WO2022223598A1 - A process for making small compacted organic framework bodies - Google Patents

A process for making small compacted organic framework bodies Download PDF

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Publication number
WO2022223598A1
WO2022223598A1 PCT/EP2022/060390 EP2022060390W WO2022223598A1 WO 2022223598 A1 WO2022223598 A1 WO 2022223598A1 EP 2022060390 W EP2022060390 W EP 2022060390W WO 2022223598 A1 WO2022223598 A1 WO 2022223598A1
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organic framework
powder
compacted
framework body
process according
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PCT/EP2022/060390
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French (fr)
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Andrew Peter MARSDEN
Nigel Patrick Somerville Roberts
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Immaterial Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3035—Compressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing

Definitions

  • the present invention relates to a process for making small compacted metal-organic framework (MOF) bodies and covalent-organic framework (COF) bodies.
  • MOF metal-organic framework
  • COF covalent-organic framework
  • the present invention provides the production of high-density metal-organic framework (MOF) bodies and covalent-organic framework (COF) bodies.
  • MOF metal-organic framework
  • COF covalent-organic framework
  • MOFs and COFs are sorbent materials that can be used to store gas. These materials can offer many performance advantages over current sorbent materials (such as zeolites) and are candidates for improved gas storage systems required for practical transport systems. MOFs and COFs are of intense interest and many research groups and companies are active in developing synthesis routes and manufacturing methods. Examples of MOFs are HKUST-1,
  • the need to store as much gas as possible in a storage vessel of a given volume means that the bulk density of the MOF and COF is extremely important. The higher the density, the more material can fit into the available working volume.
  • MOFs and COFs are typically prepared in the form of a fine powder. This powder is then typically compacted directly into small compacted bodies, such as tablets. Making MOF or COF small compacted bodies, such as tablets, at industrially relevant rates, such as is done in typical pharmaceutical tablet production, requires that the MOF or COF material is subjected to a very short and intense (high pressure) compaction step.
  • MOFs and COFs have low strengths. For example, the bonds in MOFs are based on metal coordination chemistry and, as such, they are relatively weak. If the MOFs and COFs are subjected to high- compression forces, this can collapse their internal pores. This collapse results in the MOF becoming amorphous, with a loss of surface area and consequent fluid storage capacity. High-pressure production processes to form compacted bodies of MOFs and COFs can result in small compacted bodies having a poor fluid storage capacity.
  • the flowability of the MOF or COF powder needing to be formed into a small compacted body is very often very poor. This means that it is very hard to feed the MOF or COF powder at the required rates into the small individual moulds for forming the small compacted bodies due to the small dimensions involved. Such powders will typically bridge over such a mould and not flow into and fill the mould.
  • Pharmaceutical tablets very often only contain a low level of the actual drug and much of the tablet composition is chosen so as to aid processing. This approach is not viable for MOF or COF small compacted bodies since the small body needs to have the highest possible MOF or COF level so as to maximise performance.
  • the present invention is designed to allow industrially relevant rates of production of small compacted bodies from powders or powder mixes having poor flowability and pressure sensitivity.
  • the process of the present invention minimises the loss of porosity of the MOF and COF material during the processing whilst being able to handle and process very poorly flowing powders.
  • the process of the present invention first compacts the MOF or COF into a larger body.
  • the larger dimensions of the moulds or other equipment needed to form the larger compacted body allow for the feeding and dosing of less flowable powder mixes.
  • the compaction step is done under conditions of low intensity (low pressure and for a longer compaction time), so as to minimise porosity loss, whilst still achieving a high bulk density.
  • the larger compacted body is then milled to form the smaller compacted bodies. In this manner, the porosity and bulk density of the resultant small compacted MOF or COF body is protected, whilst the production capacity of the process is high and industrially relevant.
  • Rui P. P. L. Riberio et al. “Binderless shaped metal-organic framework particles. Impact on carbon dioxide adsorption”, Microporous and mesoporous materials, vol. 275, 1 February 2019 (2019-02-01), pages 111-12, XP055735917, Amserdam, NL, ISSN: 1387-1811, DOI: 10.1016/j. micromeso. 2018.08.002 relates to a study of the carbon dioxide adsorption of metal-organic framework bodies.
  • the present invention relates to a process for making small compacted organic framework bodies, wherein the process comprises the steps of:
  • a maximum internal dimension as determined according to the method of measuring the maximum internal dimension of a body, of from greater than 2.0 mm to less than 100.0 mm;
  • an opposing surface such that one surface is shaped so as to be more convex than the opposite surface;
  • Figure 1 is a schematic illustration of the process showing the small compacted organic framework bodies (1), the organic framework body powder (2), the restraining device (3), the restrained organic framework body powder (4) and the large compacted organic framework body (5).
  • the process for making small compacted organic framework bodies comprises the steps of:
  • the process is preferably an indexing process.
  • indexing process it is typically meant a process that operates in a non-continuous, start-stop manner. For example, such that the restraining device, containing the powder to be compacted, is brought to the press by the action of a moving belt or other conveying means and the belt or conveying means is stopped for sufficient time to allow the compression step to happen before the compressed material is moved on for further processing.
  • Steps (a) and (b) may be carried out on a conveyor belt.
  • Suitable equipment for conveying the powder to the press is a horizontal conveyor belt or continuous loop.
  • the organic framework powder may be subjected to a vibration step preceding and/or during the compaction step (b).
  • the vibration of the powder helps increase the bulk density prior to and/or during the compression step.
  • the vibrating may be induced in the powder bed by a vibrating means.
  • This vibrating means may be a plate underneath the belt and in continuous contact with the belt or by the press-head during the period that it is in contact with the powder. Applying the vibration means before the compaction can help deaerate the powder and enable a denser powder bed to be presented to the compression means.
  • the preferred frequency depends on the nature of the material but is preferably less than 1000 Hz and even more preferably less than 500 Hz.
  • the organic framework powder may be contacted with a solvent prior to the compaction step (b).
  • Solvating a porous material such as a MOF or COF prior to compaction can assist in reducing the degree of porosity loss during compression. This can either be due to the supportive benefits of the internal pressure of the solvent during compression or the presence of the solvent helping disperse the pressure more uniformly throughout the MOF structure, thus avoiding stress concentrations.
  • the level of solvent that needs to be applied is such that the powder flowability of the mixture becomes very poor and problematic.
  • the solvent(s) can be applied in a mixer, such as a Kenwood FP570 to help disperse the liquid uniformly into the MOF powder.
  • the solvent(s) can be sprayed into the gently agitated MOF powder in the form of a fine spray.
  • Suitable solvents are described in more detail below.
  • the solvents typically need to be sufficiently volatile such that they can be removed by applied heat and vacuum.
  • Suitable solvents include organic liquids such as lower chain length alcohols like ethanol and methanol, acetone, DMF and mixtures thereof.
  • Suitable solvents can also include aqueous systems.
  • Suitable aqueous systems can include acidic and alkaline solutions including aqueous solutions of acetic acid, hydrochloric acid, sodium hydroxide.
  • a suitable solvent can also be a mixture of organic solvent and water, such as an alcohol and water, preferably a mixture of ethanol and water.
  • the organic framework powder may be contacted with a binder prior to the compaction step (b).
  • a binder material in the liquid applied to the powder during the solvation step.
  • binder it is meant any material that is not removed by the heat and/or vacuum used to remove the solvent.
  • Binders can be added as solutions, liquids or as powders. When the binder is added as a powder, it is preferred that a small particle size is used since the smaller the particle size, the more uniformly the binder can be dispersed throughout the mix and the more particles of material will be in contact with the binder. Binder particle sizes of less than 20 pm are preferred.
  • Suitable powder binders include polymers such as PVA or PVB, graphite, mesoporous p-alumina, PVF and cellulose-based materials such as cellulose acetate and methylcellulose. Soluble binders can obviously be added as solutions.
  • the binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyvinyl pyrrolidone, polyimide (PI), polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(l,4-phenylene- ether-ether- sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, chitosan, cellulose acetate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any combination thereof.
  • PVA polyvinyl alcohol
  • PI polyethyleneimine
  • PI polyvinyl formal
  • polyacrylic acid sodium polyacrylate
  • PFEES poly(l,4-phenylene- ether-ether- sulfone)
  • PDMS poly(dimethylsi
  • a preferred application is for a binder material to be dissolved in a solvent material as described above.
  • the binder is residual MOF material from the MOF synthesis.
  • the liquid that is applied is a reaction mixture comprising MOF crystallites, MOF reactants and solvent.
  • the residual MOF material from this can act as a binder.
  • any material that can bind the MOF crystallite together can be regarded as a binder regardless of chemical composition or nature. Suitable binders are described in more detail below.
  • the organic framework powder may be milled prior to being compacted. It is preferred if the MOF and COF are milled prior to compaction. This is to break up any large aggregates formed during prior processing. The intention is not to mill the individual crystallites of MOF as this would result in a loss of porosity. Instead, gentle milling can be applied. This milling step may be carried out in any suitable mill including a jet mill or ball mill. A preferred approach is to use a ball mill with the powder and to use lightweight media balls during milling so as to minimise unwanted milling and breakage.
  • Step (a) dosing organic framework body powder Step (a) doses organic framework body powder into a restraining device to form restrained organic framework body powder.
  • the powder needs to be spread uniformly across a mould or other restraining device such as a cavity-frame typically to form a powder bed of uniform thickness.
  • This can be achieved by the use of one or more vibratory feeders (often combined with a vibrating comb mechanism) and levelling means, such as scraper bars and/or rollers. This is especially necessary when the powder has been solvated and has a very poor flowability.
  • the powder can either be deposited onto a moving belt or restraining device by being fed from a fixed position dosing feeder, or the mould or restraining device can be filled by the action of a dosing feeder being passed over the mould or restraining device.
  • a mechanism is especially preferred when the powder is dosed onto a moving belt which includes the restraining device or which brings the powder bed to the restraining device, such as a descending knife-edge cavity frame.
  • the mould or restraining device can even be filled by hand action.
  • Step (b) compacting the restrained organic framework body powder Step (b) compacts the restrained organic framework body powder to form a large compacted organic framework body.
  • This compaction step (b) is carried out under conditions of: (i) a pressure of between 15 MPa and 200 MPa; and (ii) a compaction time of greater than 5.0 seconds.
  • the powder is typically compressed by the action of a plate which descends (relative to the powder) to compact the powder to a controlled pressure.
  • a suitable press for this is a PH690 made by SACMI or the GT2074 Lab Press from Gabbrielli Technology.
  • the plate can also be vibrated during the compression step. This is an especially preferred feature as it maximises density and compaction due to optimising powder packing during densification.
  • the pressure can be applied in a discontinuous manner.
  • the compaction step (b) may be carried out under conditions of: (i) a pressure of from 15 MPa to 75 MPa; and (ii) a compaction time of more than 60 seconds.
  • the pressure is kept to the lowest value possible to minimise loss of porosity. Extended compression times are useful, especially if the pressure is applied in an increasing manner in several non- continuous stages as the periodic release of the pressure relieves internal stresses and allows for a more uniform compaction process.
  • the pressure may be applied in a non-continuous manner.
  • non-continuous manner it is typically meant that the pressure applied to the material during the main compression period (excluding start (ramp up) and stop (ramp down) pressures) is either: (i) applied in at least two sequential discrete steps of increased pressure, often with a short intervening period during which the pressure is unloaded; or (ii) applied in at least two sequential discrete steps with a short intervening period in which the pressure is unloaded; or (iii) applied in an oscillatory manner by a superposed vibration of a plate applying the compression force; or (iv) by any combination of the above.
  • Such a non-continuous application of pressure assists in the compression and removal of air from the material being compressed.
  • the compaction means may comprise a shaped surface so as to form a large compacted organic framework body that comprises briquette or tablet-like shapes.
  • the resulting compressed powder article may have several forms or shapes.
  • One preferred form is for the compressed powder not to be of uniform thickness throughout. Instead the presence of indentations and thinner regions can make it easier for the compressed powder article to be broken in desired directions.
  • This non-uniform thickness can be formed by the compression plate having relief indentations machined into its surface. A regular pattern of indentations is preferred.
  • Step (b) may be carried out at a temperature of from 50 °C to 150 °C.
  • the use of an elevated temperature can be advantageous if it softens the material to be compressed and allows for easier plastic deformation and improved particle-particle interlocking during the compression process.
  • the heat can be applied by a variety of techniques including pre-heating the powder in an oven, using heated moulds and electrical resistance heating where current is passed through the powder bed during compression so as to generate heat by electrical resistance.
  • Step (c) breaking the large compacted organic framework body Step (c) breaks the large compacted organic framework body into small compacted organic framework bodies.
  • Step (c) may be carried out by a vibration sieving process. Subjecting the compressed bodies to a vibration sieving step, wherein the compressed bodies are passed over a vibrating sieve with a large mesh size is an effective way of breaking up the compressed body along any indentation lines in the body such that undesired small fragments are sieved off for re-use. The desired larger fragments can be collected.
  • the small compacted organic framework bodies may be subjected to a rounding or spheronisation step.
  • Optional step (d) drying the small compacted organic framework bodies drying the small compacted organic framework bodies: Optional step (d) dries the small compacted organic framework bodies, typically by subjecting them to heat and/or vacuum.
  • Organic framework body is selected from a metal-organic framework body and/or a covalent-organic framework body. It may be preferred that the organic framework body is a metal-organic framework (MOF) body.
  • MOF metal-organic framework
  • Organic framework body powder can consist of metal- organic framework (MOF) or covalent-organic framework (COF) powders. These powders typically comprise small crystallites of less than 150 nm diameter, which are aggregated into larger particles and form a powder of less than 500 g/1 envelope bulk density, for example 350 g/1.
  • Suitable metal-organic framework (MOF) materials include UiO-66 and other Zr- based MOFs, ZIF-8 and other Zn-based MOFs, HKUST-1 and other Cu-based MOFs, fumarates including aluminium and zirconium fumarates, amongst others.
  • Suitable COFs include imine-linked COFs such as 3D-COOH-COF and hydrazine-linked COFs such as COF-42-bnn.
  • Small compacted organic framework bodies have dimensions such that the maximum internal dimension is in the range of from greater than 2.0 mm to less than 100.0 mm, or from greater than 2.0 mm to less than 50.0 mm.
  • the small compacted organic framework bodies have an envelope bulk density of greater than 500 g/1.
  • a high bulk density is especially desirable due to the ability to pack more of the MOF and COF material into a given storage volume, such as in a storage container. High densities, whilst still maintaining porosity, are highly desired.
  • the small compacted organic framework bodies have: (i) a maximum internal dimension of greater than 2.0 mm, or greater than 5.0 mm; and (ii) an opposing surface such that one surface is shaped so as to be more convex than the opposite surface.
  • the bodies need to be sufficiently large that they still allow reasonable gas or fluid flow around them when packed in a vessel.
  • the use of a preferred convex surface ensures that there are always gas channels around the packed bodies.
  • the large compacted organic framework body has a dimension such that it has a maximum internal diameter between opposite edges of at least 11.0 cm, or at least 15.0 cm, or even at least 20.0 cm, or even at least 25.0 cm.
  • the large compacted organic framework body may have a dimension such that the thickness is from 1.0 mm to 100.0 mm.
  • the large body needs to be sufficiently thick that it can be handled subsequent to pressing and that the smaller compacted bodies that come from breakage of the larger body are sufficiently large to be useful.
  • Solvent Suitable solvents are selected from ethanol, methanol, propanol, other low molecular weight alcohols and mixtures thereof.
  • a preferred solvent is an alcohol, preferably ethanol.
  • Suitable solvents can also include aqueous systems.
  • Binder Suitable binders are selected from polymeric materials such as PVA, and the reactants used to form the organic framework powders.
  • the binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyvinyl pyrrolidone, polyimide (PI), polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(l,4-phenylene- ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, chitosan, cellulose acetate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any combination thereof.
  • PVA polyvinyl alcohol
  • PI polyethyleneimine
  • PI polyvinyl formal
  • polyacrylic acid sodium polyacrylate
  • PFEES poly(l,4-phenylene- ether-ether-sulfone)
  • PDMS poly(dimethylsiloxan
  • the restraining device in step (a) typically functions to restrain the powder, such as by a knife-edge framework that is lowered from above the powder bed such that it penetrates the powder bed and comes into contact with the base belt so as to isolate a portion of the powder bed for compaction.
  • the restraining device can be a mould into which the powder has been uniformly dispersed. The typical depth of these moulds is up to 1.0 cm.
  • the device typically as a dimension such that at least one edge of the restraining device has a length of at least 11.0 cm.
  • Method of measuring the maximum internal dimension of a body The dimensions of the bodies are measured by optical means due to their relatively large sizes. An optical microscope is used in conjunction with a scale so as to measure dimensions. A suitable microscope for this that includes particle size measurement capability is the Leica DVM6 though the required type of image analysis capability is virtually standard in most modern microscopes.
  • the envelope bulk density of an individual body is measured by the envelope density.
  • the envelope density of a body is defined by ASTM Standard 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. Suitable equipment for this is the GeoPyc series of Analyzers, for example the GeoPyc 1360 Envelope Density Analyzer from Micromeritics Corporation.
  • Method of measuring the maximum internal diameter between opposite edges of a body The maximum internal diameter between opposite edges is measured optically with a scale using visual estimation to determine the required endpoints. Multiple (at least 5) measurements across the internal dimensions of a particle need to be taken so as to cover the entire particle and the greatest value taken as the maximum internal diameter.
  • 300g of this milled material is then mixed with 30g of ethanol, supplied by Aldrich, to form a solvated organic framework powder mass. This happens in a kitchen mixer, Kenwood FP120.
  • the solvated powder mix is then dispersed by vibration and fed into a mould of dimensions 20 by 20 cm by 1 cm.
  • the top of the powder is levelled with the top of the mould by scraping.
  • the mould and solvated powder are then vibrated at 200 Hz for 1 minute to densify and deaerate the powder mass.
  • the partially densified powder mess is then compressed by a plate to a maximum pressure of 70 MPa.
  • the powder is first compacted at 20 MPa for 10 seconds and then the pressure is increased to 70 MPa for a further 10 seconds.
  • the large compacted body is then removed from the mould and broken to form small compacted bodies of less than 20 mm.
  • the small compacted bodies are then dried at 100°C under vacuum for 12 hours to remove the solvent.
  • the resulting bodies have envelope densities of greater than 600 g/1.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention relates to a process for making small compacted organic framework bodies, wherein the process comprises the steps of: (a) dosing organic framework body powder into a restraining device to form restrained organic framework body powder; (b) compacting the restrained organic framework body powder to form a large compacted organic framework body; (c) breaking the large compacted organic framework body into small compacted organic framework bodies; and (d) optionally, drying the small compactedorganic framework bodies, wherein the organic framework body is selected from a metal-organic framework body and/or a covalent-organic framework body, wherein the small compacted organic framework bodies have: (I) a maximum internal dimension of from greater than 2.0 mm to less than 100.0 mm; (II) an opposing surface such that one surface is shaped so as to be more convex than the opposite surface; and (III) an envelope bulk density of greater than 500 g/l, wherein the large compacted organic framework body has a dimension such that it has a maximum internal diameter between opposite edges of at least 11.0 cm, wherein the compaction step (b) is carried out under conditions of: (i) a pressure of between 15 MPa and 200 MPa; and (ii) a compaction time of greater than 5.0 seconds.

Description

A process for making small compacted organic framework bodies
Field of the invention
The present invention relates to a process for making small compacted metal-organic framework (MOF) bodies and covalent-organic framework (COF) bodies.
Background of the invention
The present invention provides the production of high-density metal-organic framework (MOF) bodies and covalent-organic framework (COF) bodies.
MOFs and COFs are sorbent materials that can be used to store gas. These materials can offer many performance advantages over current sorbent materials (such as zeolites) and are candidates for improved gas storage systems required for practical transport systems. MOFs and COFs are of intense interest and many research groups and companies are active in developing synthesis routes and manufacturing methods. Examples of MOFs are HKUST-1,
UiO-66 and ZIF-8.
The need to store as much gas as possible in a storage vessel of a given volume means that the bulk density of the MOF and COF is extremely important. The higher the density, the more material can fit into the available working volume.
MOFs and COFs are typically prepared in the form of a fine powder. This powder is then typically compacted directly into small compacted bodies, such as tablets. Making MOF or COF small compacted bodies, such as tablets, at industrially relevant rates, such as is done in typical pharmaceutical tablet production, requires that the MOF or COF material is subjected to a very short and intense (high pressure) compaction step. However, MOFs and COFs have low strengths. For example, the bonds in MOFs are based on metal coordination chemistry and, as such, they are relatively weak. If the MOFs and COFs are subjected to high- compression forces, this can collapse their internal pores. This collapse results in the MOF becoming amorphous, with a loss of surface area and consequent fluid storage capacity. High-pressure production processes to form compacted bodies of MOFs and COFs can result in small compacted bodies having a poor fluid storage capacity.
In addition, the flowability of the MOF or COF powder needing to be formed into a small compacted body is very often very poor. This means that it is very hard to feed the MOF or COF powder at the required rates into the small individual moulds for forming the small compacted bodies due to the small dimensions involved. Such powders will typically bridge over such a mould and not flow into and fill the mould. Pharmaceutical tablets very often only contain a low level of the actual drug and much of the tablet composition is chosen so as to aid processing. This approach is not viable for MOF or COF small compacted bodies since the small body needs to have the highest possible MOF or COF level so as to maximise performance. The present invention is designed to allow industrially relevant rates of production of small compacted bodies from powders or powder mixes having poor flowability and pressure sensitivity.
The process of the present invention minimises the loss of porosity of the MOF and COF material during the processing whilst being able to handle and process very poorly flowing powders. Instead of directly compacting the MOF or COF into a small compacted body, the process of the present invention first compacts the MOF or COF into a larger body. The larger dimensions of the moulds or other equipment needed to form the larger compacted body allow for the feeding and dosing of less flowable powder mixes. The compaction step is done under conditions of low intensity (low pressure and for a longer compaction time), so as to minimise porosity loss, whilst still achieving a high bulk density. The larger compacted body is then milled to form the smaller compacted bodies. In this manner, the porosity and bulk density of the resultant small compacted MOF or COF body is protected, whilst the production capacity of the process is high and industrially relevant.
Rui P. P. L. Riberio et al.: “Binderless shaped metal-organic framework particles. Impact on carbon dioxide adsorption”, Microporous and mesoporous materials, vol. 275, 1 February 2019 (2019-02-01), pages 111-12, XP055735917, Amserdam, NL, ISSN: 1387-1811, DOI: 10.1016/j. micromeso. 2018.08.002 relates to a study of the carbon dioxide adsorption of metal-organic framework bodies.
Yoldes Khabzina et al: “Synthesis and shaping scale-up study of functionalised UiO MOF for ammonia air purification filters”, Industrial & engineering chemistry research vol. 57, no. 24, 16 May 2018 (2018-06-16), pages 8200-8208, XP055735929, ISSN:0888-5885, DOI: 10.1021/acs.iecr.8b00808 relates to a study of the synthesis and scale-up of UiO MOF.
Summary of the invention
The present invention relates to a process for making small compacted organic framework bodies, wherein the process comprises the steps of:
(a) dosing organic framework body powder into a restraining device to form restrained organic framework body powder;
(b) compacting the restrained organic framework body powder to form a large compacted organic framework body;
(c) breaking the large compacted organic framework body into small compacted organic framework bodies; and
(d) optionally, drying the small compacted organic framework bodies, wherein the organic framework body is selected from a metal-organic framework body and/or a covalent-organic framework body, wherein the small compacted organic framework bodies have:
(I) a maximum internal dimension, as determined according to the method of measuring the maximum internal dimension of a body, of from greater than 2.0 mm to less than 100.0 mm; (II) an opposing surface such that one surface is shaped so as to be more convex than the opposite surface; and
(III) an envelope bulk density, as determined according to the method of measuring the envelope bulk density of a body, of greater than 500 g/1, wherein the large compacted organic framework body has a dimension such that it has a maximum internal diameter between opposite edges, as determined according to the method of measuring the maximum internal diameter between opposite edges of a body, of at least 11.0 cm, wherein the compaction step (b) is carried out under conditions of:
(i) a pressure of between 15 MPa and 200 MPa; and
(ii) a compaction time of greater than 5.0 seconds.
Brief description of the drawings
Figure 1: Figure 1 is a schematic illustration of the process showing the small compacted organic framework bodies (1), the organic framework body powder (2), the restraining device (3), the restrained organic framework body powder (4) and the large compacted organic framework body (5).
Detailed description of the invention
Process for making small compacted organic framework bodies: The process for making small compacted organic framework bodies comprises the steps of:
(a) dosing organic framework body powder into a restraining device to form restrained organic framework body powder; (b) compacting the restrained organic framework body powder to form a large compacted organic framework body;
(c) breaking the large compacted organic framework body into small compacted organic framework bodies; and
(d) optionally, drying the small compacted organic framework bodies.
The process is preferably an indexing process. By indexing process, it is typically meant a process that operates in a non-continuous, start-stop manner. For example, such that the restraining device, containing the powder to be compacted, is brought to the press by the action of a moving belt or other conveying means and the belt or conveying means is stopped for sufficient time to allow the compression step to happen before the compressed material is moved on for further processing.
Steps (a) and (b) may be carried out on a conveyor belt. Suitable equipment for conveying the powder to the press is a horizontal conveyor belt or continuous loop.
The organic framework powder may be subjected to a vibration step preceding and/or during the compaction step (b). The vibration of the powder helps increase the bulk density prior to and/or during the compression step. The vibrating may be induced in the powder bed by a vibrating means. This vibrating means may be a plate underneath the belt and in continuous contact with the belt or by the press-head during the period that it is in contact with the powder. Applying the vibration means before the compaction can help deaerate the powder and enable a denser powder bed to be presented to the compression means. The preferred frequency depends on the nature of the material but is preferably less than 1000 Hz and even more preferably less than 500 Hz.
The organic framework powder may be contacted with a solvent prior to the compaction step (b). Solvating a porous material such as a MOF or COF prior to compaction can assist in reducing the degree of porosity loss during compression. This can either be due to the supportive benefits of the internal pressure of the solvent during compression or the presence of the solvent helping disperse the pressure more uniformly throughout the MOF structure, thus avoiding stress concentrations. However, the level of solvent that needs to be applied is such that the powder flowability of the mixture becomes very poor and problematic. The solvent(s) can be applied in a mixer, such as a Kenwood FP570 to help disperse the liquid uniformly into the MOF powder. Alternatively, the solvent(s) can be sprayed into the gently agitated MOF powder in the form of a fine spray. Suitable solvents are described in more detail below. The solvents typically need to be sufficiently volatile such that they can be removed by applied heat and vacuum. Suitable solvents include organic liquids such as lower chain length alcohols like ethanol and methanol, acetone, DMF and mixtures thereof.
Suitable solvents can also include aqueous systems. Suitable aqueous systems can include acidic and alkaline solutions including aqueous solutions of acetic acid, hydrochloric acid, sodium hydroxide. A suitable solvent can also be a mixture of organic solvent and water, such as an alcohol and water, preferably a mixture of ethanol and water.
The organic framework powder may be contacted with a binder prior to the compaction step (b). In a similar manner to above, there may be a binder material in the liquid applied to the powder during the solvation step. By binder, it is meant any material that is not removed by the heat and/or vacuum used to remove the solvent. Binders can be added as solutions, liquids or as powders. When the binder is added as a powder, it is preferred that a small particle size is used since the smaller the particle size, the more uniformly the binder can be dispersed throughout the mix and the more particles of material will be in contact with the binder. Binder particle sizes of less than 20 pm are preferred. Suitable powder binders include polymers such as PVA or PVB, graphite, mesoporous p-alumina, PVF and cellulose-based materials such as cellulose acetate and methylcellulose. Soluble binders can obviously be added as solutions.
Preferably, the binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyvinyl pyrrolidone, polyimide (PI), polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(l,4-phenylene- ether-ether- sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, chitosan, cellulose acetate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any combination thereof.
A preferred application is for a binder material to be dissolved in a solvent material as described above. Another possibility is that the binder is residual MOF material from the MOF synthesis. In this case, the liquid that is applied is a reaction mixture comprising MOF crystallites, MOF reactants and solvent. The residual MOF material from this can act as a binder. This is an especially preferred solution. However, any material that can bind the MOF crystallite together can be regarded as a binder regardless of chemical composition or nature. Suitable binders are described in more detail below.
The organic framework powder may be milled prior to being compacted. It is preferred if the MOF and COF are milled prior to compaction. This is to break up any large aggregates formed during prior processing. The intention is not to mill the individual crystallites of MOF as this would result in a loss of porosity. Instead, gentle milling can be applied. This milling step may be carried out in any suitable mill including a jet mill or ball mill. A preferred approach is to use a ball mill with the powder and to use lightweight media balls during milling so as to minimise unwanted milling and breakage.
Step (a) dosing organic framework body powder: Step (a) doses organic framework body powder into a restraining device to form restrained organic framework body powder. During this dosing step, the powder needs to be spread uniformly across a mould or other restraining device such as a cavity-frame typically to form a powder bed of uniform thickness. This can be achieved by the use of one or more vibratory feeders (often combined with a vibrating comb mechanism) and levelling means, such as scraper bars and/or rollers. This is especially necessary when the powder has been solvated and has a very poor flowability. The powder can either be deposited onto a moving belt or restraining device by being fed from a fixed position dosing feeder, or the mould or restraining device can be filled by the action of a dosing feeder being passed over the mould or restraining device. Such a mechanism is especially preferred when the powder is dosed onto a moving belt which includes the restraining device or which brings the powder bed to the restraining device, such as a descending knife-edge cavity frame. The mould or restraining device can even be filled by hand action.
Step (b) compacting the restrained organic framework body powder: Step (b) compacts the restrained organic framework body powder to form a large compacted organic framework body. This compaction step (b) is carried out under conditions of: (i) a pressure of between 15 MPa and 200 MPa; and (ii) a compaction time of greater than 5.0 seconds. The powder is typically compressed by the action of a plate which descends (relative to the powder) to compact the powder to a controlled pressure. A suitable press for this is a PH690 made by SACMI or the GT2074 Lab Press from Gabbrielli Technology. The plate can also be vibrated during the compression step. This is an especially preferred feature as it maximises density and compaction due to optimising powder packing during densification. The pressure can be applied in a discontinuous manner.
The compaction step (b) may be carried out under conditions of: (i) a pressure of from 15 MPa to 75 MPa; and (ii) a compaction time of more than 60 seconds. Preferably, the pressure is kept to the lowest value possible to minimise loss of porosity. Extended compression times are useful, especially if the pressure is applied in an increasing manner in several non- continuous stages as the periodic release of the pressure relieves internal stresses and allows for a more uniform compaction process.
During the compaction step (b) the pressure may be applied in a non-continuous manner. By non-continuous manner it is typically meant that the pressure applied to the material during the main compression period (excluding start (ramp up) and stop (ramp down) pressures) is either: (i) applied in at least two sequential discrete steps of increased pressure, often with a short intervening period during which the pressure is unloaded; or (ii) applied in at least two sequential discrete steps with a short intervening period in which the pressure is unloaded; or (iii) applied in an oscillatory manner by a superposed vibration of a plate applying the compression force; or (iv) by any combination of the above. Such a non-continuous application of pressure assists in the compression and removal of air from the material being compressed.
During step (b), the compaction means may comprise a shaped surface so as to form a large compacted organic framework body that comprises briquette or tablet-like shapes. The resulting compressed powder article may have several forms or shapes. One preferred form is for the compressed powder not to be of uniform thickness throughout. Instead the presence of indentations and thinner regions can make it easier for the compressed powder article to be broken in desired directions. This non-uniform thickness can be formed by the compression plate having relief indentations machined into its surface. A regular pattern of indentations is preferred. Step (b) may be carried out at a temperature of from 50 °C to 150 °C. The use of an elevated temperature can be advantageous if it softens the material to be compressed and allows for easier plastic deformation and improved particle-particle interlocking during the compression process. The heat can be applied by a variety of techniques including pre-heating the powder in an oven, using heated moulds and electrical resistance heating where current is passed through the powder bed during compression so as to generate heat by electrical resistance.
Step (c) breaking the large compacted organic framework body: Step (c) breaks the large compacted organic framework body into small compacted organic framework bodies.
Step (c) may be carried out by a vibration sieving process. Subjecting the compressed bodies to a vibration sieving step, wherein the compressed bodies are passed over a vibrating sieve with a large mesh size is an effective way of breaking up the compressed body along any indentation lines in the body such that undesired small fragments are sieved off for re-use. The desired larger fragments can be collected.
It may be preferred for the small compacted organic framework bodies to be subjected to a rounding or spheronisation step.
Optional step (d) drying the small compacted organic framework bodies: Optional step (d) dries the small compacted organic framework bodies, typically by subjecting them to heat and/or vacuum.
Organic framework body: The organic framework body is selected from a metal-organic framework body and/or a covalent-organic framework body. It may be preferred that the organic framework body is a metal-organic framework (MOF) body.
Organic framework body powder: The organic framework powder can consist of metal- organic framework (MOF) or covalent-organic framework (COF) powders. These powders typically comprise small crystallites of less than 150 nm diameter, which are aggregated into larger particles and form a powder of less than 500 g/1 envelope bulk density, for example 350 g/1. Suitable metal-organic framework (MOF) materials include UiO-66 and other Zr- based MOFs, ZIF-8 and other Zn-based MOFs, HKUST-1 and other Cu-based MOFs, fumarates including aluminium and zirconium fumarates, amongst others. Suitable COFs include imine-linked COFs such as 3D-COOH-COF and hydrazine-linked COFs such as COF-42-bnn.
Small compacted organic framework bodies: The small compacted organic framework bodies have dimensions such that the maximum internal dimension is in the range of from greater than 2.0 mm to less than 100.0 mm, or from greater than 2.0 mm to less than 50.0 mm.
The small compacted organic framework bodies have an envelope bulk density of greater than 500 g/1. A high bulk density is especially desirable due to the ability to pack more of the MOF and COF material into a given storage volume, such as in a storage container. High densities, whilst still maintaining porosity, are highly desired.
The small compacted organic framework bodies have: (i) a maximum internal dimension of greater than 2.0 mm, or greater than 5.0 mm; and (ii) an opposing surface such that one surface is shaped so as to be more convex than the opposite surface. The bodies need to be sufficiently large that they still allow reasonable gas or fluid flow around them when packed in a vessel. The use of a preferred convex surface ensures that there are always gas channels around the packed bodies.
Large compacted organic framework body: The large compacted organic framework body has a dimension such that it has a maximum internal diameter between opposite edges of at least 11.0 cm, or at least 15.0 cm, or even at least 20.0 cm, or even at least 25.0 cm.
The large compacted organic framework body may have a dimension such that the thickness is from 1.0 mm to 100.0 mm. The large body needs to be sufficiently thick that it can be handled subsequent to pressing and that the smaller compacted bodies that come from breakage of the larger body are sufficiently large to be useful.
Solvent: Suitable solvents are selected from ethanol, methanol, propanol, other low molecular weight alcohols and mixtures thereof. A preferred solvent is an alcohol, preferably ethanol. Suitable solvents can also include aqueous systems. Binder: Suitable binders are selected from polymeric materials such as PVA, and the reactants used to form the organic framework powders. Preferably, the binder is selected from polyvinyl alcohol (PVA), polyethyleneimine, polyvinyl pyrrolidone, polyimide (PI), polyvinyl formal, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polypropylene glycol, poly(l,4-phenylene- ether-ether-sulfone) (PFEES), poly(dimethylsiloxane) (PDMS), poly(tetrahydrofuran) (PTHF), polyolefin, polyamide, chitosan, cellulose acetate, hydroxypropyl methyl cellulose (HPMC), methyl cellulose, hydroxypropyl methylcellulose phthalate (HPMCP), and any combination thereof.
Restraining device: The restraining device in step (a) typically functions to restrain the powder, such as by a knife-edge framework that is lowered from above the powder bed such that it penetrates the powder bed and comes into contact with the base belt so as to isolate a portion of the powder bed for compaction. Alternatively, the restraining device can be a mould into which the powder has been uniformly dispersed. The typical depth of these moulds is up to 1.0 cm. The device typically as a dimension such that at least one edge of the restraining device has a length of at least 11.0 cm.
Method of measuring the maximum internal dimension of a body: The dimensions of the bodies are measured by optical means due to their relatively large sizes. An optical microscope is used in conjunction with a scale so as to measure dimensions. A suitable microscope for this that includes particle size measurement capability is the Leica DVM6 though the required type of image analysis capability is virtually standard in most modern microscopes.
Method of measuring the envelope bulk density of a body: The envelope bulk density of an individual body is measured by the envelope density. The envelope density of a body is defined by ASTM Standard 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. Suitable equipment for this is the GeoPyc series of Analyzers, for example the GeoPyc 1360 Envelope Density Analyzer from Micromeritics Corporation. Method of measuring the maximum internal diameter between opposite edges of a body: The maximum internal diameter between opposite edges is measured optically with a scale using visual estimation to determine the required endpoints. Multiple (at least 5) measurements across the internal dimensions of a particle need to be taken so as to cover the entire particle and the greatest value taken as the maximum internal diameter.
Examples
Production of UiO-66 bodies by tabletting.
100 g of commercially available UiO-66 powder supplied by MOFapps of Oslo is ground in a laboratory ball mill (MITR, model YXQM-8L), using rubber media balls for 5 minutes at 80 rpm to form a milled powder material. This is repeated multiple times.
300g of this milled material is then mixed with 30g of ethanol, supplied by Aldrich, to form a solvated organic framework powder mass. This happens in a kitchen mixer, Kenwood FP120.
The solvated powder mix is then dispersed by vibration and fed into a mould of dimensions 20 by 20 cm by 1 cm. The top of the powder is levelled with the top of the mould by scraping. The mould and solvated powder are then vibrated at 200 Hz for 1 minute to densify and deaerate the powder mass.
The partially densified powder mess is then compressed by a plate to a maximum pressure of 70 MPa. The powder is first compacted at 20 MPa for 10 seconds and then the pressure is increased to 70 MPa for a further 10 seconds.
The large compacted body is then removed from the mould and broken to form small compacted bodies of less than 20 mm. The small compacted bodies are then dried at 100°C under vacuum for 12 hours to remove the solvent.
The resulting bodies have envelope densities of greater than 600 g/1.

Claims

Claims
1. A process for making small compacted organic framework bodies, wherein the process comprises the steps of:
(a) dosing organic framework body powder into a restraining device to form restrained organic framework body powder;
(b) compacting the restrained organic framework body powder to form a large compacted organic framework body;
(c) breaking the large compacted organic framework body into small compacted organic framework bodies; and
(d) optionally, drying the small compacted organic framework bodies, wherein the organic framework body is selected from a metal-organic framework body and/or a covalent-organic framework body, wherein the small compacted organic framework bodies have:
(I) a maximum internal dimension of from greater than 2.0 mm to less than 100.0 mm;
(II) an opposing surface such that one surface is shaped so as to be more convex than the opposite surface; and
(III) an envelope bulk density of greater than 500 g/1, wherein the large compacted organic framework body has a dimension such that it has a maximum internal diameter between opposite edges of at least 11.0 cm, wherein the compaction step (b) is carried out under conditions of:
IB (i) a pressure of between 15 MPa and 200 MPa; and
(ii) a compaction time of greater than 5.0 seconds.
2. A process according to any previous claim, wherein the organic framework powder is subjected to a vibration step preceding and/or during the compaction step (b).
3. A process according to any preceding claim, wherein the organic framework powder is contacted with a solvent prior to the compaction step (b).
4. A process according to claim 3, wherein the solvent is ethanol.
5. A process according to claim 3, wherein the solvent is a mixture of ethanol and water.
6. A process according to any preceding claim wherein the organic framework powder is contacted with a binder prior to the compaction step (b).
7. A process according to any preceding claim, wherein the organic framework powder is milled prior to being compacted.
8. A process according to claim 7, wherein the milling step is carried out in a ball-mill.
9. A process according to any preceding claim, wherein the compaction step (b) is carried out under conditions of:
(i) a pressure of from 15 MPa to 75 MPa; and
(ii) a compaction time of more than 60 seconds.
10. A process according to any preceding claim, wherein steps (a) and (b) are carried out on a conveyor belt.
11. A process according to any preceding claim, wherein the large compacted organic framework body has a dimension such that the thickness is from 1.0 mm to 100.0 mm.
12. A process according to any preceding claim, wherein step (c) is carried out by a vibration sieving process.
13. A process according to any preceding claim, wherein step (b) is carried out at a temperature of from 50 °C to 150 °C.
14. A process according to any preceding claim, wherein during step (c) the small compacted organic framework bodies are be subjected to a rounding or spheronisation step.
15. A process according to any preceding claim, wherein the organic framework body is a metal-organic framework body.
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Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2015040593A1 (en) * 2013-09-23 2015-03-26 Basf Se Process for the recovery of components forming a metal-organic framework material

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WO2015040593A1 (en) * 2013-09-23 2015-03-26 Basf Se Process for the recovery of components forming a metal-organic framework material

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ANONYMOUS: "Density Analysis", 1 January 2001 (2001-01-01), pages 1 - 6, XP055954913, Retrieved from the Internet <URL:https://www.micromeritics.com/Repository/Files/Density_Brochure.pdf> [retrieved on 20220825] *
ANONYMOUS: "Geopyc 1360 Envelope Density Analyzer", 25 August 2022 (2022-08-25), pages 1 - 2, XP055954908, Retrieved from the Internet <URL:https://www.micromeritics.com/Repository/Files/GeoPyc_1360_reg_and_TAP.pdf> [retrieved on 20220825] *
RUI P. P. L. RIBERIO ET AL.: "Binderless shaped metal-organic framework particles. Impact on carbon dioxide adsorption", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 275, 1 February 2019 (2019-02-01), pages 111 - 12
RUI P.P.L. RIBEIRO ET AL: "Binderless shaped metal-organic framework particles: Impact on carbon dioxide adsorption", MICROPOROUS AND MESOPOROUS MATERIALS, vol. 275, 1 February 2019 (2019-02-01), Amsterdam ,NL, pages 111 - 121, XP055735917, ISSN: 1387-1811, DOI: 10.1016/j.micromeso.2018.08.002 *
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