FR3124093A1 - Process for making MOF product and grain powder into MOF product - Google Patents

Abstract

A method of manufacturing an MOF-based product comprising mixing raw materials to form a feedstock, said feedstock comprising an MOF powder and a polysaccharide gellable under the action of a gelling agent, the ratio mass of the quantity of said polysaccharide out of the total quantity of said polysaccharide and of the MOF powder(s) in the said mixture being greater than or equal to 0.1% and less than or equal to 10%, shaping of the said starting charge by a technique chosen from extrusion, tape casting and screen printing, so as to obtain a preform, and bringing said preform into contact with said agent for gelling and gelling said polysaccharide, so as to obtain said MOF-based product. Grain powder, said grains consisting of MOF-based products, each of said products comprising particles bound by a binder, said binder comprising a gelled polysaccharide, said particles being MOF particles, said powder having an average circularity of less than 0 .90.

Description

Process for manufacturing MOF product and grain powder into MOF product

The present invention relates to a process for manufacturing an MOF product and grain powder into an MOF product.

In a well-known way, a metallo-organic network, or " Metal Organic Framework", most often called "MOF" according to the English abbreviation, is a material consisting of metal ions or metal clusters and organic ligands, organized in to form a porous crystal lattice.

Their high microporosity and specific surface make it possible to envisage many industrial applications, particularly in the fields of gas storage or separation, as well as in catalysis. However, MOFs are conventionally presented in the form of powders, which makes them difficult to use in said applications.

Patent GB2490473 describes products based on MOF in the form of spheres, the MOF particles being bound by a gelled alginate.

There is a need for MOF-based products, in particular powders, obtained by shaping an MOF powder, said products being able to be easily handled, having a high adsorption capacity, for a mass of MOF substantially identical.

An object of the invention is to meet, at least partially, this need.

According to the invention, this object is achieved by means of a method for manufacturing a product based on MOF comprising at least the following steps:

a) mixture of raw materials to form a starting charge, said starting charge comprising an MOF powder, or a mixture of at least two MOF powders, and a polysaccharide which can be gelled under the action of a gelling agent,

the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the MOF powder(s) in the said mixture being greater than or equal to 0.1% and less than or equal to 10%,

b) shaping of said starting charge according to a shaping technique chosen from extrusion, tape casting and screen printing, so as to obtain a preform,

c) bringing said preform into contact with said gelling agent and gelling said polysaccharide so as to obtain said MOF-based product,

d) optionally, drying said MOF-based product.

The inventors have discovered that the process according to the invention allows the manufacture of products based on MOF, having a surprisingly high adsorption capacity per gram of MOF contained in said product. In particular, it has been discovered that the selection of the shaping technique in step b) associated with gelation of the polysaccharide, preferably alginate, makes it possible to achieve this result, unlike the beads manufactured according to GB2490473 in a drip process (or "dripping" in English).

It has been discovered in particular that the shaping of said product according to one of the techniques described above and leading in particular to products whose shapes deviate from the sphere, unexpectedly makes it possible to improve its absorption capacity.

According to preferred but non-limiting embodiments of the present invention, which can, where appropriate, be combined with each other:

• the mass ratio of the amount of polysaccharide to the total amount of said polysaccharide and of the MOF powder(s) is greater than or equal to 1% and less than or equal to 8%;
• the MOF particles are particles of an MOF or a mixture of at least two populations of MOF particles chosen from MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36 , MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF -110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9 , IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2 , AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29 , NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-100 and MIL101;
• the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent, said group being chosen from a carboxylate COO group^-or a sulfonate group SO₃ ^- ;
• the polysaccharide capable of forming an ionic bond with a gelling agent comprises a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations, tetravalent cations, organic molecules comprising at least two groups each having an elementary or partial positive charge, and mixtures thereof;
• the polysaccharide is an alginate or a pectin, preferably an alginate;
• the starting charge consists of the MOF powder(s), the polysaccharide capable of forming an ionic bond with a gelling agent, a solvent, an acid, a base, a binder organic, a plasticizer, a lubricant and pore-forming particles;
• the gelling agent is chosen from Ca, Sr, Ba and mixtures thereof, preferably Ca;
• in step b), the starting charge is shaped by screen printing;
• the method comprises a step d) of drying.

In particular, a product finally obtained according to the manufacturing process according to the invention advantageously has a circularity Ci of less than 0.90, and preferably less than 0.88, or even less than 0.86. A sum of products according to the invention can advantageously constitute, at least partially and preferably entirely, the grains of a powder which is also the subject of the present invention. Preferably at least 50% by number and preferably at least 80%, or even at least 90%, and even more preferably substantially all of the grains of said powder are products capable of being obtained or obtained according to a process according to invention.

The invention thus also relates to a grain powder, said grains being made up of MOF-based products, each of said products comprising particles linked by a binder, said binder comprising a gelled polysaccharide, said particles being essentially, preferably being, MOF particles, said powder having an average circularity of less than 0.90.

Preferably, at least a portion and preferably all of the products of said powder are obtained or capable of being obtained by a process as described above.

By "MOF-based product" is meant that said product may comprise particles of a single MOF or a mixture of at least two populations of MOF particles, preferably at least two of said populations of MOF particles are in one different MOF, in particular chosen from the following list.

According to preferred but non-limiting embodiments of the present invention, which can, where appropriate, be combined with each other:

• The powder has an average circularity of less than 0.88, or even less than 0.86;
• said binder comprises a gelled polysaccharide comprising a group establishing an ionic bond with divalent cations, trivalent cations, tetravalent cations, organic molecules comprising at least two groups each having an elementary or partial positive charge, and mixtures thereof;
• said gelled polysaccharide is a gelled alginate or a gelled pectin;
• said MOF particles are particles of an MOF or a mixture of at least two populations of MOF particles chosen from MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36 , MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF -110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9 , IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2 , AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29 , NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-100 and MIL101;
• the MOF-based product of the grains of the powder contains a mass quantity of MOF particles greater than or equal to 90% and less than or equal to 99.9%, based on the mass of said MOF-based product after drying, said drying being carried out for 12 hours:

• at the MOF degradation temperature minus 5°C or at the lowest MOF degradation temperature minus 5°C, if said temperature is below 100°C, or

• at 100°C if the degradation temperature of the MOF minus 5°C or the lowest degradation temperature of the MOFs minus 5°C is greater than or equal to 100°C.

The invention finally relates to a liquid filtration device, a gas filtration device, a liquid storage device, a gas storage device, a catalyst support, comprising a powder according to the invention or a powder of grains comprising and preferably consisting of MOF-based products obtained or capable of being obtained by a process according to the invention.

Definitions

• By MOF powder is conventionally meant a set of MOF particles.
• The term “polysaccharides”, according to the classic definition, refers to polymers composed of sequences of saccharide units linked by glycosidic bonds.
• The term “gellable polysaccharide” under the action of a gelling agent means a polysaccharide capable of forming a gel under the action of said gelling agent.
• A gelled polysaccharide results from the association of polysaccharide chains under the action of a gelling agent. By way of example, the alginate has the formula (C ₆ H ₇ O ₆ ^- ) _n . Alginate is a polyosidic chain comprising carboxylate groups (COO ^- ). Ca ²⁺ calcium ions (gelling agent) react with two strands of alginate, that is to say with the carboxylate groups COO ^- , leading to the polymerization of the alginate chains and the bonding of the molecules between them. The reaction thus allows the creation of a gel.
• The term “MOF degradation temperature” refers to the start temperature of the last mass loss peak of the MOF (in other words, the peak found at the highest temperatures), as observed in thermogravimetric analysis (TGA) .
• The term "median size" of a powder of grains or particles means the size dividing said grains or said particles of the powder into first and second populations equal in number, these first and second populations comprising only grains, respectively particles having a size greater than or equal to, or less than, respectively, the median size. The median size can for example be determined using a laser particle sizer.
• We call “circularity” of a product or a grain observed in a powder, the ratio P _D /P _r , P _r designating the perimeter of said product or grain as observed, and P _D designating the perimeter of the disc having the same surface as that of said product or grain as observed. The circularity depends on the viewing direction.

As shown on the , to evaluate the circularity “Ci” of a grain G, the perimeter P _D of the disc D having an area equal to the area A _G of the grain G is determined on a photograph of this grain. The perimeter P _r of this grain is also determined. The circularity is equal to the ratio of P _D /P _r .

Thereby .

The more elongated the grain, the lower the circularity.

• The “average circularity” Ci ₅₀ of a set of grains is the arithmetic mean of the circularities of the grains of this set, said circularities being able to be evaluated using a device of the Morphologi® G3 type marketed by the company Malvern. According to the invention, the average circularity is determined from at least 1000 grains of the powder, so that the direction of observation does not or substantially does not impact the value thereof.

All percentages herein are percentages by weight, unless otherwise indicated.

The adsorption of a powder of MOF-based product grains can be conventionally measured using a breakthrough curve, making it possible to determine the maximum mass quantity of a molecule (for example toluene) that can be adsorbed. Adsorption is expressed as the ratio of said quantity to the mass of MOF particles present in the MOF product of the powder grains.

The verbs “contain”, “understand” and “present” must be interpreted in a broad, non-limiting way, unless otherwise indicated.

The describes the elements taken into account for the determination of the circularity Ci of a grain.

The shows the number distribution of the circularity of the grains of the powder according to Comparative Example 1.

The shows the number distribution of the circularity of the grains of the powder according to example 2 according to the invention.

The shows 10 2D images of the grains of the powder according to comparative example 1.

The shows 10 2D images of the grains of the powder according to example 2 according to the invention.

Claims (20)

Process for manufacturing an MOF-based product comprising at least the following steps:
a) mixture of raw materials to form a starting charge, said starting charge comprising an MOF powder or a mixture of at least two MOF powders and a gellable polysaccharide under the action of a gelling agent,
the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the MOF powder(s) in the said mixture being greater than or equal to 0.1% and less than or equal to 10%,
b) shaping of said starting charge according to a technique chosen from extrusion, tape casting and screen printing, so as to obtain a preform,
c) bringing said preform into contact with said gelling agent and gelling said polysaccharide so as to obtain said MOF-based product,
d) optionally, drying said MOF-based product. Process for the manufacture of a product based on MOF according to the preceding claim, in which the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the MOF powder(s) is greater than or equal to 1% and less than or equal to 8%. Process for the manufacture of a product based on MOF according to one of the preceding claims, in which the particles of MOF are particles of an MOF or a mixture of at least two populations of particles of MOF chosen from MOF-0 , MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF- 26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF- 4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-66, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-100 and MIL101. Process for the manufacture of a product based on MOF according to one of the preceding claims, in which the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent, the said group being chosen from a carboxylate group COO ^- or a sulphonate group SO ₃ ^- . Process for the manufacture of a product based on MOF according to one of the preceding claims, in which the polysaccharide capable of forming an ionic bond with a gelling agent comprises a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations, tetravalent cations, organic molecules comprising at least two groups each having an elementary or partial positive charge, and mixtures thereof. Process for the manufacture of an MOF-based product according to one of the preceding claims, in which the polysaccharide is an alginate or a pectin, preferably an alginate. Process for the manufacture of a product based on MOF according to one of the preceding claims, in which the starting charge consists of the powder(s) of MOF, of the polysaccharide capable of forming an ionic bond with a gelation, of a solvent, of an acid, of a base, of an organic binder, of a plasticizer, of a lubricant and of the pore-forming particles. Process for the manufacture of a product based on MOF according to one of the preceding claims, in which the gelling agent is chosen from Ca, Sr, Ba and their mixtures, preferably Ca. Process for manufacturing a product based on MOF according to one of the preceding claims, in which, in step b), the starting charge is shaped by screen printing. Process for the manufacture of a product based on MOF according to one of the preceding claims, comprising a step d) of drying. Grain powder, said grains consisting of MOF-based products, each of said products comprising particles bound by a binder, said binder comprising a gelled polysaccharide, said particles being MOF particles, said powder having an average circularity of less than 0 .90. Powder according to the preceding claim, comprising, or consisting of, products obtained or capable of being obtained by a process according to one of Claims 1 to 10. Powder according to one of Claims 11 and 12, having an average circularity of less than 0.86. Powder according to one of Claims 11 to 13, in which the said binder comprises a gelled polysaccharide comprising a group establishing an ionic bond with the divalent cations, the trivalent cations, the tetravalent cations, the organic molecules comprising at least two groups each having a elementary or partial positive charge, and mixtures thereof. Powder according to one of Claims 11 to 14, in which the said gelled polysaccharide is a gelled alginate or a gelled pectin. Powder according to one of Claims 11 to 15, in which the said MOF particles are particles of an MOF or a mixture of at least two populations of MOF particles chosen from MOF-0, MOF-2, MOF-3 , MOF-4, MOF-5, MOF-6, MOF-7, MOF-8 MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF- 32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF- 6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO- 66, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, HKUST-1, MIL-100 and MIL101. Powder according to one of Claims 11 to 16, in which the MOF-based product of the grains of the said powder contains a mass quantity of MOF particles greater than or equal to 90% and less than or equal to 99.9%, on the based on the mass of said MOF-based product after drying, said drying being carried out for 12 hours:

• at the MOF degradation temperature minus 5°C or at the lowest MOF degradation temperature minus 5°C, if said temperature is below 100°C, or
• at 100°C if the degradation temperature of the MOF minus 5°C or the lowest degradation temperature of the MOFs minus 5°C is greater than or equal to 100°C.

Device for filtering liquids or gases, comprising a powder according to one of Claims 11 to 17 or a powder of grains consisting of MOF-based products obtained or capable of being obtained by a process according to one of Claims 1 at 10. Device for storing liquids or gases comprising a powder according to one of Claims 11 to 17 or a powder of grains consisting of MOF-based products obtained or capable of being obtained by a process according to one of Claims 1 to 10. Catalyst support comprising a powder according to one of Claims 11 to 17 or a powder of grains consisting of MOF-based products obtained or capable of being obtained by a process according to one of Claims 1 to 10.