epoxide, preferably the cellulose-based polymer is hydroxyethyl cellulose or methyl cellulose and the blend contains one or more components having cross-linking functionality, or(ii) an inorganic binder selected from one or more of the following: silica including colloidal silica suspension, alumina including hydrated alumina, aluminosilicate, Zeolite, magnesium silicate, sodium silicate, calcium silicate, titanium dioxide (TiO2), magnesium oxide (MgO), calcium carbonate (CaCO3), boron nitride (BN), kaolin (hydrated aluminium silicate), clay (e.g., bentonite, montmorillonite), calcium phosphate, zirconium oxide (ZrO2), and wollastonite (CaSiO3).

12. A process according to any preceding claim, wherein the metal-organic framework (MOF) comprises metal ions selected from the group consisting of: Zn2+, Zr2+, Cu2+, Al3+, Mn2+,Mg2+, Nb2+, Fe2+, Fe3+, Ti2+, Ti3+, Ti4+, Co2+, Cr2+, Ni2+, Ca2+and mixtures and combinations thereof, preferably wherein the metal-organic framework is a Zn-containing MOF, an Al- containing MOF, or a Zr-containing MOF, preferably wherein the metal-organic framework precursor materials comprise a Zr metal salt that has been pre-reacted to form Zr6metal clusters.

13. A process according to any preceding claim, wherein(i) the reaction solvent comprises one or more of the following: water, acetone, DMSO, C1-C4 short-chain length alcohols, C1-C4 short-chain organic acids, glycols and mixtures thereof, preferably wherein the reaction solvent comprises more than 50 wt% water, and / or(ii) the washing solvent is selected from one or more of the following: water, acetone, DMSO, C1-C4 short-chain length alcohols, glycols, C1-C4 organic acids and mixtures thereof.

14. A process according to any preceding claim wherein the binder is partially solvated by premixing with one or more solvents selected from the group consisting of: water, acetone, DMSO, short-chain length alcohols, short-chain organic acids, glycols and mixtures thereof.

15. A process according to any preceding claim, wherein the adsorbent body comprises: (i) more than about 70% metal-organic framework material by weight of the adsorbent body; and (ii) less than about 30% binder by weight of the adsorbent body.

16. A process according to any preceding claim, wherein the shaped MOF body is subjected to a spheronisation treatment.

17. A process according to any preceding claim, wherein the metal-organic framework comprises MOF crystallites, preferably wherein the MOF crystallites have a mean particle size of from about 5 nm to about 900 nm.

18. An adsorbent body made according to the process of any preceding claim wherein the adsorbent body is a coating layer on a substrate, wherein the coating has a thickness of less than about 200 microns.

19. An adsorbent body or bodies made according to the process of any of claims 1 to 17 wherein the bodies have an envelope density of greater than about 0.3 g / cm3and less than about 1.5 g / cm3.

0. The use of an adsorbent body or bodies according claim 18 or claim 19 for:(i) a gas separation process, preferably the gas separation process may be selected from the group consisting of carbon dioxide capture, krypton recovery, krypton purification, and combinations thereof;(ii) carbon dioxide adsorption;(iii) removing CO2 directly from the flue gas of an industrial process and / or directly from the air;(iv) separation of Kr from a mixture of Kr / CF4 / N2, to obtain pure Kr from a mixture of Kr, CF4and N2;(v) water adsorption, preferably water harvesting or heating, ventilation, and air conditioning (HVAC);(vi) gas storage, preferably hydrogen storage;(vii) field catalysis; and / or(viii) hydrocarbon separation and / or purification.

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