Method for producing an adsorbent

Abstract

The present invention relates to a method of making an adsorbent, the method comprising: (a) contacting an adsorbent material with an initial mixture to form an adsorbent mixture solvated in a first solvent; (b) removing the first solvent to remove at least a portion of the first solvent from the adsorbent mixture solvated in the first solvent to form an initial adsorbent; (c) contacting the initial adsorbent with a second solvent to form a binder-reduced adsorbent in the second solvent; and (d) solvent drying the binder-reduced adsorbent to form an adsorbent. The present invention further provides an adsorbent and a method of using said adsorbent in gas storage.

Description

[Technical field]

[0001] The present invention relates to a method for producing an adsorbent, the adsorbent(s) and the use of said adsorbent(s). The produced adsorbent is robust, resistant to wear and has high performance. The adsorbent is suitable for use in gas storage systems, and in particular in gas storage systems where the adsorbent is subject to movement and vibration during use, such as vehicle fuel tanks. The adsorbent typically has a desired porosity profile with high levels of micro- and meso-porosity and relatively low levels of macro-porosity, providing a dense adsorbent with high surface area. [Background technology]

[0002] Virtually all sorbent materials are synthesized or formed as fine powders and are not self-supporting. To be useful in industrial processes, these materials typically need to be formed into larger bodies to avoid problems such as compaction and channeling that reduce fluid flow and performance. Such larger bodies need to be mechanically robust and wear resistant to be industrially useful.

[0003] Many industrial methods exist for forming such fine powders into larger bodies, such as tablets or extrusions, usually by application of high pressure or the use of binder materials, or both. However, these methods very often result in a decrease in the adsorption properties of the adsorbent material. For example, the application of high pressures, often used in tablet formation methods, can destroy the internal pores of the adsorbent material. This is particularly relevant for more delicate materials, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). An example of a metal-organic framework (MOF) that is particularly prone to the collapse of internal pores is Zr-fumarate. Another MOF that is very difficult to form into tablets is Al-fumarate, which is believed to be due to its platelet-like crystals. The high pressures required to counter this microcrystalline morphology tend to collapse the internal pores, resulting in a significant loss of adsorbent capacity. Achieving a high density adsorbent body by simply applying high pressure during processing can be counterproductive if doing so results in significant collapse of the internal pores of the adsorbent material.

[0004] An alternative to tablet formation is the extrusion of porous materials with a binder. However, the use of binders introduces other problems. High levels of particulate binders, such as alumina, reduce the amount of adsorbent material within the body, thereby reducing the performance of the adsorbent body. High levels of binders applied as solutions or liquids very typically block the pores of the adsorbent material, reducing performance. However, if low levels of binders are used, the mechanical robustness of the adsorbent body, e.g., wear resistance, is typically not high enough.

[0005] An ideal adsorbent combines high adsorbent properties (usually measured by BET area and N2 adsorption isotherm) with physical robustness, e.g., wear resistance. It is also industrially preferable if the adsorbent combines high density with high surface area and good adsorption performance. High density means that less body volume is required for a given process requirement compared to a low density adsorbent. This can have enormous industrial advantages, such as smaller equipment, lighter weight, and therefore lower cost. These requirements are usually mutually contradictory. High surface area adsorbents are typically associated with low density.

[0006] Whether the internal pores of the MOFs or COFs within the adsorbent body have collapsed during processing is typically indicated by the relative density of the resulting MOF or COF bodies.

[0007] Relative density is defined as the bulk density of the MOF or COF body divided by the crystalline density of the MOF or COF. The crystalline density of a MOF or COF is the theoretical density of a single crystal of the MOF or COF. A large number of crystalline densities have been calculated and are available in the Cambridge Structural Database.

[0008] Different MOFs or COFs can have different crystalline densities depending on their structure. If the bulk density of the adsorbent is greater than the crystalline density (i.e., the relative density is >1), this is likely due to internal pore collapse. The greater the relative density is, the more the internal pores have collapsed, reducing the adsorption capacity. Limiting high relative densities is necessary to avoid inefficient internal pore collapse. However, it is typically desirable not to allow the relative density of the adsorbent to be much less than 1, as this would be volumetrically inefficient. Very low relative densities typically indicate excessive levels of undesirable larger macropores.

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

[0010] The bulk density of a body is calculated by multiplying the weight of the body (in grams) by its bulk volume (in cm 3 Bulk volume can be measured by dividing the mass by the mass of the solid matter (units of 10 ...

[0011] An ideal sorbent body may simultaneously satisfy what may appear to be contradictory requirements. It is desirable for the sorbent body to be robust and wear resistant. It is desirable for the sorbent body to have a high surface area to have good adsorption capacity. The sorbent body should ideally have a high relative density and bulk density to minimize the volume of material required for a given process. These requirements often appear to be incompatible. For example, high levels of particulate binders (such as aluminas or clays) are often required for robustness, but this reduces the sorption capacity of the sorbent body by reducing the amount of sorbent material present in the body. High levels of binders applied as a solution or liquid can block the pores of sorbent materials such as MOFs, thus reducing performance. However, the mechanical robustness of the sorbent body is typically not high enough when low levels of binders are used, especially in demanding applications.

[0012] The present invention addresses, at least to some extent, these and other problems with the prior art. Summary of the Invention [Means for solving the problem]

[0013] Thus, in a first aspect, the present invention provides a method for producing a composition comprising: (a) contacting an adsorbent material with an initial mixture to form a solvated adsorbent mixture in a first solvent, wherein the adsorbent material is selected from metal organic frameworks or precursors thereof, covalent organic frameworks or precursors thereof, zeolites, activated carbon, organic cages, aluminum formate, and any combination thereof, the initial mixture comprising a polymeric organic binder and a first solvent, the solvated adsorbent mixture comprising an adsorbent material, the polymeric organic binder, and the first solvent, wherein the polymeric organic binder is adsorbed onto a surface of the adsorbent material, and the first solvent is distributed throughout the solvated adsorbent mixture; (b) removing at least a portion of the first solvent from the adsorbent mixture solvated in the first solvent to form an initial adsorbate; (c) contacting the initial adsorbent with a second solvent to form a binder-reduced adsorbent, wherein during step (c) 20 wt % to 80 wt % of the polymeric organic binder (initially present in the initial adsorbent) is removed from the initial adsorbent and dissolved in the second solvent, the binder-reduced adsorbent comprising the adsorbent material, the polymeric organic binder, the second solvent, and residual first solvent, the polymeric organic binder being adsorbed on a surface of the adsorbent material, and the second solvent being distributed throughout the binder-reduced adsorbent; (d) solvent drying the reduced-binder adsorbent to form an adsorbent; A method for producing an adsorbent comprising: A method is provided, wherein the solubility of the polymeric organic binder in the first solvent is the same as or higher than the solubility of the polymeric organic binder in the second solvent.

[0014] The present invention also provides adsorbent(s), in particular adsorbent(s) produced by the methods of the present invention, and the use of such adsorbent(s) in adsorption-based processes (e.g. gas storage, in particular carbon dioxide or hydrogen storage). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Method for producing an adsorbent The method for producing the adsorbent comprises: (a) contacting an adsorbent material with an initial mixture to form a solvated adsorbent mixture in a first solvent, wherein the adsorbent material is selected from metal organic frameworks or precursors thereof, covalent organic frameworks or precursors thereof, zeolites, activated carbon, organic cages, and any combination thereof, the initial mixture comprising a polymeric organic binder and a first solvent, the solvated adsorbent mixture comprising the adsorbent material, the polymeric organic binder, and the first solvent, wherein the polymeric organic binder is adsorbed onto a surface of the adsorbent material, and the first solvent is distributed throughout the solvated adsorbent mixture; (b) removing at least a portion of the first solvent from the adsorbent mixture solvated in the first solvent to form an initial adsorbate; (c) contacting the initial adsorbent with a second solvent to form a binder-reduced adsorbent, wherein during step (c) 20 wt % to 80 wt % of the polymeric organic binder initially present is removed from the initial adsorbent and dissolved in the second solvent, the binder-reduced adsorbent comprising the adsorbent material, the polymeric organic binder, the second solvent, and residual first solvent, the polymeric organic binder being adsorbed on a surface of the adsorbent material, and the second solvent being distributed throughout the binder-reduced adsorbent; (d) solvent drying the reduced-binder adsorbent to form an adsorbent; comprising The solubility of the polymeric organic binder in the first solvent is the same as or higher than the solubility of the polymeric organic binder in the second solvent.

[0016] During the method, the adsorbent material may be contacted with a polymeric organic binder prior to contacting with the first solvent.

[0017] It may be preferred that the sorbent material is selected from Al fumarate or Zr fumarate, or UTSA-16, or CPO-27, or UiO-66, or aluminum formate, or NbOFFIVE, or CALF-15, or CALF-20, or Zeolite-4A. It may be preferred that the polymeric organic binder is selected from biopolymeric materials such as polyvinyl alcohol and / or polyvinyl acetate, or polyimides, or polyamides, or polyvinylpyrrolidone, or cellulosic polymers such as hydroxyethyl cellulose or hydroxypropyl methyl cellulose or methyl cellulose, or gums such as xantham gum, or mixtures thereof. It may be preferred that the polymeric organic binder is more hydrophobic. It may be preferred in some embodiments if the polymeric organic binder(s) is soluble in water or an aqueous mixture of solvents, or is only soluble in non-aqueous solvents. In some embodiments, it may be preferable to use binders that are hydrophobic in nature, and thus are typically not highly soluble or even insoluble in water.

[0018] For clarity, reference to MOFs or other adsorbent materials includes derivatives of that material, including derivatives of the ligands, and modifications to the metal ions used, as well as combinations and mixtures thereof, for example, reference to CPO-27 may include CPO-27-Ni, CPO-27-Mg, and other variations.

[0019] (a) forming a solvated adsorbent mixture; Step (a) involves contacting an adsorbent material with the initial mixture to form an adsorbent mixture solvated in a first solvent.

[0020] The sorbent materials are described in further detail below.

[0021] The initial mixture comprises a polymeric organic binder and a first solvent. The first solvent may comprise a single solvent or may comprise a mixture of multiple solvents.

[0022] The solvated adsorbent mixture comprises an adsorbent material, a polymeric organic binder, and a first solvent.

[0023] During step (a), the polymeric organic binder is adsorbed onto the surface of the adsorbent material.

[0024] During step (a), the first solvent is distributed throughout the solvated adsorbent mixture.

[0025] During step (a), a portion of the first solvent may provide the continuous liquid medium and / or the dispersion medium. Herein, an adsorbent material having an organic binder adsorbed thereon may provide the dispersed phase.

[0026] The first solvent may comprise "free solvent." For purposes of the present invention, "free solvent" is the portion of the solvent (first or second) that is external to the particle or body of the adsorbent material. Free solvent is not adsorbed or retained within the internal pores of the adsorbent material. Typically, free solvent can be at least partially removed by processes such as centrifugation, decantation, or filtration.

[0027] Typically, the first free solvent is a first solvent that surrounds the adsorbent material and a portion of the surrounding matrix, and that can be at least partially separated from the adsorbent material by a physical process such as centrifugation followed by decantation or filtration.

[0028] Step (a) may comprise one or more processing steps. Suitable processing steps include: (i) a concentration step, e.g., by filtration, sedimentation, and / or centrifugation, in which at least some of the first solvent, e.g., free solvent, is removed from the more dilute mixture of adsorbent material in the first solvent; (ii) a mixing step; (iii) an extrusion step; (iv) and any combination thereof.

[0029] During step (a), the adsorbent material may be recovered as a filtrate or precipitate, either before or after contact with the initial mixture. The adsorbent material may be extruded, spheronized, and / or tableted, but typically the adsorbent material is extruded after being recovered as a filtrate or precipitate. It may be preferred to extrude and then spheronize the adsorbent material during step (a). Suitable extrusion equipment includes a single or twin screw extruder, optionally with a die-face cutter, and a spheronizer. Suitable equipment is supplied by Caleva Ltd.

[0030] During step (a), the initial mixture may be formed by adding a powdered polymer binder to a mixture of the adsorbent material and the first solvent.

[0031] Step (b) of forming an initial adsorbate Step (b) removes at least a portion of the first solvent from the solvated adsorbent mixture in the first solvent to form an initial adsorbate. Typically, step (b) involves the removal, preferably substantially all, of the first free solvent. Typically, the removal of the first solvent in step (b) is accompanied by hardening of the initial adsorbate, since the first solvent, particularly the first free solvent, acts as a plasticizer and lubricant, thus softening the initial adsorbate. The first solvent can also be reduced during step (b) by adding an adsorbent powder to the solvated adsorbent mixture. The adsorbent powder can adsorb a portion of the first solvent, particularly the first free solvent, into its own internal pores, thus reducing the amount of free first solvent. This can simplify processing.

[0032] Step (b) is: (i) a low temperature drying step carried out at a temperature below 50°C and a pressure between 0.5 bar and 1.0 bar for a time period longer than 5 hours, the first solvent having a boiling point below 100°C; (ii) a supercritical drying step; (iii) a freeze-drying step; (iv) drying at a temperature greater than 50° C. and less than 200° C., where the first solvent has a boiling point greater than 100° C.; and (v) drying at a temperature above 50° C., where the gas concentration of the first solvent being removed in the headspace of the solvated adsorbent mixture is maintained between 60% and 95% of its saturation value at the given drying temperature for at least 1 hour; You can choose from.

[0033] Preferably, step (b) comprises a centrifugation and / or filtration step followed by a solvent drying step. Step (b) may also comprise only a solvent drying step.

[0034] Typically, step (b) is carried out under mild conditions. The conditions of step (b) may depend on the type of first solvent used. A less volatile first solvent may be dried at a higher temperature than a more volatile first solvent. During drying, the surface tension of the drying liquid, which pulls on the solids in contact, is preferably minimized. Rapid drying is undesirable and may affect the dense and consistent packing of the adsorbent material in forming the adsorbent body. It is preferable to reduce the drying rate during step (b).

[0035] Any suitable heat source can be used in step (b), including microwave drying.

[0036] Step (b) may also include a size reduction step to reduce the size of the initial adsorbent bodies prior to step (c). Such a size reduction step, for example using a cutting mill, may produce even smaller initial adsorbent bodies, for example bodies having a diameter of less than 2 mm or even less than 1 mm, which may accelerate subsequent steps.

[0037] Step (c) of forming a binder-reduced adsorbent Step (c) contacts the initial adsorbate with a second solvent to form a binder-reduced adsorbate and a second solvent. Typically, the second solvent comprises free solvent, e.g., a second free solvent.

[0038] Here, the second free solvent is the second solvent surrounding the initial adsorbate. Typically, the dissolved polymeric organic binder material diffuses out of the initial adsorbate into the second solvent (second free solvent). It is preferred if the solubility of the polymeric organic binder is lower in the second solvent than in the first solvent.

[0039] The second free solvent typically refers to the second solvent that is external to the initial adsorbent and comprises part of the surrounding matrix. Typically, the second free solvent can be easily removed by a process of filtration.

[0040] During step (c), at least 20 wt% to 80 wt% of the polymeric organic binder is removed from the initial adsorbent and dissolved in the second solvent. Typically, the amount of removed polymeric binder can be assessed using thermogravimetric analysis, as described herein.

[0041] Without wishing to be bound by theory, it is believed that the removal of the polymeric organic binder from the initial adsorbent during step (c) removes the most accessible polymeric organic binder, which is the binder least likely to participate in binding the adsorbent material together, and rather is the one most likely to block the pores of the adsorbent material in the binder-reduced adsorbent.

[0042] During step (c), the second solvent is distributed throughout the binder-reduced adsorbent.

[0043] Preferably, during step (c), the initial adsorbent is in contact with the second solvent for a period of more than 10 hours, or more than 15 hours, or more than 20 hours, or more than 25 hours, or more than 30 hours, or more than 50 hours, or even more than 96 hours.

[0044] Without wishing to be bound by theory, contacting the initial adsorbent with the second solvent dissolves a portion of the polymeric organic binder from the outer surface of the initial adsorbent. The inventors believe that the polymeric organic binder in closest contact with the adsorbent material is the least accessible and therefore dissolves the slowest. The polymeric organic binder left behind is believed to be the most effective in binding the adsorbent material particles together. In this way, step (c) removes the polymeric organic binder that is most likely blocking any pores of the initial adsorbent. Step (c) may also remove any residual reactants from the initial adsorbent. Step (c) may be performed in several steps with smaller amounts of the second solvent exchanged periodically, rather than using a large amount of the second solvent in one step. This may have advantages in limiting the macroporosity by controlling the rate at which the polymeric binder is removed from the initial adsorbent. For example, in Example 1 of the present invention, it was found that exchanging the methanol (second solvent) every 12 hours was more advantageous than adding the initial adsorbent to 85 ml of methanol for the same total time.

[0045] During step (c), the solubility of the polymeric organic binder in the second solvent need not be high. The objective of step (c) is not to remove all of the polymeric organic binder from the initial adsorbate.

[0046] Step (d) of forming an adsorbent Step (d) involves solvent drying the reduced binder adsorbent to form an adsorbent, which may be carried out over one or more process steps and typically involves higher temperatures (e.g., >100° C.) to remove residual solvent from within the internal pores of the adsorbent material.

[0047] Adsorbent The sorbent body comprises a sorbent material and a polymeric organic binder.

[0048] Typically, the weight ratio of adsorbent material to polymeric organic binder present in the adsorbent body is from 1:1 to 25:1, or from 2:1 to 20:1, or even from 4:1 to 15:1. It may be preferred that the weight ratio of adsorbent material to polymeric organic binder present in the adsorbent body is greater than 5:1. These levels of polymeric organic binder are sufficient to provide good mechanical robustness to the adsorbent body of the invention.

[0049] The adsorbent is: (a) Metal and metal salt nanoparticles; (b) enzymes; (c) magnetic materials; (d) dyes and pigments; (e) graphene; and (f) any combination thereof; The composition may comprise a material selected from the group consisting of

[0050] Suitable nanoparticles include metal and metal oxide nanoparticles selected from Pd, Au, Ru, Rh, Pt, Fe, Sn, Zn, Ti, Pd, and any combination thereof. The nanoparticles can be photoactive, for example photocatalytically active. The photoactive nanoparticles can be perovskites, particularly halogen perovskites, and the like. The nanoparticles can be embedded in the adsorbent, where they can help bond the adsorbent particles together, or can be trapped within the particles of the adsorbent material. If any nanoparticles are present, their level in the adsorbent is typically less than 0.15% by volume of the adsorbent. Suitable nanoparticles typically have a weight average particle size of less than 200 nm.

[0051] These added materials are typically added prior to step (d) and typically added during step (a).Materials such as nanoparticles are preferably incorporated into the adsorbent material particles during synthesis of the adsorbent material.

[0052] The adsorbent may be subjected to a size reduction step to reduce the size of the adsorbent prior to use. Such a size reduction step, for example using a cutting mill, may produce even smaller adsorbents, for example bodies having diameters of less than 2 mm or even less than 1 mm.

[0053] Metal-organic framework (MOF) adsorbent The MOF adsorbents produced by the above process typically have the following properties: Without wishing to be bound by theory, it is believed that the partial removal of the binder from the initial adsorbent results in a favorable porosity profile with high levels of micropores and mesopores and low levels of macroporosity. Thus, producing these adsorbents is particularly suitable for gas storage. Other processes typically result in high levels of macropores and therefore low density.

[0054] Thus, in a further aspect, the present invention provides an adsorbent, preferably produced according to the method or methods described herein, wherein the adsorbent material comprises a metal-organic framework (MOF), and the adsorbent comprises: (a) at least 50 wt % metal-organic framework (MOF) particles; (b) 5.0 wt % to 25 wt % of an organic polymer binder; comprising The adsorbent is: (i) 0.3 g / cm 3 With greater bulk density; (ii) a relative density greater than 0.3 and less than 1.2; (iii) 100 m 2 / g and a BET area greater; (iv) microporosity greater than 40% of the total pore volume, as measured by N2 adsorption; (v) having a macroporosity of less than 15% as measured by mercury intrusion porosimetry.

[0055] The adsorbent is 100m 2 / g or greater than 200m 2 / g or greater than 300m 2 / g or greater than 400m 2 / g or greater than 700m 2 The BET area of ​​the adsorbent may be greater than 2000 m / g. 2 / g.

[0056] The macropores of the sorbent preferably comprise less than 15% of the sorbent. Preferably, the macroporosity is less than 12%, or less than 10%, or less than 7%, or even less than 5% of the bulk volume as measured by mercury intrusion porosimetry.

[0057] For the purposes of the present invention, and according to the IUPAC definition, micropores have a diameter of less than 2 nm, mesopores have a diameter of 2 to 50 nm, and macropores have a diameter of more than 50 nm.

[0058] Adsorbent Materials The adsorbent material is selected from metal organic frameworks (MOFs) or their precursors, covalent organic frameworks (COFs) or their precursors, zeolites, activated carbon, organic cages, aluminum formates, and any combination thereof. Preferably, the adsorbent material is a metal organic framework (MOF) or its precursors, or any combination thereof, or a covalent organic framework (COF) or its precursors, or any combination thereof. More preferably, the adsorbent material is a metal organic framework (MOF). The adsorbent material can be a combination of two or more metal organic frameworks (MOFs).

[0059] The adsorbent material may be metal organic framework bodies in particulate form. When the adsorbent material is a metal organic framework body in particulate form, it may be preferred that the weight ratio of adsorbent material to polymeric organic binder present in the solvated adsorbent mixture ranges from 1:1 to 10:1.

[0060] Preferably, the adsorbent material is in particulate form. The adsorbent material can be dispersed in a gel or slurry. More preferably, the adsorbent material is in particulate form with an average particle size of less than 900 nm. Preferably, the SAXS particle size distribution of the adsorbent particulate material is monomodal. However, the SAXS particle size distribution of the adsorbent particulate material can be bimodal. By monomodal, it is typically intended that the size of the adsorbent material comprises one distribution with one peak. By ensuring that the adsorbent material has a monomodal particle size distribution, it is believed that the adsorbent material can be packed more densely, allowing the formation of an adsorbent body with a high density.

[0061] Preferably, the adsorbent material is in microcrystalline form.

[0062] Preferably, the adsorbent material has a small particle size, preferably having a weight average particle size of 5 nm to 900 nm, or 10 nm to 800 nm, or 12 nm to 700 nm, or 15 nm to 500 nm. Methods for measuring particle size are described in further detail below. The particle size of the adsorbent material is measured once the material is formed into an adsorbent body, preferably using XRD techniques as described below. However, the particle size of the adsorbent material can also be measured prior to step (a) if in the form of a slurry. In this case, dynamic light scattering techniques for measuring particle size must be used.

[0063] In cases where results are inconsistent, XRD testing of the adsorbent is most appropriate.

[0064] Particle size control of the adsorbent material is believed to be important to ensure the formation of a consistent adsorbent of high quality. If the particles are too large, this can lead to the formation of a poor (low) density profile and / or a poorly robust adsorbent.

[0065] Preferably, the adsorbent material comprises: (i) Zr-containing MOF; (ii) Zn-containing MOFs such as Zeolite Imidazolate Frameworks, Zn-containing UTSA-16, CALF-15, and CALF-20. (iii) MOF-74, MOF-274, and their derivatives; (iv) Al-based MOFs; (v) Fe-based MOFs; (vi) M(F 6-x )L x Family MOF; (vii) Cu-based MOFs; (viii) Co-based MOFs including Co-UTSA-16; (ix)Cr-based MOF (x)Nb-based MOF; (xi) Ni-based MOFs; (xii) Mn-based MOFs; (xiii) mixed metal MOFs; and (xiv) any combination thereof; The metal-organic framework (MOF) body is selected from the group consisting of:

[0066] Suitable Zr-containing MOFs include UiO-66, UiO-67, UiO-68, NU-1000, PCN-222, MOF-808, and Zr-fumarate.

[0067] Suitable ZIF monoliths include ZIF-8, ZIF-67, ZIF-71, and ZIF-90.

[0068] Suitable MOF-74s derivatives include Mn, Ni, Co, Cu, and Zn variations.

[0069] Suitable Al-based MOFs include Al-fumarate, MIL-53, CAU-10, MIL-160(Al), and Al-soc-MOF-1.

[0070] Suitable Cr-based MOFs include MIL-101(Cr).

[0071] M(F 6-x )L x Suitable MOFs of the family include SIFSIX-3-Ni, TIFSIX-3-Ni, NbOFFIVE-1-Ni, and SIFSIX-2-Cu-i.

[0072] Suitable Cu-based MOFs include HKUST-1, and ROS-17.

[0073] Suitable Co-based MOFs include the cobalt-based UTSA-16 and its derivatives.

[0074] Suitable Fe-based MOFs include MIL-100(Fe), and MIL-101(Fe).

[0075] A suitable sorbent comprising a MOF body is: (i) the MOF is selected from UiO-66, and / or a derivative thereof, such as UiO-66-NH2, and the organic polymer binder is selected from polyvinyl alcohol (PVA), polyimide, polyamide, methylcellulose, and any combination thereof; or (ii) the MOF compound is selected from ZIF-8, and / or its derivatives, and the organic polymer binder is selected from PVA, methylcellulose, and any combination thereof; or (iii) the MOF is selected from Al-fumarate, and / or its derivatives, and the organic polymer binder is selected from PVA, polyamide, and any combination thereof; or (iv) the MOF is selected from Zr-fumarate and / or its derivatives and the organic polymer binder is PVA; or (v) The MOF is Co UTSA-16 or Zn UTSA-16, and / or derivatives thereof, and the organic polymer binder is selected from polyvinyl alcohol, polyimide, polyamide, methyl cellulose, and any combination thereof; It can be the main body, etc.

[0076] Suitable mixed metal MOFs include MOFs based on a mixture of two or more metals selected from Fe, Ti, and Zn.

[0077] Suitable MOFs may comprise mixed-ligand or co-crystallinity MOFs, which comprise at least two chemically distinct organic ligands bound to the same metal ion, a feature that can be used to help tailor the chemical behavior of the MOF.

[0078] Two chemically distinct organic ligands may preferably be chemical analogs, by which it is intended that the structural aspects of the ligands, specifically the backbone as well as the portions involved in binding to the metal ion, are identical.

[0079] A particularly preferred feature is that the chemically distinct organic ligands are chemical analogs that have the same framework structure but differ from each other due to the functionalization of the framework. The structural similarity of how the different organic ligand anions bind to the metal ion means that certain MOF variants can be formed. If the dissimilarity of the organic ligands is too great, the MOF may be amorphous or full of defects.

[0080] For example, many MOFs have dicarboxylic acids as their organic ligands. Each carboxylic acid group participates in a bond with a metal ion. The framework structure refers to the structure between the two carboxylic acid binding groups.

[0081] The dimensions of the framework determine the size of the pores formed by the organic ligands that bind to the metal ions. The chemical differences come from the functional pendant groups attached to the framework.

[0082] Representative examples are shown below: In these cases, the backbone structure is (deprotonated) terephthalic acid (A).

[0083] [ka]

[0084] Further representative examples are described below. Two representative chemical analogs are terephthalic acid (CAS 100-21-0) and 2-aminoterephthalic acid (CAS 10312-55-7). Other representative analogs of terephthalic acid include 2-bromoterephthalic acid (CAS 586-35-6), 2-nitroterephthalic acid (CAS 610-29-7), trimellitic acid (CAS 528-44-9), and 2-hydroxyterephthalic acid (CAS 636-94-2).

[0085] The use of such chemical analogs allows the preparation of specific MOFs with variable chemical properties. It may also be preferable for the two chemically distinct organic ligands to comprise different framework structures. The use of organic ligands with different framework structures can allow the introduction of "defects" into the monolith body where the structure of the MOF is incomplete, or allow for more complex MOF structures. These defects can increase the porosity in some circumstances.

[0086] Preferably, the molar ratio of the first organic ligand to the second organic ligand is greater than 1: 2. More preferably, the molar ratio of the first organic ligand to the second organic ligand is greater than 1: 3. Such ratios are effective to improve the physical and / or chemical properties of monoliths produced from such co-crystals.

[0087] Adsorbent bodies comprising a mixture of adsorbent materials can be prepared by mixing different adsorbent materials together prior to adding a polymeric organic binder.

[0088] A suitable MOF adsorbent may comprise a mixture of MOF crystallites made with different ligands, for example a suitable UiO-66 based MOF may comprise a mixture of UiO-66 BDC and UiO-66 BDC-NH2.

[0089] Suitable COFs for use with the present invention include imine- and / or hydrazone-linked COFs. Thus, the adsorbent may comprise an imine- and / or hydrazone-linked COF.

[0090] Examples of imine-linked COFs include 3D-COOH-COF, 3D-COOH-COF, 3D-CuPor-COF, 3D-CuPor-COF-0P, 3D-OH-COF, 3D-Por-COF, 3D-Por-COF-0P, 3D-Py-COF, 3D-Py-COF-2P, 4PE-1P, 4PE-1P-oxi, 4PE-2P, 4PE-3P, 4PE-TT, BF-COF-1, BF-COF-2, BW-COF-AA, BW-COF-AB, CCOF-1, CCOF-2, CC-TAPH-COF, COF-112, COF-300, COF-320, COF-366-Co, COF-366-F4-Co, COF-366-F-Co, COF-366, COF-366-(Ome)2-Co, COF-505, COF-AA-H, COFBTA-PDA, COF-DL229, COF-LZU1, COF-SDU1, COF-TpAzo, CuP-Ph COF, CuP-TFPh COF, DAAQ-TFP COF, DABQ-TFP-COF, DAQ-TFP COF, DaTP, DhaTab, 2,3-DhaTab, 2,5-DhaTab, 2,3-DhaTph, 2,5-DhaTph, 2,3-DhaTta, 2,3-DmaTph、DMTA-TPB1 / 2’、DMTA-TPB1 / 3’、DMTA-TPB1 / 4’、DMTA-TPB1 / 5’、DMTA-TPB2、DMTA-TPB3、DMTA-TPB4、EB-COF:Br、EB-COF:Cl、EB-COF:F、EB-COF:I、FL-COF-1、HAT-COF、HAT-NTBA-COF、HBC-COF、HB-COF-AA、HB-COF-AB、HCC-H2P-COF、HO2C-H2P-COF、SIOC-COF-5、SIOC-COF-6、SIOC-COF-7、TAPB-BMTTPA-COF、TAPB-PDA COF、TAPB-TFP、TAPB-TFPB、Tb-DANT-COF、TBI-COF、TDFP-1、TEMPO-COF、TFB-COF、TfBD、TfpBDH、TH-COF-1、Thio-COF、TPA-COF-1、TPA-COF-2、TpBD、TpBD-2NO2、TP-BDDA-COF、TpBDH、TPBD-ME2、TPB-DMTP-COF、TpBD-NH2、TpBD-NHCOCH3、TpBD-NO2、TpBD-(OMe)2、TpBPy、TP-COF-BZ、TP-COF-DAB、Tp-DANT-COF、TPE-COF-I、TPE-COF-II、TPE-COF-III、TPE-COF-IV、TP-EDDA-COF、TpMA、TpPa-1、TpPa-2、TpPa-F4、TpPa-NO2、TpPa-Py、TpPa-SO3H、TpPa-SO3H-Py、Tp-Stb、TPT-COF-1、TPT-COF-2、TpTD、TpTG-Br、TpTG-Cl、TpTG-I、TpPa-1-F2、Tp-Ttba、TRIPTA、TTF-COF、TTF-Py-COF、TTI-COF、TzDa、Tp-Azo、HPB-COF、ILCOF-1-AA、ILCOF-1-AB、iPrTAPB-TFP、iPrTAPB-TFPB、LZU-301、LZU-301-sol、LZU-70、LZU-72、LZU-76、N3-COF、NN-TAPH-COF、NS-COF、NUS-10、NUS-14、NUS-15、NUS-9、HO-H2P-COF、OH-TAPH-COF、PC-COF、PI-2-COF、PI-3-COF、Por-COF、Py-1P COF、Py-1PF COF、Py-2,Examples include 2’-BPyPh-COF, Py-2,3-BPyPh-COF, Py-2,3-DHPh-COF, Py-2PE COF, Py-3PEBTD COF, Py-3PE COF, Py-An COF, Py-DHPh COF, PyTTA-BFBIm-iCOF, RT-COF-1, SA-COF, Salen-COF, SB-PORPy, SIOC-COF-3-AB, and SIOC-COF-4-AB, etc.

[0091] Examples of hydrazone-bonded COFs include COF-42-bnn, COF-42-gra, COF-43-bnn, COF-43-gra, COF-ASB, COF-LZU8, CPF-1, CPF-2, and TFPT-COF, etc.

[0092] Suitable zeolites include aluminosilicate zeolites having the chemical formula Na n Al n Si 96 - n O 192 ·16H2O (0 < n < 27), etc. Aluminosilicate zeolites having this chemical formula include catalytic zeolites such as Zeolite Socony Mobil-5, or ZSM-5, which is commercially known and widely used. Alternatively, each zeolite body may have an SiO2:Al2O3 ratio of about 50:1 to about 120:1, preferably about 80:1 to about 100:1. Commonly used aluminosilicate zeolites include type A, type X, and type Y zeolites, etc.

[0093] Other types of zeolites, such as titanium silicate (e.g., TS-1) or pure siliceous (e.g., Silicalite-1) zeolites are also suitable.

[0094] Initial mixture The initial mixture comprises a polymeric organic binder and a first solvent.

[0095] Typical weight ratios of the polymeric organic binder to the first solvent range from 1:50 to 1:4, or even 1:2. The initial mixture is typically formed by dissolving or dispersing the polymeric organic binder in the first solvent, often at high temperature and with vigorous stirring. If the initial mixture is too concentrated, it may not mix well with the adsorbent material. If it is too dilute, the first solvent may be wasted, limiting the efficiency of deposition of the polymeric organic binder on the surface of the adsorbent material. The initial mixture may be formed prior to or simultaneously with contact with the adsorbent material. However, to maximize mixing uniformity and contact between the adsorbent material particles and the binder material, it is preferred that the initial mixture be formed prior to contact with the adsorbent material.

[0096] Polymer Organic Binder The solubility of the polymeric organic binder in the first solvent is the same as or higher than the solubility of the polymeric organic binder in the second solvent. Preferably, the solubility of the polymeric organic binder in the first solvent is higher than the solubility of the polymeric organic binder in the second solvent.

[0097] Preferably, the polymeric organic binder is selected from polyvinyl alcohol (PVA), polyvinyl acetate, polyethyleneimine, polyvinylpyrrolidone, polyimide (PI), polyvinyl formal, polyacrylic acid and its salts, polyethylene glycol, polypropylene glycol, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefins, polyamide, chitosan, cellulose acetate, hydroxypropylmethylcellulose (HPMC), methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose phthalate (HPMCP), and any combination thereof. A preferred binder mixture comprises PVA and a cellulosic polymer, in particular hydroxyethylcellulose or methylcellulose.

[0098] Free Solvent The term "free solvent" refers to solvent that is external to the particles or bodies of the adsorbent material. Free solvent is not adsorbed within the internal pores of the adsorbent material. Typically, free solvent can be at least partially removed by processes such as centrifugation and decantation, or by filtration.

[0099] First Solvent The first solvent may be chemically the same as the second solvent or may be chemically different. Preferably, the first solvent is chemically different from the second solvent. A preferred first solvent is water (a polar protic solvent) or dimethylsulfoxide (DMSO; a polar aprotic solvent). Other polar aprotic solvents such as dimethylformamide (DMF), dimethylacetamide (DMS), and N-methyl-2-pyrrolidone are also preferred. Other first solvents may include alcohols, glycols, acetone, and distilled paraffin oil, and mixtures thereof.

[0100] Solvated adsorbent mixture The solvated sorbent mixture comprises an adsorbent material, a polymeric organic binder, and a first solvent, where the polymeric organic binder is adsorbed onto the surface of the adsorbent material and the first solvent is distributed throughout the solvated sorbent mixture. The solvated sorbent mixture may contain residual reactants and solvents from any previous process steps, such as synthesis and washing of the adsorbent material.

[0101] The solvated sorbent mixture comprises the sorbent material, the polymeric organic binder, and the first solvent. Typically, the solvated sorbent material comprises the sorbent material and the polymeric organic binder in a weight ratio of from 0.75:1 to 12.5:1, or from 1:1 to 9:1, or from 2:1 to 6:1.

[0102] First free solvent Typically, the first free solvent is the first solvent that surrounds the adsorbent material and is part of the surrounding matrix. It is not the first solvent that is adsorbed within the pores of the adsorbent material. The free solvent can typically be at least partially separated from the adsorbent material by a physical process such as centrifugation followed by decantation or filtration.

[0103] Initial adsorbent Typically, the initial adsorbate comprises the polymeric organic binder, the adsorbent material, and any remaining first solvent. The initial adsorbate may also comprise residual reactants. Typically, it is thermodynamically favorable for any polymer in solution to deposit on the surface of the adsorbent material rather than remaining in solution.

[0104] Typically, the initial adsorbent body has a high ratio of polymeric organic binder to adsorbent material and is typically very robust mechanically, but has poor adsorption capacity due to pore blockage. The weight ratio of adsorbent material to polymeric organic binder can range from 1:1 to 12:1, for example 10:1.

[0105] Second Solvent The second solvent may be chemically the same as the first solvent or may be chemically different. Preferably, the second solvent is chemically different from the first solvent. The second solvent may comprise a mixture of solvents, including a mixture comprising the first solvent. The second solvent may be the same as the first solvent, but at a lower or different temperature to reduce the solubility of the polymer binder in the solvent. The solubility of the binder in the second solvent must be lower than in the first solvent.

[0106] Preferably, the second solvent is selected from alcohols and glycols. Preferably, the second solvent has a molecular weight of less than 600 Da. More preferably, the second solvent has a molecular weight of less than 600 Da and is selected from alcohols and glycols. Particularly preferred second solvents are methanol and ethanol. Typically, up to 40% of another solvent can be added to the second solvent. For example, a 90:10 mixture of methanol and water can be used as the second solvent.

[0107] Binder-reduced adsorbent The binder-reduced sorbent comprises a sorbent material, a polymeric organic binder, a second solvent, and residual first solvent.

[0108] Typically, the weight ratio of polymeric organic binder to adsorbent material in the binder-reduced adsorbent is lower than the ratio of polymeric organic binder to adsorbent material in the initial adsorbent. Typically, it is necessary to remove a significant proportion of the polymeric organic binder, for example from the surface of the adsorbent material, to significantly increase the available surface area. Even at higher adsorbent material to binder ratios, it is typically necessary to remove at least 20 wt% of the polymeric organic binder present to have a beneficial effect on surface area. It may be preferable to remove at least 30 wt%, or at least 40 wt%, or even at least 50 wt% of the polymeric organic binder present. It may be preferable to remove 20 wt% to 80 wt%, or 30 wt% to 80 wt%, or 40 wt% to 80 wt%, or 50 wt% to 80 wt% of the polymeric organic binder present.

[0109] Second Free Solvent The second free solvent is the second solvent surrounding the initial adsorbate. Typically, the dissolved polymeric organic binder material diffuses from the initial adsorbate into the free second solvent. It is preferred if the solubility of the polymeric organic binder is lower in the second solvent than in the first solvent.

[0110] Second free solvent typically refers to the second solvent that is external to the initial adsorbate and comprises part of the surrounding matrix. Typically, the second free solvent can be easily removed by a process of filtration or by simply removing the adsorbate from the second solvent.

[0111] Test Method Average particle size measurement by XRD nNi The weight average particle size of the adsorbent material in the adsorbent body can be measured by X-ray diffraction (XRD). The weight average particle size of the adsorbent material constituting the adsorbent body can be determined by X-ray diffraction using the Scherrer equation, which calculates the particle size from a measurement of the full width at half maximum (FWHM) of the diffraction peak. Since the adsorbent material particles are often very isotropic in shape and there is no single preferred orientation for crystallite growth, it is not critical which reflection to use, but for consistency the (0 1 0) reflection is used and the K value is constant at 0.94. Suitable instruments include the X'ert Pro from PANalytical.

[0112] Measuring the adsorbent material particle size prior to step (a) The particle size distribution of the adsorbent particles can also be measured prior to step (a) if in a slurry or suspension by dynamic light scattering (DLS); however, XRD is the preferred method. Suitable instruments for DLS include the NANO-flex II from Colloid Metrix. Dilution of the suspension is usually not necessary.

[0113] How to measure binder solubility in a solvent The solubility of the binder in the solvent can be determined by adding 10 g of powdered binder to 100 g of solvent at ambient temperature and stirring for 2 hours. The mixture is then preferably filtered through a filter paper such as Whatman Grade 1 with a pore size of 11 microns, the filtrate dried at 100 °C until no weight loss occurs, and the dry weight is measured. If all the binder dissolves during the test, a further 10 g of binder should be added and the mixture stirred for a further 2 hours. If necessary, this should be repeated until the measured solubility is the saturated solubility and at the end of the stirring period only solid binder remains. The solubility of the binder in the solvent is the total weight of the dissolved binder divided by the weight of the solvent.

[0114] A method for measuring the BET area of ​​an adsorbent. The BET surface area of ​​the adsorbent can be measured using ASTM method D3663-03 "Standard test method for surface area of ​​catalysts and catalyst carriers". BET surface area is determined by measuring the volume of nitrogen gas adsorbed by the monolith sample at various low pressure levels. The pressure difference caused by introducing the monolith surface area into a constant volume of nitrogen in a test apparatus is measured and used to calculate the BET surface area. Suitable instruments for measuring BET surface area include the 3Flex from Micromeritics Corporation and are used according to the manufacturer's guidelines.

[0115] Microporosity The MOF body preferably has a microporosity of greater than 40% and less than 75% of the total pore volume as measured by N2 adsorption. A portion of the mesoporosity (having pores larger than the micropores but smaller than the macropores) may beneficially aid in the transport of fluids throughout the MOF body.

[0116] The micro- and mesoporosity profile of the body can be determined by test method ASTM D4641-17. A suitable instrument for performing such a test is the ASAP 2020 Plus from Micrometrics Corporation. The test method is as follows:

[0117] A test sample (0.5 g) is typically heated to 300° C. under vacuum to remove adsorbed gases and vapors from the surface. The nitrogen adsorption branch of the isotherm is then determined by placing the sample under vacuum, cooling it to the boiling point of liquid nitrogen (about 77.3 K), and then gradually adding known amounts of nitrogen gas at increasing pressures P to the sample in an amount such that the shape of the adsorption isotherm is well defined and the saturation pressure of nitrogen is reached.

[0118] Each amount of added nitrogen is introduced into the sample only after the preceding amount of nitrogen has reached adsorption equilibrium with the sample.

[0119] Typically, equilibrium is reached if the gas pressure is changed by less than 0.1 torr / 5 min interval. This is continued until P0 (gas saturation pressure) is reached.

[0120] The data are typically plotted as the amount of gas adsorbed / desorbed (and the derived porosity profile) as a function of P / P0. Desorption isotherms are determined by desorbing nitrogen from a saturated sample in stages, with precautions taken to ensure desorption equilibration identical to those applied under adsorption conditions. Microporosity relates to the volume of gas adsorbed at P / P0 values ​​<0.1, while mesoporosity relates to the volume of gas adsorbed at P / P0 values ​​between 0.1 and 0.98.

[0121] How to measure macroporosity by mercury porosimetry. Mercury porosity values ​​can be measured according to ASTM D4284-12. Suitable instruments for performing ASTM D4284-12 include the Micromeritics AutoPore VI 9510 from Micrometrics Corporation, USA. The surface tension and contact angle of mercury are taken as 485 mN / m and 130°, respectively. In ASTM D4284-12, mercury is forced into the pores under pressure. A sample size of 1 g is preferably used. The sorbent is fragmented and sieved between 710 and 250 microns, and the sieved material is used.

[0122] The pressure required to force mercury into the pores of a sample is inversely proportional to the size of the pores according to the Washburn equation. For characterization purposes, all pores are assumed to be cylindrical. The porosimeter applies increasing pressure to the mercury in the sample holder, causing it to progressively intrude into the smaller sample pores. AutoPore VI automatically converts the applied pressure to an equivalent pore diameter using the Washburn equation and the contact angle and surface tension values ​​listed above.

[0123] The bulk volume of the sample is determined by the volume of mercury displaced by atmospheric pressure. As the applied pressure is increased, mercury is forced into the interior pores. Thus, the % macroporosity of a sample is the volume of mercury that enters the sample as the pressure is increased from 1.001 atm to 292 atm as a percentage of the excluded volume at atmospheric pressure.

[0124] Mercury porosimetry is not suitable for measuring micro- or mesoporosity because the pressures required to force mercury into small pores are too high to be practical.

[0125] Method for measuring bulk density of adsorbent The adsorbent is 0.4 g / cm 3 Greater than 0.6g / cm 3 Greater than 0.8g / cm 3 Greater than or equal to 1.0 g / cm 3It may have a greater bulk density.

[0126] The bulk density of a body is calculated by multiplying the weight of the body (in grams) by its bulk volume (in mm 3 Bulk density can be measured by dividing the mass of the particle by the mass of the solid matter in each piece (units of mass per unit mass). Bulk volume is defined in ASTM D3766 as "the ratio of the mass of the particle to the sum of the volume of the solid matter within each piece and the volume of the voids inside each piece, i.e., within a tightly sealed imaginary envelope completely surrounding each piece." The bulk density of a body can be measured using techniques based on Archimedes' principle of volumetric exclusion. For example, bulk density can be measured by mercury porosimetry. At atmospheric pressure, mercury does not penetrate into internal pores. Thus, the volume of mercury excluded by a body at atmospheric pressure is the bulk volume of the object. Dividing the weight of the sample by this volume gives the bulk density. The use of mercury porosimetry is described above.

[0127] An alternative viable approach for larger bodies, typically those with diameters >2 mm, is to measure the volume of the body using an accurate 3D scanner. Suitable instruments include the Leika BLK360. Preferably, a powder pycnometer, such as the Micrometrics Instrument Corp GeoPyc Model 1360, can also be used to measure the bulk volume and density of the body. If necessary, the bulk volume measured by these techniques can be used interchangeably with the bulk volume measured by mercury porosimetry.

[0128] Method for determining binder level in an adsorbent body The level of polymeric organic binder in the adsorbent can be determined by thermogravimetry based on weight loss at high temperature. At the high temperature used (600°C), the organic species are burned off leaving behind metal oxide species etc. The difference in % weight loss between a sample of the adsorbent material and a sample of the adsorbent material plus binder indicates the level of binder. The adsorbent is crushed and a sample of the adsorbent material is heated to 600°C and the steady state weight loss is measured and normalized. A sample of the adsorbent material is then heated under the same conditions and the weight loss normalized. The difference between the % wt losses is the % of binder present. This method is particularly suitable where the adsorbent comprises MOFs and / or zeolites.

[0129] The residual solvent level in the sample can be determined by the weight loss of the sample after heating it to 120° C. under vacuum for 12 hours. The binder level in the sample can then be determined by thermogravimetric analysis as described above.

[0130] Mechanical Integrity Assessment The relative mechanical integrity of the sorbent MOF body can be assessed by placing 10 g of the sorbent MOF body in a closed glass bottle (100 ml capacity may be suitable) and shaking vigorously by hand for 1 min. The robustness of the sorbent can be visually assessed by the presence of dust on the inner surface of the glass bottle. A more quantitative test, typically suitable for testing more stressful environments, e.g. vehicle storage tanks, can be performed by placing the same amount, e.g. 10 g, of sorbent in a tumbling mixer, e.g. Eriez's Macsalab Mixer, and comparing the relative amount of fine material (<150 microns) produced by tumbling the sample for a similar time and speed, e.g. 200 rpm, and then sieving the material. Grinding media, e.g. balls, can be added to increase the stress of the test.

[0131] Relative Density Relative density refers to the ratio of the bulk density of the crystalline adsorbent compared to the crystal density of the adsorbent material.

[0132] The crystal density of a crystalline material such as a MOF is the density of a single crystal and is theoretically calculated from the structure. Structural and other information for crystalline adsorbent materials such as MOFs is available from the Cambridge Crystal Structure Database.

[0133] A relative density much less than 1, for example less than 0.3, implies excess porosity, most of which is in the form of larger (and therefore less useful) pores within the bulk. A relative density greater than 1 suggests a wasteful loss of porosity, since such a high value can only be achieved by destroying some of the useful pores.

[0134] The adsorbent body preferably has a relative density greater than 0.3, or greater than 0.5, or greater than 0.7 and less than 1.2. EXAMPLES

[0135] Example 1 (Invention) Preparation of an adsorbent comprising Zr-fumarate and polyvinyl alcohol (PVA). Preparation of the initial mixture. 1.6 g of PVA (Mowiol 10-98, Sigma Aldrich) was dissolved in 40 ml of anhydrous 99.9% DMSO (dimethylsulfoxide supplied by Sigma Aldrich) by heating at 80° C. for 1 hour.

[0136] Adsorbent material – Preparation of Zr-fumarate MOF. 2.34 g of Zr-acetylacetonate (supplied by TCI, CAS 17501-44-9) and 0.557 g of fumaric acid (99%, Acros Organics) were mixed with 7.8 ml of water, followed by the addition of 4.2 ml of glacial acetic acid (99%, Fisher Scientific). The resulting suspension was then stirred at ambient temperature (20-25 °C) for 3 days. After 3 days, the resulting mixture was transferred to a Falcon tube and 30 ml of acetone was added. The mixture was centrifuged (Beckman-Coulter J-15R) at 5250 rpm for 25 min. The supernatant was removed and another 30 ml of acetone was added with vigorous hand stirring, the centrifugation step was repeated, and the supernatant was decanted. After this, the Falcon tube contained a concentrated gel pellet of approximately 1.0 g of sorbent material.

[0137] Contacting the adsorbent material with the initial mixture. 5ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing the adsorbent material and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed together. This was repeated 5 times and the sample was left overnight for 14 hours. The sample was then centrifuged at 5250 rpm for 30 minutes using a J-15R and the supernatant was poured off. The open Falcon tube was then dried at 35°C for 2 weeks to obtain the initial adsorbent.

[0138] The initial adsorbent had a composition of 18.3% PVA, 73.4% Zr-fumarate, and 8.3% residual DMSO.

[0139] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of methanol. Every 12 hours, the methanol was replaced with 5 ml of fresh sample. This was repeated for a total of 9 days to obtain a binder-reduced adsorbent.

[0140] Adsorbent formation. The binder-reduced adsorbent was then removed from the methanol and dried at room temperature overnight. The solvent-dried binder-reduced adsorbent was then further dried and activated by heating at 120° C. under vacuum for 12 hours to yield an adsorbent comprising 91.74% Zr-fumarate and 8.26% PVA.

[0141] For clarification - the above analysis meant that the initial sorbent had 24.9 parts PVA per 100 parts MOFs. The sorbent (and therefore the binder-reduced sorbent) was 9 parts PVA per 100 parts MOFs. This represented the removal of 63.8% of the PVA originally present. The first solvent is DMSO and the second solvent is methanol. The solubility of PVA in methanol is lower than in DMSO.

[0142] Example 2 (Comparison) Preparation of an adsorbent comprising Zr-fumarate. Zr-Fumarate was synthesized according to the procedure described above in "Preparation of the Adsorbent Material - Zr-Fumarate MOF". The open Falcon tube containing the pellets of concentrated adsorbent material gel was then dried at 35°C for 2 weeks. The dried bodies were contacted with 5 ml of methanol for 12 hours, after which the methanol was replaced with 5 ml of fresh methanol. This was repeated every 12 hours for 3 days to solvent exchange the residual DMSO. The Zr-Fumarate bodies were then activated by drying at 120°C under vacuum for 12 hours.

[0143] Example 3 (Comparison) An initial adsorbent comprising Zr-fumarate and PVA was prepared as in Example 1.

[0144] This initial adsorbate did not go through a binder reduction step or the like, but was directly activated by heating at 120°C under vacuum to remove residual DMSO, retaining essentially all of the PVA in the resulting dried adsorbate.

[0145] Example 4 (Comparison) Zr-fumarate (the adsorbent material) and the initial mixture were prepared as in Example 1.

[0146] The adsorbent material was contacted with the initial mixture in the same manner as in Example 1, except that instead of adding 5 ml of the initial mixture, 2 ml of the initial mixture and 3 ml of DMSO were added. Then, the initial adsorbent was prepared according to the procedure as in Example 1, resulting in an initial adsorbent comprising 7.5% PVA, 86% Zr-fumarate, and 6.5% residual DMSO.

[0147] This initial adsorbent was then activated by drying at 120° C. under vacuum for 12 hours to obtain an adsorbent comprising 8% PVA and 92% Zr-fumarate.

[0148] Example 4 shows the difference between samples with similar levels of binder, but in this case one sample (Example 1) was prepared by the method of the present invention and the other sample (Example 4) was not. Example 1 was clearly more robust than Example 4. The test data is shown below:

[0149] [Table 1]

[0150] Example 5 (invention) Preparation of an adsorbent comprising UiO-66 MOF and a polyimide (PI) binder. Preparation of the initial mixture. 1.6 g of polyimide (CAS 62929-02-6, supplied by Alfa Aesar) was dissolved in 40 ml of 99.9% anhydrous DMSO (dimethyl sulfoxide, supplied by Sigma-Aldrich) by heating at 80° C. for 1 h.

[0151] Adsorbent material – preparation of UiO-66 MOF. Benzene-1,4-dicarboxylic acid (98%, Sigma-Aldrich, 7.25 mmol) and ZrOCl2·8H2O (98%, Acros Organics, 5.0 mmol) were completely dissolved in 30 ml of N,N-dimethylformamide (DMF) (99%, Alfa Acer), followed by the addition of 1.5 ml of concentrated hydrochloric acid (37%, Honeywell Fluka) and 2.0 ml (99+%, Alfa Acer) of glacial acetic acid. The resulting solution was then sealed and heated in a 100°C thermostat for 2 h, resulting in a thick white gel of UiO-66. The above synthesized gel was diluted by adding 50 ml of DMF and then centrifuged (5 min, 5250 rpm, Beckman Coulter J-15R). The gel was further washed with 50 ml of fresh DMF and centrifuged again under the same conditions. The supernatant was then poured off. Each Falcon tube contained approximately 0.5 g of concentrated gel pellets of sorbent material.

[0152] Contacting the adsorbent material with the initial mixture. 2.5ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing the adsorbent material, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed together. This was repeated 5 times, and the sample was left overnight for 14 hours. The sample was then centrifuged at 5250 rpm for 120 minutes using a J-15R, and the supernatant was poured off. The open Falcon tube was then dried at 35°C for 2 weeks to obtain the initial adsorbent.

[0153] The initial adsorbent had a composition of 17.9% polyimide, 70.6% UiO-66, and 12.5% ​​residual DMF.

[0154] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of methanol. Every 12 hours, the methanol was replaced with 5 ml of fresh sample. This was repeated for a total of 2 days to obtain a binder-reduced adsorbent.

[0155] Adsorbent formation. It was then removed from the methanol and dried at room temperature overnight. The solvent dried binder reduced adsorbent was then further dried under vacuum at 120° C. for 12 hours to yield an adsorbent comprising 76.9% UiO-66 and 13.1% polyimide. The adsorbent had the following properties:

[0156] For clarification - the above analysis meant that the initial adsorbent had 25.3 parts polyimide per 100 parts MOFs. The adsorbent (and therefore the binder-reduced adsorbent) had 17.0 parts polyimide per 100 parts MOFs. This represented the removal of 32.8% of the polyimide originally present. The solubility of polyimide in DMSO is higher than in methanol.

[0157] Example 6 (Comparison) Preparation of UiO-66 adsorbent. UiO-66 was synthesized as in Example 5. The concentrated gel pellet of UiO-66 in a Falcon tube was then left to dry at 35°C for 2 weeks. The dried body was then immersed in 5 ml of methanol. Every 12 hours, the methanol was replaced with a fresh 5 ml sample. This was repeated for a total of 2 days to obtain a purified adsorbent of UiO-66. It was then activated by heating at 120°C under vacuum for 12 hours.

[0158] Example 7 (Comparison) Preparation of an adsorbent comprising UiO-66 MOF and a polyimide (PI) binder without a binder reduction step. UiO-66 and the initial mixture were prepared as in Example 5.

[0159] 2.5ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing the adsorbent material and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed together. This was repeated 5 times and the sample was left overnight for 14 hours. The sample was then centrifuged at 5250 rpm for 120 minutes using a J-15R and the supernatant was poured off. The open Falcon tube was then dried at 35°C for 2 weeks to obtain the initial adsorbent. This was activated by heating at 120°C under vacuum for 12 hours.

[0160] The test data is shown below.

[0161] [Table 2]

[0162] Example 8 (Invention) Preparation of an adsorbent comprising Al-Fumarate MOF and a polyvinyl alcohol organic polymer binder. Preparation of the initial mixture. 1.8 g of PVA (Mowiol 10-98, Sigma-Aldrich) was dissolved in 50 ml of 99.9% anhydrous DMSO (dimethylsulfoxide supplied by Sigma-Aldrich) by heating at 80° C. for 1 h.

[0163] Adsorbent material – Preparation of Al-fumarate MOF. Fumaric acid (1.40 g, lab grade supplied by Fisher Scientific) and aluminum acetylacetonate (1.55 g, CAS 13963-57-0, supplied by Merck) were mixed with 12 ml of sodium hydroxide solution (8.3 mM) in a 25 ml vial with stirring at 90 °C for 20 h. The resulting material was then diluted by adding 50 ml of ethanol and centrifuged (4750 rpm, 15 min, Beckman Coulter J-15R). The supernatant was decanted. This centrifugation step was repeated four times with the addition of fresh ethanol to wash the resulting Al-fumarate. After this, the Falcon tube contained a concentrated gel pellet of approximately 0.65 g of sorbent material.

[0164] Contacting the adsorbent material with the initial mixture. 3.0 ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing 0.65 g of the adsorbent material mixture, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed. The Falcon tube was left to stand for 1 hour to form a gel. This gel was dried at 60°C for 4 days to form the initial adsorbent.

[0165] The initial adsorbent had the following composition: 12.3% polyvinyl alcohol, 82.1% Al-fumarate, and 5.6% residual DMSO.

[0166] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of methanol. Every 12 hours, the methanol was replaced with 5 ml of fresh sample. This was repeated for a total of 5 days to obtain a binder-reduced adsorbent.

[0167] Adsorbent formation. It was then removed from the methanol and dried at room temperature overnight. The solvent dried binder-reduced adsorbent was then further dried in vacuum at 130° C. for 12 hours to yield an adsorbent comprising 92.4.2% Al-fumarate and 7.6% PVA.

[0168] Example 9 (Invention) Preparation of an adsorbent comprising Al-Fumarate MOF and a methylcellulose organic polymer binder.

[0169] Preparation of the initial mixture. 20.0 g of methylcellulose (MO262 from Sigma-Aldrich) was dissolved in 80 g of deionized (DI) water by adding it to heated water and then cooling the mixture under continuous stirring. In this example, the first solvent was water.

[0170] Adsorbent material – Preparation of Al-fumarate MOF. Fumaric acid (1.40 g, lab grade supplied by Fisher Scientific) and aluminum acetylacetonate (1.55 g, CAS 13963-57-0, supplied by Merck) were mixed with 2 ml of sodium hydroxide solution (0.05 M) and 10 ml of DI water in a 25 ml vial with stirring at 90 °C for 20 h. The resulting material was then diluted by adding 30 ml of methanol and centrifuged (4750 rpm, 15 min, Beckman Coulter J-15R). The supernatant was decanted. This centrifugation step was repeated twice with the addition of fresh methanol to wash the resulting Al-fumarate. After this, the Falcon tube contained a concentrated gel pellet of approximately 1 g of sorbent material.

[0171] Contacting the adsorbent material with the initial mixture. 2 ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing 1 g of the adsorbent material mixture, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure that everything was dispersed and mixed. The mixture was centrifuged and the supernatant was removed. The Falcon tube was then dried at 60°C for 4 days to form the initial adsorbent.

[0172] The initial adsorbent had a composition of 64% aluminum fumarate, 27% methylcellulose, minus residual solvent.

[0173] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of a 95:5 ethanol:water mixture (second solvent). Every 12 hours, the second solvent was replaced with a fresh 5 ml sample. This was repeated for a total of 5 days to obtain a binder-reduced adsorbent.

[0174] Adsorbent formation. It was then removed from the second solvent and dried at room temperature overnight. The solvent dried binder reduced adsorbent was then further dried under vacuum at 130° C. for 12 hours to yield an adsorbent comprising 77% Al-fumarate and 23% methylcellulose.

[0175] Example 10 (Comparison) Preparation of Al-fumarate adsorbent. Al-fumarate was synthesized and concentrated into gel pellets as in Example 8.

[0176] The gel was dried at 60°C for 4 days. The dried body was then immersed in 5 ml of methanol. Every 12 hours the methanol was replaced with 5 ml of fresh sample. This was repeated for a total of 5 days to obtain the purified adsorbent, which was then removed from the methanol and allowed to dry overnight at room temperature. The solvent dried binder-reduced adsorbent was further dried under vacuum at 130°C for 12 hours.

[0177] Example 11 (Comparison) Preparation of an adsorbent comprising Al-Fumarate MOF and PVA binder without a binder reduction step. The initial adsorbent was prepared as in Example 8. The initial adsorbent was activated by heating at 130° C. under vacuum for 12 hours. This resulted in a body containing 13% PVA and 87% Al-fumarate. The test data are shown below.

[0178] [Table 3]

[0179] Example 12 (Invention) Preparation of the adsorbent of the present invention comprising Zr-fumarate and polyvinyl alcohol (PVA). Preparation of the initial mixture. 1.6 g of PVA (Mowiol 10-98, Sigma-Aldrich) is dissolved in 40 ml of 99.9% anhydrous DMSO (dimethylsulfoxide supplied by Sigma-Aldrich) by heating at 80° C. for 1 hour.

[0180] Adsorbent material – Preparation of Zr-fumarate MOF. 2.34 g of Zr-acetylacetonate (CAS 17501-44-9, supplied by TCI) and 0.557 g of fumaric acid (99%, Acros Organics) are mixed with 7.8 ml of water, followed by the addition of 4.2 ml of glacial acetic acid (99%, Fisher Scientific). The resulting suspension is then stirred at ambient temperature (20-25 °C) for 3 days. After 3 days, the resulting mixture is transferred to a Falcon tube and 30 ml of acetone is added. The mixture is then centrifuged (Beckman Coulter J-15R) at 5250 rpm for 25 min. The supernatant is removed and another 30 ml of acetone is added with vigorous hand stirring, the centrifugation step is repeated, and the supernatant is decanted. After this, the Falcon tube contains a concentrated gel pellet of approximately 1.0 g of adsorbent MOF material.

[0181] Contact of the adsorbent MOF material with the initial mixture. Add 5ml of the initial mixture prepared above at ambient temperature to the Falcon tube containing the adsorbent MOF material, and vigorously vortex the Falcon tube by hand for 5 minutes to ensure everything is dispersed and mixed. Repeat this 5 times and leave the sample overnight for 14 hours. The sample is then centrifuged at 5250 rpm for 30 minutes using a J-15R and the supernatant is poured off. The open Falcon tube is then dried at 35°C for 2 weeks to obtain the initial adsorbent MOF body.

[0182] The initial adsorbent MOF body has a composition of 18.3% PVA, 73.4% Zr-fumarate, and 8.3% residual DMSO.

[0183] Formation of binder-reduced adsorbent MOF bodies. The initial adsorbent MOF body is then immersed in 5 ml of methanol. Every 12 hours, the methanol is replaced with a fresh 5 ml sample. This is repeated for a total of 9 days to obtain the binder-reduced adsorbent MOF body.

[0184] Formation of the adsorbent MOF body. The binder-reduced adsorbent MOF body is then removed from the methanol and dried overnight at room temperature. The solvent-dried binder-reduced adsorbent MOF body is then further dried and activated by heating at 120° C. under vacuum for 12 hours to yield an adsorbent MOF body comprised of 91.3% Zr-fumarate and 8.7% PVA.

[0185] Example 13 (Comparison) Preparation of adsorbent MOF bodies comprising Zr-fumarate. Zr-Fumarate is synthesized according to the procedure described above in "Adsorbent Material - Preparation of Zr-Fumarate MOF" (Example 12). The open Falcon tube containing the pellets of concentrated adsorbent MOF material gel is then dried at 35°C for 2 weeks. The dried bodies are contacted with 5 ml of methanol for 12 hours, during which the methanol is replaced with 5 ml of fresh methanol. This is repeated every 12 hours for 3 days to solvent exchange the residual DMSO. The Zr-Fumarate bodies are then activated by drying under vacuum at 120°C for 12 hours.

[0186] Example 14 (Comparison) The initial adsorbent MOF body comprising Zr-fumarate and PVA is prepared as in Example 12, except that 7 ml of the initial mixture is added instead of 5 ml.

[0187] This initial adsorbent MOF body does not go through a binder reduction step or the like, but is directly activated by heating at 120° C. under vacuum for 12 hours to remove residual DMSO.

[0188] The test data is shown below:

[0189] [Table 4]

[0190] Only Example 12 of the present invention provided both mechanical integrity and high adsorption capacity.

[0191] Example 15 (Invention) Preparation of an adsorbent comprising Al-fumarate and methylcellulose (MC). Preparation of the initial mixture. 1.6 g of methylcellulose (MC), CAS 9004-67-5, viscosity 400 cPs, Thermo Scientific, was dissolved in 40 ml of ambient water (first solvent) with stirring for 1 hour.

[0192] Adsorbent material – Preparation of Al-fumarate MOF. Fumaric acid (1.40 g, lab grade supplied by Fisher Scientific) and aluminum acetylacetonate (1.55 g, CAS 13963-57-0, supplied by Merck) were mixed with 12 ml of sodium hydroxide / water solution (8.3 mM) in a 25 ml vial at 90 °C for 20 h with stirring. The resulting material was then diluted by adding 50 ml of ethanol and centrifuged (4750 rpm, 15 min, Beckman Coulter J-15R). The supernatant was decanted. This centrifugation step was repeated three times with the addition of fresh methanol to wash the Al-fumarate.

[0193] Contacting the adsorbent material with the initial mixture. 5 ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing 1 g of Al-Fumarate adsorbent material, and the Falcon tube was vigorously stirred by hand for 5 minutes, Example 15 (Invention).

[0194] Preparation of an adsorbent comprising Al-fumarate and methylcellulose (MC). Preparation of the initial mixture. 1.6 g of methylcellulose (MC), CAS 9004-67-5, viscosity 400 cPs, Thermo Scientific, was dissolved in 40 ml of ambient water (first solvent) with stirring for 1 hour.

[0195] Adsorbent material – Preparation of Al-fumarate MOF. Fumaric acid (1.40 g, lab grade supplied by Fisher Scientific) and aluminum acetylacetonate (1.55 g, CAS 13963-57-0, supplied by Merck) were mixed with 12 ml of sodium hydroxide / water solution (8.3 mM) in a 25 ml vial at 90 °C for 20 h with stirring. The resulting material was then diluted by adding 50 ml of ethanol and centrifuged (4750 rpm, 15 min, Beckman Coulter J-15R). The supernatant was decanted. This centrifugation step was repeated three times with the addition of fresh methanol to wash the Al-fumarate.

[0196] Contacting the adsorbent material with the initial mixture. 5 ml of the initial mixture prepared above at ambient temperature was added to the Falcon tube containing 1 g of Al-Fumarate adsorbent material, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed. This was repeated 5 times, and the sample was left overnight for 14 hours. The sample was then centrifuged at 4750 rpm for 30 minutes using a J-15R, and the supernatant was poured off. The open Falcon tube was then left to dry at 35°C for 5 days to obtain the initial adsorbent.

[0197] The initial adsorbent had the following composition: 26.2% MC, 65.5% Al-fumarate, and 8.3% water.

[0198] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of methanol (second solvent). Every 12 hours, the methanol was replaced with 5 ml of fresh sample. This was repeated for a total of 9 days to obtain a binder-reduced adsorbent.

[0199] Adsorbent formation. The binder-reduced adsorbent was then removed from the methanol and dried at room temperature overnight. The solvent-dried binder-reduced adsorbent was then further dried and activated by heating at 130° C. under vacuum for 12 hours to yield an adsorbent comprising 78.4% Al-fumarate and 21.6% MC.

[0200] For clarification - the above analysis meant that the initial sorbent had 40 parts methylcellulose per 100 parts MOF. The sorbent (and therefore the binder-reduced sorbent) had 27.6 parts methylcellulose per 100 parts MOF. This represented the removal of 31% of the binder originally present.

[0201] Example 16 (Invention) Preparation of an adsorbent comprising UTSA-16 and polyvinyl alcohol (PVA). Preparation of the initial mixture. 1.6 g of PVA (Mowiol 10-98, Sigma-Aldrich) was dissolved in 40 ml of water (first solvent) by heating at 80° C. for 1 h.

[0202] Adsorbent material – Preparation of UTSA-16 MOF. Zinc acetate dihydrate (3.1 g, CAS 5970-45-6, lab grade supplied by Thermo Scientific) and citric acid (2.7 g, CAS 77-92-9, supplied by Thermo Scientific) were mixed with 26 mL of deionized water in a 50 ml vial. 2.3 g of potassium hydroxide (85%, CAS 1310-58-3, supplied by Thermo Scientific) was dissolved in 11.3 mL of deionized water in a beaker. The KOH solution was added to the zinc solution and mixed using a stirrer. 12.2 mL of ethanol was then added and the temperature of the reaction mixture was increased to 85° C. for 4 hours and then allowed to cool to ambient temperature. The product was then centrifuged, redispersed in 50 mL of water, and washed three times with water by centrifuging at 4750 rpm for 20 minutes using a J-15R. After the final centrifugation, the supernatant was decanted off leaving a wet pellet of UTSA-16 adsorbent material.

[0203] Contacting the adsorbent material with the initial mixture. 5 ml of the initial mixture prepared above at ambient temperature was added to a Falcon tube containing 1.0 g of wet UTSA-16 adsorbent material pellets prepared above, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed. This was repeated 5 times, and the sample was left overnight for 14 hours. The sample was then centrifuged at 4750 rpm for 30 minutes using a J-15R, and the supernatant was poured off. The open Falcon tube was then left to dry at 35° C. for 4 days to obtain the initial adsorbent.

[0204] This resulted in an initial adsorbent with a water level of 12%, 70% UTSA-16, and 18% PVA.

[0205] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of ethanol (second solvent), which was replaced with fresh 5 ml of sample every 12 hours, and this was repeated for a total of 9 days to obtain a binder-reduced adsorbent.

[0206] Adsorbent formation. The binder-reduced adsorbent was then removed from the second solvent and allowed to dry overnight at room temperature. The solvent-dried binder-reduced adsorbent was then further dried and activated by heating at 130° C. under vacuum for 12 hours. This resulted in an adsorbent comprising 90.1% UTSA-16 and 9.9% PVA.

[0207] For clarification - the above analysis meant that the initial sorbent had 25.7 parts PVA per 100 parts MOF. The sorbent (and therefore the binder-reduced sorbent) had 11.0 parts PVA per 100 parts MOF. This represented the removal of 57.3% of the organic binder originally present.

[0208] Example 17 (Invention) Preparation of an adsorbent comprising HKUST-1 and a PVA / methylcellulose mixed binder. Preparation of the initial mixture. 0.53 g of methylcellulose (viscosity 400 cPs, Thermo Scientific) and 1.07 g of PVA were dissolved in 40 ml of 99.9% anhydrous DMSO (dimethyl sulfoxide supplied by Sigma-Aldrich) by heating at 90° C. for 1 h.

[0209] Preparation of adsorbent material-HKUST-1 MOF. Copper acetate monohydrate (2.4 g, CAS 6046-93-1, Sigma-Aldrich) and 1,3,5-benzenetricarboxylic acid (3.36 g, CAS 528-44-9, Sigma-Aldrich) were dissolved in a water / ethanol (30%) mixture and stirred at room temperature or 50 °C for 45 min. After the desired time, the formed HKUST-1 was centrifuged (4750 rpm, 15 min, Beckman Coulter J-15R), washed with ethanol, and centrifuged. The supernatant was decanted.

[0210] Contacting the adsorbent material with the initial mixture. 5 ml of the initial mixture prepared above was added to the Falcon tube containing 1.0 g of HKUST-1 adsorbent material, and the Falcon tube was vigorously stirred by hand for 5 minutes to ensure everything was dispersed and mixed. This was repeated several times, and the sample was left for several hours. The sample was then centrifuged at 4750 rpm for 30 minutes using a J-15R, and the supernatant was poured off. The open Falcon tube was then left to dry at 35°C for 4 days to obtain the initial adsorbent.

[0211] The initial adsorbent had the following composition: 18.3% PVA / MC, 73.4% HKUST-1, and 8.3% DMSO. Note that the TGA method was unable to distinguish between PVA and methylcellulose, so total binder levels were measured.

[0212] Formation of binder-reduced adsorbents. The initial adsorbent was then immersed in 5 ml of a 97:3 mixture of methanol:PEG 600 (second solvent). Every 12 hours the solvent was replaced with 5 ml of fresh sample. This was repeated for a total of 9 days to obtain a binder-reduced adsorbent.

[0213] Adsorbent formation. The binder-reduced adsorbent was then removed from the second solvent and dried overnight at room temperature. The solvent-dried binder-reduced adsorbent was then further dried and activated by heating at 130° C. under vacuum for 12 hours to yield an adsorbent comprising 92.9% HKUST-1 and 7.1% PVA / MC.

[0214] For clarification - the above analysis meant that the initial sorbent had 24.9 parts PVA / MC per 100 parts MOF. The sorbent (and therefore the binder-reduced sorbent) had 7.6 parts PVA per 100 parts MOF. This represented the removal of 69.5% of the PVA / MC binder originally present.

[0215] The adsorbents prepared above had the following properties: An equivalent adsorbent prepared without the binder removal step had no significant BET area. HKUST-1 powder prepared according to the synthesis described and then dried at 120°C under vacuum for 12 hours had a BET area of ​​1560 m 2 g -1 The BET area was 1.01 mm.

[0216] [Table 5]

Claims

1. (a) contacting an adsorbent material with an initial mixture to form a solvated adsorbent mixture in a first solvent, wherein the adsorbent material is selected from metal organic frameworks or precursors thereof, covalent organic frameworks or precursors thereof, zeolites, activated carbon, organic cages, and any combination thereof, the initial mixture comprising a polymeric organic binder and a first solvent, the solvated adsorbent mixture comprising an adsorbent material, a polymeric organic binder, and a first solvent, wherein the polymeric organic binder is adsorbed onto a surface of the adsorbent material, and the first solvent is distributed throughout the solvated adsorbent mixture; (b) removing at least a portion of the first solvent from the adsorbent mixture solvated in the first solvent to form an initial adsorbate; (c) contacting the initial adsorbent with the second solvent to form a binder-reduced adsorbent, wherein during step (c) at least 20 wt % to 80 wt % of the polymeric organic binder is removed from the initial adsorbent and dissolved in the second solvent, the binder-reduced adsorbent comprising an adsorbent material, a polymeric organic binder, a second solvent, and residual first solvent, the polymeric organic binder being adsorbed on the surface of the adsorbent material, and the second solvent being distributed throughout the binder-reduced adsorbent; (d) solvent drying the binder-reduced adsorbent to form an adsorbent; wherein the solubility of the polymeric organic binder in the first solvent is the same as or higher than the solubility of the polymeric organic binder in the second solvent.

2. The method of claim 1 , wherein the solubility of the polymeric organic binder in the first solvent is higher than the solubility of the polymeric organic binder in the second solvent.

3. 10. The method of claim 1, wherein the adsorbent material is metal-organic framework bodies in particulate form, and the weight ratio of adsorbent material to polymeric organic binder present in the solvated adsorbent mixture ranges from 1:1 to 9:

1.

4. 4. The method of claim 3, wherein the weight ratio of adsorbent material to polymeric organic binder present in the adsorbent body is greater than 3:

1.

5. 10. The method of claim 1, wherein the adsorbent material is in particulate form having an average particle size of less than 900 nm.

6. 6. The method of any one of claims 1 to 5, wherein step (b) comprises a solvent drying step or a solvent drying step followed by a centrifugation and / or filtration step.

7. The solvent drying step in step (b): (i) a low temperature drying step carried out at a temperature below 50°C and a pressure of 0.5 to 1.0 bar for a time longer than 5 hours, wherein said first solvent has a boiling point below 100°C; (ii) a supercritical drying step; (iii) a freeze-drying step; (iv) drying at a temperature greater than 50°C and less than 200°C, wherein the first solvent has a boiling point greater than 100°C; and (v) drying at a temperature above 50°C, wherein the gas concentration of the first solvent removed in the headspace of the solvated adsorbent mixture is maintained between 60% and 95% of its saturation value at the given drying temperature for at least 1 hour; The method of claim 6, wherein the compound is selected from the group consisting of:

8. 6. The method of any one of claims 1 to 5, wherein during step (c), the initial adsorbent is in contact with the second solvent for a period of time greater than 10 hours.

9. the adsorbent material comprising: (i) Zr-containing MOF; (ii) Zn-containing MOFs such as Zeolite Imidazolate Frameworks, Zn-containing UTSA-16, CALF-15, CALF-20, ZnNi(NA); (iii) MOF-74 and its derivatives; (iv) Al-based MOF; (v) Fe-based MOFs; (vi) M(F ６－ｘ ) L ｘ Family MOF; (vii) Cu-based MOF; (viii) Co-based MOF; (ix) Cr-based MOF; (x) Nb-based MOFs such as NbOFFIVE; (xi) Ni-based MOFs; (xii) Mn-based MOF; (xiii) mixed metal MOFs; and (xiv) any combination thereof; 6. The method of claim 1, wherein the metal-organic framework (MOF) body is selected from:

10. the polymeric organic binder is selected from the group consisting of polyvinyl alcohol (PVA), polyvinyl acetate, polyethyleneimine, polyimide (PI), polyvinylpyrrolidone, polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(1,4-phenylene-ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefins, polyamides, chitosan, cellulose acetate, hydroxypropyl methylcellulose (HPMC), methylcellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any combination thereof; The method according to any one of claims 1 to 5, wherein the compound is selected from the group consisting of:

11. 6. The method of claim 1, wherein the second solvent is selected from alcohols and glycols, and the second solvent has a molecular weight of less than 600 Da.

12. The adsorbent comprises: (a) nanoparticles of metals and metal salts; (b) an enzyme; (c) magnetic material; (d) dyes and pigments; (e) graphene and graphene oxide; and (f) any combination thereof; 6. The method of claim 1, comprising a material selected from the group consisting of:

13. 6. The method of claim 1, wherein the adsorbent material is selected from Al fumarate or Zr fumarate, and the polymeric organic binder is selected from polyvinyl alcohol, methyl cellulose, or polyimide.

14. An adsorbent produced according to the method of any one of claims 1 to 5.

15. 15. The adsorbent of claim 14, wherein the adsorbent material comprises a metal-organic framework (MOF): (a) at least 50 wt % metal-organic framework (MOF) particles; (b) 5.0 wt % to 25 wt % of an organic polymer binder; comprising (i) 0.3g / cm ３ Greater bulk density and; (ii) a relative density greater than 0.3 and less than 1.2; (iii) 100 m ２ / g and a BET area greater than (iv) N ２ a microporosity greater than 40% of the total pore volume as measured by adsorption; (v) a macroporosity of less than 15% as measured by mercury porosimetry; An adsorbent having

16. 15. Use of the adsorbent according to claim 14 in gas storage, preferably carbon dioxide or hydrogen storage.