Process for preparing a material comprising cristobalite silica, a lithium salt, and a potassium and / or cesium phosphate salt

Abstract

The invention relates to a method for preparing a macroporous material comprising an active phase comprising at least one potassium and / or cesium phosphate salt, at least one lithium salt, and a support comprising silica in the crystalline form cristobalite, comprising the following steps: a) at least one source of silica is brought into contact with at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor to obtain a material precursor; b) the material precursor obtained at the end of step a) is allowed to mature for a period of between 1 minute and 72 hours to obtain a matured material precursor; c) the matured material precursor obtained at the end of step b) is calcined at a temperature of between 800°C and 1200°C to obtain said material.

Description

Title of the invention: Process for preparing a material comprising cristobalite silica, a lithium salt, and a potassium and / or cesium phosphate salt Field of invention

[0001] The invention relates to a process for preparing a novel macroporous material comprising an active phase comprising at least one potassium and / or cesium phosphate salt, at least one lithium salt, and a silica-based support in the crystalline form cristobalite. The material obtained by the process according to the invention can be advantageously used as a support or as a catalyst in catalytic processes. State of the art

[0002] Silica is an interesting compound to use as a catalyst support. However, silica cannot be extruded like other materials in conventional extrusion equipment to give products sufficiently strong to be implemented in catalytic processes. Indeed, from its manufacture to its implementation, the catalyst comprising such a support is confronted with numerous stages which can impact its physical integrity. In particular, it must be resistant to crushing, attrition and pressure variations linked to the operating conditions of the catalytic reactor in which it is operated. Thus, there is a constant need to provide catalysts having improved mechanical and physical properties.

[0003] Patent application WO2003 / 026795 discloses a method for producing a catalyst comprising a silica support which consists in impregnating a silica component with a catalytic metal by means of an aqueous alkaline bath before drying in order to improve its mechanical strength. More particularly, the preparation method consists in forming and washing a silica component, of the silica gel or co-gel type, for example a silica-zirconia co-gel. Then, the washed silica component is brought into contact with an alkaline bath in order to impregnate the catalytic metal, of the cesium type, and to form an activated silica component. The activated silica component is then dried in order to form the catalyst without a calcination step.

[0004] Patent application WO17040383 discloses a plurality of catalysts comprising at least one mixture of alkali phosphates, some of which have the formula M xPOy (with M = K or Cs or Li) and a non-porous silicic binder. The catalysts are prepared by mechanical mixing, using a planetary mill, of an amorphous fused silica ("Fused silica" according to English terminology) which is a dense material with no surface properties or porosity, and potassium phosphate precursors. The catalyst precursor is then calcined in air at 450°C to obtain a material composed of a LiPO3 / (LiPO3 + SiO2) mixture with a mass ratio of 13 and 26% by weight of LiPO3 relative to the total weight of said material. This document also discloses a catalyst in the form of a powder of variable particle size sieved between 106 and 212 pm. The silica contained in the final material is in its amorphous form.

[0005] However, none of the prior art documents discloses a macroporous material formed from a lithium phosphate salt, and a potassium and / or cesium phosphate salt, and silica at least partially in the crystalline form of cristobalite. Objects of the invention

[0006] The subject of the present invention is a process for preparing a macroporous material comprising an active phase comprising at least one potassium phosphate salt and / or at least one cesium phosphate salt, at least one lithium salt, and a support comprising silica at least partially in the crystalline form cristobalite, comprising at least the following steps:

[0007] a) at least one source of silica is brought into contact with at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor to obtain a material precursor;

[0008] b) the material precursor obtained at the end of step a) is allowed to mature for a period of between 1 minute and 72 hours to obtain a matured material precursor;

[0009] c) the matured material precursor obtained at the end of step b) is calcined at a temperature between 800°C and 1200°C to obtain said material.

[0010] According to one or more embodiments of the invention, in step a) said phosphate, potassium and / or cesium precursors are supplied in the form of at least one potassium phosphate salt and / or at least one cesium phosphate salt.

[0011] According to one or more embodiments of the invention, said potassium phosphate salt is chosen from: KH2PO4, KH2P20i2, K6P6O7, K3H2P3Oi0, K4H2P40i3, K3P3O 9, IQP.O12, k6p6oi8, K8P8O24, K10Pio03o, potassium phosphate (tripotassium) (PO4 3.3K+), alone or as a mixture.

[0012] According to one or more embodiments of the invention, said cesium phosphate salt is chosen from: CsH2PO4, Cs2H2P3Oi0, Cs4H2P40i3, Cs3P3O9, Cs4P40i2, Cs6P6O 18, Cs8P8O24, (CsPO3), alone or as a mixture.

[0013] According to one or more embodiments of the invention, in step a) said lithium precursor is supplied in the form of at least one lithium salt chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts, in amorphous or crystalline oxide form, taken alone or as a mixture.

[0014] According to one or more embodiments of the invention, said lithium salt is chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts from the following list: LiH2PO4, Li2H2P2O7 Li3P3O9, Li4P40i2, Li6P60i8, Li8P8O 24, Li2SO4, LiNO3, Li2CO3 LiOH, taken alone or as a mixture.

[0015] According to one or more embodiments of the invention, said lithium salt is chosen from lithium nitrate (LiNO3), lithium hydroxide (LiOH), or lithium carbonate (Li2CO3).

[0016] According to one or more embodiments of the invention, said potassium phosphate salt and / or said cesium phosphate salt and said lithium salt are supplied in step a) in the form of a powder.

[0017] According to one or more embodiments of the invention, said powder of at least one potassium and / or cesium phosphate salt and / or said powder of at least one lithium salt are ground and sieved to a grain size of less than 100 μm prior to their introduction into step a).

[0018] According to one or more embodiments of the invention, which step a) comprises the following sub-steps:

[0019] i) at least one powder of precipitated silica, silica gel or zeolite with a Si / Al ratio >100, at least one colloidal silica sol, at least one powder of at least one potassium and / or cesium phosphate salt and at least one powder of at least one lithium salt are mixed in at least one solvent to obtain a mixture;

[0020] ii) the mixture obtained at the end of step i) is shaped.

[0021] According to one or more embodiments of the invention, step a) comprises the following sub-steps:

[0022] i') at least one colloidal silica sol is mixed with at least one powder of at least minus one potassium and / or cesium phosphate salt to obtain a suspension;

[0023] ii') a powder of at least one precipitated silica, a silica gel, or a zeolite with a Si / Al ratio >100, at least one powder of at least one lithium salt, and at least one solvent are added to said suspension obtained at the end of step i');

[0024] iii') the dough obtained at the end of step ii') is shaped.

[0025] According to one or more embodiments of the invention, step a) comprises the following sub-steps:

[0026] i”) a liquid solution is supplied in aqueous or organic phase comprising at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor;

[0027] ii”) said solution obtained at the end of step i”) is impregnated onto a shaped support containing silica as a source of silica.

[0028] According to one or more embodiments of the invention, the impregnation solution of step i”) comprises a mixture of alkali metal precursors Ml and M2, with Ml chosen from K and / or Cs, and M2 being lithium.

[0029] According to one or more embodiments of the invention, said alkali metal precursors M1 and M2 are chosen from the salts of carbonate M2CO3, nitrate MNO3, sulfate, formate HCOOM, acetate CH2COOM, citrate, lactate, chloride MCI, hydroxide MOH and oxide M2O, with M = M1 and / or M2.

[0030] According to one or more embodiments of the invention, said phosphate precursor is chosen from H3PO4, (NH4)H2PO4, (NH4)2HPO4, (NH4)PO4, and P2O5.

[0031] According to one or more embodiments of the invention, said method further comprises the following steps:

[0032] d) said material obtained at the end of step c) is brought into contact with at least one second phosphate precursor, and at least one second potassium and / or cesium precursor to obtain a second material precursor;

[0033] e) calcining the second material precursor obtained at the end of step d) at a temperature between 300°C and 600°C. Detailed description 1. Definitions

[0034] Within the meaning of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.

[0035] In the sense of the present invention, the different parameter ranges for a given step such as pressure ranges and temperature ranges may be used alone or in combination. For example, in the sense of the present invention, a preferred pressure value range may be combined with a more preferred temperature value range.

[0036] By “macropores” is meant pores with an opening greater than 50 nm.

[0037] By “mesopores” is meant pores whose opening is between 2 nm and 50 nm, inclusive.

[0038] The total pore volume (TPV) of the material according to the invention is understood to mean the volume measured by intrusion with a mercury porosimeter according to standard ASTM D4284-83 at a maximum pressure of 4000 bars (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140°. The wetting angle was taken equal to 140° following the recommendations of the work “Techniques de l'ingénieur, traité analyse et caractérisation”, pages 1050-1055, written by Jean Charpin and Bernard Rasneur.

[0039] In order to obtain better precision, the value of the total pore volume corresponds to the value of the total pore volume measured by intrusion with the mercury porosimeter. measured on the sample minus the value of the total pore volume measured by mercury porosimeter intrusion measured on the same sample for a pressure corresponding to 30 psi (approximately 0.2 MPa).

[0040] The volume of macropores and mesopores is measured by mercury intrusion porosimetry according to ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140°. The value at which mercury fills all intergranular voids is set at 0.2 MPa, and it is considered that beyond this, mercury penetrates into the pores of the sample.

[0041] The macroporous volume of the material according to the invention is defined as being the cumulative volume of mercury introduced at a pressure between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm.

[0042] The mesoporous volume of the material according to the invention is defined as being the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa, corresponding to the volume contained in the pores with an apparent diameter of between 2 nm and 50 nm.

[0043] The median diameter of the macropores (Dmacro in nm) is also defined as being a diameter such that all pores smaller than this diameter constitute 50% of the macropore volume, measured by mercury porosimetry.

[0044] Throughout the rest of the text, the term “mechanical resistance to lateral crushing” means the mechanical resistance of the material according to the invention determined by the grain-to-grain crushing (EGG) test. This is a standardized test (ASTM D4179-01 standard) which consists of subjecting a material in the form of a millimetric object, such as a ball, a pellet or an extrudate, to a compressive force generating rupture. This test is therefore a measurement of the tensile strength of the material. The analysis is repeated on a certain number of solids taken individually and typically on a number of solids between 10 and 200. The average of the measured lateral breaking forces constitutes the average EGG which is expressed in the case of granules in units of force (N), and in the case of extrudates in units of force per unit of length (daN / mm or decaNewton per millimeter of extrudate length).

[0045] In the remainder of the text, the grain size or particle size distribution of the constituents of the materials obtained according to the invention is measured by the laser scattering particle size distribution technique. This indirect measurement technique makes it possible to determine the particle size distribution (scale from micron to millimeter). This analysis method uses the principle of diffusion (Mie theory) and / or light diffraction (Fraunhoffer theory and Mie theory). The particles illuminated by the laser light deflect the light from its main axis. The quantity of deflected light and The importance of the deflection angle allows the particle size to be measured precisely. The powder is conveyed either by a solvent (water, isopropanol) or by air before passing in front of the laser beam: two paths are thus distinguished: the wet path and the dry path.

[0046] The wet method makes it possible to characterize dispersions (elementary particle size after dispersion) or suspended solids ("aggregated" particle size). The particles measured are in the range 0.02 microns to 2000 microns.

[0047] Dry process granulometry makes it possible to characterize powders whose initial aggregation is not destroyed. The measurement range extends from 0.2 microns to 2000 microns. In the present invention, the dry process is used to measure the grain size of the constituents of the material of the invention.

[0048] By hourly volumetric velocity “PPH”, we mean the mass flow rate of the feed at the reactor inlet in kg / h at 15°C, 0.1 MPa divided by the mass of material in kg contained in the reactor. 2. Detailed Description Material

[0049] An object according to the invention relates to a macroporous material comprising an active phase comprising at least one potassium and / or cesium phosphate salt, at least one lithium salt, and a silica-based support, it being understood that the silica is at least partially in the crystalline form cristobalite.

[0050] Indeed, the Applicant has surprisingly discovered that the use of such a macroporous material as a catalyst for the dehydration of hydroxypropanoic acid allows a significant increase in its stability under load compared to a catalyst obtained according to conventional preparation methods in which the silica is in amorphous form. The macroporous structure of the material and the particular crystallinity of the silica included in this material could be obtained by carrying out a specific preparation method comprising a step in which a calcination step is carried out at a temperature greater than or equal to 800°C on the basis of a material precursor comprising at least one source of silica, at least one precursor of potassium and / or cesium, and at least one precursor of lithium.

[0051] X-ray diffraction makes it possible to verify that the material according to the invention does indeed contain silica totally or partially crystallized in its cristobalite form by comparing the diffractogram obtained with those existing in a database such as the crystallographic database PDF4+ 2020 of the ICDD® (International Centre for Diffraction Data). The X-ray diffraction diagram is obtained by radiocrystallographic analysis using a diffractometer using the classic powder method with the Kal radiation of copper (X = 1.54060Â). A From the position of the diffraction peaks represented by the angle 20, the characteristic reticular equidistances dhkl of the sample are calculated using the Bragg relation. The measurement error A(dhkl) on dhkl is calculated using the Bragg relation as a function of the absolute error A (20) assigned to the measurement of 20. An absolute error A (20) equal to ± 0.02° is commonly accepted.

[0052] More specifically, the 20 line of 21.8° is associated mainly with the crystallographic form cristobalite. The 28.3°; 31.3° and 36° lines are also attributed to the formation of cristobalite.

[0053] Advantageously, said potassium phosphate and / or cesium phosphate salt is potassium metaphosphate (KPO3) and / or cesium metaphosphate (CsPO3).

[0054] Advantageously, said lithium salt is chosen from lithium metaphosphate (LiPO3), preferably of monoclinic structure, lithium tri-potassium diphosphate (LiK3P2O7), preferably of orthorhombic structure, or lithio-phosphate (Li3PO4), preferably of orthorhombic structure, taken alone or as a mixture.

[0055] Advantageously, said material has a mass ratio MPO3 / (MPO3+SiO2+Li2O) of between 13 and 50, preferably between 15 and 45, and even more preferably between 17 and 40, even more preferably between 20 and 40 with M being chosen from potassium and / or cesium (M = K and / or Cs). Preferably M is potassium.

[0056] Advantageously, said material has a Li / M molar ratio (M = K or Cs) of between 0 and 2, preferably between 0.1 and 1.5, very preferably between 0.2 and 1.

[0057] Preferably, said material has a total pore volume of between 0.01 and 0.6 cmVg, more preferably of between 0.04 and 0.5 cmVg, even more preferably of between 0.10 and 0.40 cmVg, and even more preferably of between 0.14 and 0.39 cmVg.

[0058] Preferably, said material has a macroporous volume of between 0.01 and 0.6 cmVg, more preferably of between 0.04 and 0.5 cmVg, even more preferably of between 0.1 and 0.4 cmVg, and even more preferably of between 0.14 and 0.39 cmVg.

[0059] Preferably, the macroporous volume of the material represents between 50% and 100% of the total pore volume of said material, preferably between 60% and 100% and even more preferably between 80% and 100%.

[0060] In one embodiment according to the invention, said material has a specific surface area of ​​less than 1 m2 / g.

[0061] In another embodiment according to the invention, said material has a specific surface area greater than or equal to 1 m2 / g and less than 50 m2 / g, preferably between 1 and 20 m2 / g, and more preferably between 1 and 18 m2 / g, still preferred between 1 and 15 m2 / g.

[0062] Advantageously, said material has a mechanical resistance value measured by grain-to-grain crushing greater than 0.5 daN / mm, preferably greater than 0.7 daN / mm, more preferably greater than 0.9 daN / mm and preferably greater than 1.2 daN / mm.

[0063] The material advantageously has between 1% and 99% by weight, preferably between 5% and 99% by weight, preferably from 10% to 95% by weight, and very preferably from 20% to 75% by weight of at least one potassium and / or cesium phosphate salt.

[0064] The material advantageously has between 1% and 30% by weight, preferably between 3% and 25% by weight, preferably from 5% to 20% by weight, of at least one lithium phosphate salt.

[0065] The material advantageously has between 50% and 90% by weight, preferably between 55% and 85% by weight, preferably from 60% to 85% by weight, and very preferably from 60% to 80% by weight of silica, relative to the total weight of said material.

[0066] Said material according to the invention advantageously has a macroporous median diameter of between 80 nm and 7000 nm, preferably between 200 nm and 6500 nm, and more preferably between 500 nm and 4000 nm.

[0067] Said material is advantageously in the form of beads, extrudates, pellets, or irregular and non-spherical agglomerates. Preparation process

[0068] In accordance with the invention, the present invention relates to a process for preparing a macroporous material comprising an active phase comprising at least one potassium phosphate salt and / or at least one cesium phosphate salt, at least one lithium salt, and a support comprising silica at least partially in the crystalline form cristobalite, comprising at least the following steps:

[0069] a) at least one source of silica is brought into contact with at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor to obtain a material precursor;

[0070] b) the material precursor obtained at the end of step a) is allowed to mature for a period of between 1 minute and 72 hours to obtain a matured material precursor;

[0071] c) the matured material precursor obtained at the end of step b) is calcined at a temperature between 800°C and 1200°C to obtain said material.

[0072] All of steps a) to c) are detailed below. Optional steps d) and e) may also be envisaged to obtain the material according to the invention. Step a)

[0073] Step a) can be carried out according to several embodiments. Embodiment 1

[0074] In a first embodiment according to the invention, step a) comprises the following sub-steps:

[0075] i) at least one powder of precipitated silica, silica gel or zeolite with a Si / Al ratio >100, at least one colloidal silica sol, at least one powder of at least one potassium and / or cesium phosphate salt and at least one powder of at least one lithium salt are mixed in at least one solvent to obtain a mixture;

[0076] ii) the mixture obtained at the end of step i) is shaped.

[0077] According to this embodiment, said step i) consists of mixing at least one precipitated silica powder, silica gel or zeolite with a Si / Al ratio >100 with at least one colloidal silica sol, at least one powder of at least one potassium phosphate salt and / or at least one cesium salt and at least one powder of at least one lithium salt in at least one solvent to obtain a mixture.

[0078] Preferably, the precipitated silica powder, silica gel or zeolite with a Si / Al ratio >100 is chosen, without being restrictive, from the following commercial sources: Nyasil20 (Nyacol ®), Siliaflash P60 (Silicycle ®), Siliaflash C60 (Silicycle ®), Ultrasil VN3 GR, EXP4232 (Evonik ®), ZSM-5 (CBV 28014; Zeolyst®), HY (CBV780; Zeolyst®) taken alone or as a mixture.

[0079] Preferably, the precipitated silica, silica gel or zeolite powder with a Si / Al ratio >100 has a grain size of less than 10 pm, and preferably less than 5 pm, more preferably less than 1 pm.

[0080] Preferably, the colloidal silica sols are chosen, without being restrictive, from the following commercial sources: Ludox (WR Grâce Davison®), Nyacol (Nyacol Nano Technologies®, Inc. or PQ Corp®.), Nalco (Nalco Chemical Company®), Ultra-Sol (RESI Inc®), NexSil (NNTI®), Levasil (Nouryon) taken alone or in a mixture.

[0081] Most colloidal silica sols are prepared from sodium silicate and inevitably contain sodium. Since the presence of sodium can be detrimental to catalytic activity, an ion exchange step may be necessary to reduce or even eliminate the residual sodium. In order to avoid this step, the use of low-sodium colloidal silica sols is preferable. For example, Ludox AS40 stabilized with an ammonium counterion, or Nyacol 2034DI, Nalco 1034A, Ultra-Sol 7H or NexSil 20A can be cited.

[0082] The said source(s) of silica used in the process according to the present invention are advantageously synthetic amorphous silicas or zeolites with Si / Al ratios >100.

[0083] The potassium phosphate salt(s) used in step i) are advantageously chosen from potassium phosphate salts in amorphous or crystallized oxide form, taken alone or as a mixture.

[0084] The potassium phosphate salt(s) are advantageously chosen from the following list: KH2PO4, KH2P20i2, K6P6O7, K3H2P3Oi0, K4H2P40i3, K3P3O9, K4P4O,2, K6P6O i8, K8P8O24, K10Pio03o, potassium phosphate (tripotassium) (PO43,3K+), alone or as a mixture. Preferably, the preferred potassium phosphate salt is chosen from potassium phosphate (tripotassium) (PO43,3K+) and KH2PO4, alone or as a mixture.

[0085] The cesium phosphate salt(s) are advantageously chosen from the following list: CsH2PO4, Cs2H2P3O10, Cs4H2P4O13, Cs3P3O9, Cs4P4O12, Cs6P6O18, Cs8P8O24, (CsPO3), alone or as a mixture. Preferably the preferred cesium phosphate salt is CsH2PO4.

[0086] Preferably, the potassium phosphate or cesium phosphate salt(s) are chosen from potassium phosphate (tripotassium) (PO43.3K+), KH2PO4, CsH2 PO4 in their hydrated or non-hydrated form.

[0087] The lithium salt(s) used in step i) are advantageously chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts, in amorphous or crystalline oxide form, taken alone or as a mixture.

[0088] Preferably, the lithium salt(s) are chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts from the following list: LiH 2PO4, Li2H2P2O7 Li3P3O9, Li4P4O12, Li6P6O18, Li8P8O24, Li2SO4, LiNO3, Li2CO3jLiOH, taken alone or as a mixture.

[0089] Very preferably, the lithium salt(s) are chosen from the following list: lithium nitrate (LiNO3), lithium hydroxide (LiOH), or lithium carbonate Li2CO3, in their hydrated or non-hydrated form, taken alone or as a mixture.

[0090] Even more preferably, the lithium salt is lithium nitrate (LiNO3), in its hydrated or non-hydrated form. Preferably, at least one organic adjuvant is also mixed during step i).

[0091] Said organic adjuvant may also be chosen from all the additives known to those skilled in the art. In the case where at least one organic adjuvant is added in step i), said organic adjuvant is advantageously chosen from cellulose derivatives, polyethylene glycols, aliphatic monocarboxylic acids, alkylated aromatic compounds, sulfonic acid salts, fatty acids, polyvinyl pyrrolidone, polyvinyl alcohol, methylcellulose, polyacrylates, polymethacrylates, polyisobutene, polytetrahydrofuran, starch, polysaccharide-type polymers (such as xanthan gum), scleroglucan, hydroxyethylated cellulose-type derivatives, carboxymethylcellulose, lignosulfonates and galactomannan derivatives, taken alone or in mixture.

[0092] Preferably, said organic adjuvant can be mixed in powder form or in solution in said solvent.

[0093] Said solvent is advantageously chosen from water, ethanol, alcohols and amines. Preferably, said solvent is water.

[0094] Within the framework of the invention, it is entirely possible to make mixtures of several different silica powders and / or different silica sols and / or different potassium or cesium phosphate powders, and / or different lithium salt powders.

[0095] The order in which the mixing of the powders of at least the silica sources, of at least one potassium and / or cesium phosphate salt powder, of at least one lithium salt powder, and optionally of at least one organic adjuvant in the case where these are mixed in the form of powders, with at least one solvent is carried out is indifferent.

[0096] The mixing of said powders and said solvent can advantageously be carried out in a single operation.

[0097] The additions of powders and solvent can also advantageously be alternated.

[0098] The potassium phosphate and / or cesium phosphate salt(s) used in step i) are advantageously in the form of powders.

[0099] Preferably, the potassium and / or cesium phosphate salt(s) in the case where these are mixed in the form of powders, can advantageously be ground and sieved to a particle size of less than 100 μm.

[0100] The lithium salt(s) used in step i) are advantageously in the form of powders.

[0101] Preferably, said lithium salt in the case where it is mixed in powder form, can advantageously be ground and sieved to a particle size of less than 100 μm. Preferably, the silica source used in step i) has a grain size of less than 60 μm, and preferably less than 25 μm, more preferably less than 5 μm, very preferably less than 2 μm.

[0102] In a particularly preferred embodiment, the use of a silica source used in step i) has a grain size of less than 60 μm, and preferably less than 25 μm, more preferably less than 5 μm, very preferably less than 2 μm, combined with the use of a powder of at least one potassium and / or cesium phosphate salt ground and sieved to a grain size of less than 100 μm, allows a significant improvement in the mechanical strength of the materials obtained according to the invention.

[0103] Preferably, said powders of at least one source of silica, of at least one salt of potassium and / or cesium phosphate, of lithium salt, and optionally of at least one at least one organic adjuvant, in the case where these are mixed in the form of powders, are first pre-mixed, dry, before the introduction of the solvent. Said pre-mixed powders are then advantageously brought into contact with said solvent.

[0104] In another embodiment, at least said silica sources and at least said organic adjuvant may be previously in solution or suspension in said solvent when said solvent is brought into contact with the potassium and / or cesium phosphate powders, and the lithium salt powder. Contact with said solvent results in obtaining a mixture which is then advantageously kneaded.

[0105] In the case where at least one cesium phosphate salt powder is used, ammonia is advantageously added to the mixture to obtain an extrudable mixture.

[0106] Preferably, said mixing step i) is carried out by kneading, discontinuously (batch according to English terminology) or continuously.

[0107] In the case where said step i) is carried out discontinuously, said step i) is advantageously carried out in a mixer preferably equipped with Z-shaped arms, or cams, or in any other type of mixer such as for example a planetary mixer. Said mixing step i) makes it possible to obtain a homogeneous mixture of the powdered constituents.

[0108] Preferably, said step i) is carried out at a temperature of between 13 and 25°C, for a duration of between 5 minutes and 60 minutes, and preferably between 10 minutes and 50 minutes. The rotation speed of the mixer arms is advantageously between 10 and 75 revolutions / minute, preferably between 25 and 50 revolutions / minute.

[0109] Preferably, the following quantities are introduced into mixing step i) of the process according to the invention:

[0110] - 1% to 99% by weight, preferably 5% to 99% by weight, preferably 10% at 95% by weight, and very preferably from 15% to 65% by weight of at least one precipitated silica, silica gel or a zeolite with a Si / Al ratio>100; [YES] - 1% to 99% by weight, preferably 5% to 99% by weight, more preferably 10% to 95% by weight, and very preferably 5% to 50% by weight of at least one colloidal silica sol;

[0112] - 1% to 99% by weight, preferably 5% to 99% by weight, preferably 10% at 95% by weight, and very preferably from 20% to 75% by weight of at least one potassium or cesium phosphate salt powder;

[0113] - 1% to 30% by weight, preferably from 3% to 25% by weight, preferably from 5% to 20% by weight of at least one lithium salt powder;

[0114] - 0% to 20% by weight, preferably from 1% to 15% by weight, more preferably from 1% to 10% by weight, and very preferably from 1% to 7% by weight of at least one organic adjuvant, the weight percentages being expressed relative to the total weight of said material (i.e. the final material obtained at the end of step c) and the sum of the contents of each of the compounds of said material being equal to 100%.

[0115] According to the invention, said step ii) consists of shaping the mixture obtained at the end of step i). Preferably, the mixture obtained at the end of step i) is advantageously shaped by extrusion.

[0116] In the case where the shaping of the mixture resulting from step i) is carried out by extrusion, said step ii) is advantageously carried out in a piston, single-screw or twin-screw extruder. In this case, an organic adjuvant may optionally be added in the mixing step i). The presence of said organic adjuvant facilitates shaping by extrusion. Said organic adjuvant is described above and is introduced in step i) in the proportions indicated above.

[0117] In the case where said preparation method is implemented continuously, said mixing step i) may be coupled with step ii) of shaping by extrusion in the same equipment. According to this implementation, the extrusion of the mixture also called "kneaded paste" may be carried out either by extruding directly at the end of a continuous mixer of the twin-screw type for example, or by connecting one or more batch mixers to an extruder. The geometry of the die, which gives the extrudates their shape, may be chosen from dies well known to those skilled in the art. They may thus be, for example, cylindrical or multi-lobed, and more preferably tri-lobed or quadri-lobed.

[0118] In the case where the shaping of the mixture resulting from step i) is carried out by extrusion, the quantity of solvent added in the mixing step i) is adjusted so as to obtain, at the end of this step and whatever the variant implemented, a mixture or a paste which does not flow but which is also not too dry in order to allow its extrusion under suitable pressure conditions well known to those skilled in the art and dependent on the extrusion equipment used.

[0119] Preferably, said step ii) of shaping by extrusion is carried out at an extrusion pressure greater than 1 MPa and preferably between 3 MPa and 10 MPa. Embodiment 2

[0120] In a second embodiment according to the invention, step a) comprises the following sub-steps:

[0121] i') at least one colloidal silica sol is mixed with at least one powder of at least minus one potassium and / or cesium phosphate salt to obtain a suspension;

[0122] ii') a powder of at least one precipitated silica, a silica gel, or a zeolite with a Si / Al ratio >100, at least one powder of at least one lithium salt, and at less one solvent in said suspension obtained at the end of step i');

[0123] iii') the dough obtained at the end of step ii') is shaped.

[0124] According to the second embodiment, said step i') consists of mixing at least one colloidal silica sol, with at least one powder of at least one potassium and / or cesium phosphate salt to obtain a suspension.

[0125] A solvent, preferably water, may advantageously be added in step i').

[0126] Preferably, the colloidal silicas or silica sols are chosen, without being restrictive, from the following commercial sources and are in liquid form: Ludox (WR Grâce Davison®), Nyacol (Nyacol Nano Technologies®, Inc. or PQ Corp®), Nalco (Nalco Chemical Company®), Ultra-Sol (RESI Inc®), NexSil (NNTI®), taken alone or as a mixture.

[0127] The source(s) of colloidal silica sol used in the process according to the present invention are advantageously synthetic amorphous silicas.

[0128] The potassium phosphate and / or cesium phosphate salt(s) used in step a) are advantageously chosen from potassium or cesium phosphate salts in amorphous or crystallized oxide form, taken alone or as a mixture.

[0129] The potassium phosphate salt(s) are advantageously chosen from the following list: KH2PO4, KH2P2O12, K6P6O7, K3H2P30io, K4H2P4O13, K3P3O9, K4P4O12, K6P6O 18, K8P8O24, K10P10O30, potassium phosphate (tripotassium) (PO43,3K+), alone or as a mixture. Preferably the preferred potassium phosphate salt is KH2PO4.

[0130] The cesium phosphate salt(s) are advantageously chosen from the following list: CsH2PO4, CS2H2P3O10, CS4H2P4O13, CS3P3O9, Cs4P40i2, Cs6P6O18, Cs8P8O24, (CsPO3), alone or as a mixture. Preferably the preferred cesium phosphate salt is CsH2PO4.

[0131] Preferably, the potassium phosphate or cesium phosphate salt(s) are chosen from KH2PO4, CsH2PO4 in their hydrated or non-hydrated form.

[0132] Preferably, said powders of at least one potassium and / or cesium phosphate salt can advantageously be ground and sieved to a grain size of less than 100 μm prior to their introduction into step i'). The grain size of the potassium phosphate and / or cesium phosphate salts is advantageously measured by dry laser granulometry.

[0133] Very preferably, said step i') is advantageously carried out in a centrifugal planetary mixer. Said powders of at least one potassium and / or cesium phosphate salt, preferably ground and sieved to a particle size of less than 100 μm, are previously dispersed by means of a centrifugal planetary mixer in the presence of the source of colloidal silica sol so as to obtain said suspension.

[0134] Said step i') is advantageously carried out at a mixing speed applied to the centrifugal planetary mixer, between 100 and 2000 revolutions per minute, preferably between 200 and 500 revolutions per minute.

[0135] Preferably, said step i') is carried out for a duration of between 5 seconds and 60 seconds and preferably between 20 seconds and 60 seconds.

[0136] The additions of powders, colloidal silica sol and solvent can also advantageously be alternated.

[0137] According to the second embodiment, the method comprises a step ii') of adding a powder of at least one precipitated silica, a silica gel, or a zeolite with a Si / Al ratio >100, at least one powder of at least one lithium salt, and at least one solvent in said suspension obtained at the end of step i').

[0138] Preferably, the precipitated silicas, silica gels, or zeolites with a Si / Al ratio >100 added in step ii') are chosen, without being restrictive, from the following commercial sources: Nyasil20 (Nyacol ®), Siliaflash P60 (Silicycle ®), Siliaflash C60 (Silicycle ®), Ultrasil VN3 GR (Evonik ®), ZSM-5 (CBV 28014; Zeolyst®), HY (CBV780; Zeolyst®) taken alone or as a mixture.

[0139] Preferably, the powder of at least one precipitated silica or silica gel or zeolite with a Si / Al ratio >100 added in step ii') has a grain size of less than 60 pm, and preferably less than 25 pm, more preferably less than 5 pm, very preferably less than 2 pm.

[0140] The size of the grains of precipitated silica or silica gel or zeolite with a Si / Al ratio >100 is advantageously measured by dry laser granulometry.

[0141] Preferably, the precipitated silica or silica gel is in amorphous form.

[0142] The lithium salt(s) added in step ii') are advantageously chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts, in amorphous or crystalline oxide form, taken alone or as a mixture.

[0143] Preferably, the lithium salt(s) are chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts from the following list: LiH 2PO4, Li2H2P2O7 Li3P3O9, Li4P4O12, Li6P6O18, Li8P8O24, Li2SO4, LiNO3, Li2CO3jLiOH, taken alone or as a mixture.

[0144] Very preferably, the lithium salt(s) are chosen from lithium nitrate (LiNO3), lithium hydroxide (LiOH), or lithium carbonate (Li2CO3) in their hydrated or non-hydrated form.

[0145] Even more preferably, the lithium salt is lithium nitrate (LiNO3), in its hydrated form or not.

[0146] In a variant of the second embodiment of the preparation process according to the invention, the introduction of the lithium salt can be carried out in step i') instead of step ii) under the same conditions as mentioned above.

[0147] Furthermore, within the framework of the invention, it is entirely possible to proceed to mixtures of several different silica powders and / or different silica sols and / or different potassium and / or cesium phosphate salt powders and / or different lithium salt powders.

[0148] According to the invention, at least one solvent is added in step ii'). Said solvent is advantageously chosen from water, ethanol, alcohols and amines. Preferably, said solvent is water.

[0149] Preferably, at least one organic adjuvant may also be added during step ii').

[0150] Said organic adjuvant can also be chosen from all the additives known to those skilled in the art.

[0151] In the case where at least one organic adjuvant is added in step ii'), said organic adjuvant is advantageously chosen from cellulose derivatives, polyethylene glycols, aliphatic monocarboxylic acids, alkylated aromatic compounds, sulphonic acid salts, fatty acids, polyvinyl pyrrolidone, polyvinyl alcohol, methylcellulose, polyacrylates, polymethacrylates, polyisobutene, polytetrahydrofuran, starch, polysaccharide-type polymers (such as xanthan gum), scleroglucan, hydroxyethylated cellulose-type derivatives, carboxymethylcellulose, lignosulfonates and galactomannan derivatives, taken alone or as a mixture.

[0152] Preferably, said organic adjuvant can be mixed in powder form or in solution in said solvent.

[0153] Step i') and step ii') can advantageously be implemented in the same equipment and preferably in a centrifugal planetary mixer.

[0154] In another embodiment, step i') and step ii') can advantageously be implemented in different equipment. In this case, step i') is preferably implemented in a centrifugal planetary mixer and then the suspension obtained at the end of step i') is then transferred to a Z-arm type batch mixer in which are added to said suspension, a powder of at least one precipitated silica or silica gel, a powder of at least one lithium salt and at least one solvent, according to step ii').

[0155] In the case where step i') and step ii') are not carried out in the same equipment, preferably, the source of a precipitated silica, a silica gel or zeolite with a Si / Al ratio>100, a powder of at least one lithium salt, at least one solvent and optionally at least one organic adjuvant are added first, preferably in the Z-arm type batch mixer, before the introduction of the suspension obtained in step i').

[0156] In the case where a cesium phosphate salt powder is used, an addition of ammonia can be made so as to obtain an extrudable mixture in step ii').

[0157] Preferably, said mixing step ii') is carried out by kneading, discontinuously or continuously.

[0158] In the case where said step ii') is carried out discontinuously, said step ii') is advantageously carried out in a mixer preferably equipped with Z-shaped arms, or cams, or in any other type of mixer such as for example a planetary mixer. Said mixing step ii') makes it possible to obtain a paste or a homogeneous mixture of the constituents.

[0159] In the case of the implementation of a “Z-arm” type mixer in step ii'), the rotation speed of the mixer arms is advantageously between 10 and 75 revolutions / minute, preferably between 25 and 50 revolutions / minute.

[0160] In the case of implementing step ii') in a centrifugal planetary mixer, the rotation speed is advantageously between 300 and 2000 revolutions / minute, preferably between 1500 and 2000 revolutions / minute so as to obtain a paste.

[0161] In a particularly preferred embodiment, the use of a powder of at least one potassium and / or cesium phosphate salt ground and sieved to a particle size of less than 100 pm in step i') combined with the use of a source of precipitated silica or silica gel, or zeolite with a Si / Al ratio>100 having a reduced size and preferably less than 10 pm, preferably less than 5 pm, even more preferably less than 1 pm, in step ii') allows a significant improvement in the mechanical strength of the materials obtained according to the invention.

[0162] Preferably, the following quantities are introduced in steps i') and ii'):

[0163] - 1% to 99% by weight, preferably from 5% to 99% by weight, preferably from 5% to 95% by weight, and very preferably from 5% to 40% by weight and even more preferably from 5 to 20% by weight of at least one colloidal silica sol;

[0164] - 1% to 99% by weight, preferably 5% to 99% by weight, preferably 10% at 95% by weight, and very preferably from 10% to 60% by weight of at least one potassium and / or cesium phosphate salt;

[0165] - 1% to 99% by weight, preferably 5% to 99% by weight, preferably 10% at 95% by weight, and very preferably from 30% to 80% by weight of at least one precipitated silica, silica gel or zeolite with a Si / Al ratio>100;

[0166] - 1% to 30% by weight, preferably from 3% to 25% by weight, preferably from 5% to 20% by weight of at least one lithium salt powder;

[0167] - 0% to 20% by weight, preferably from 1% to 15% by weight, more preferably from 1% to 10% by weight, and very preferably from 1% to 7% by weight of at least one organic adjuvant, the weight percentages being expressed relative to the total weight of said material and the sum of the contents of each of the compounds of said material being equal to 100%.

[0168] According to the second embodiment, said method comprises a step iii') of shaping the dough obtained at the end of step ii') of mixing.

[0169] Preferably, the paste obtained at the end of step ii') is advantageously shaped by extrusion.

[0170] In the case where the shaping of the mixture resulting from step ii') is carried out by extrusion, said step ii') is advantageously carried out in a piston, single-screw or twin-screw extruder.

[0171] In this case, an organic adjuvant may optionally be added in mixing step ii'). The presence of said organic adjuvant facilitates shaping by extrusion. Said organic adjuvant is described above and is introduced in step ii') in the proportions indicated above.

[0172] The extrusion of the mixture also called "kneaded paste" can be carried out either by extruding directly at the end of a continuous mixer of the twin-screw type for example, or by connecting one or more batch mixers to an extruder. The geometry of the die, which gives the extrudates their shape, can be chosen from dies well known to those skilled in the art. They can thus be, for example, cylindrical, multi-lobed, grooved or slotted.

[0173] In the case where the shaping of the mixture resulting from step ii') is carried out by extrusion, the quantity of solvent added in the mixing step ii') is adjusted so as to obtain, at the end of this step and whatever the variant implemented, a mixture or a paste which does not flow but which is also not too dry in order to allow its extrusion under suitable pressure conditions well known to those skilled in the art and dependent on the extrusion equipment used.

[0174] Preferably, said step iii') of shaping by extrusion is carried out at an extrusion pressure greater than 1 MPa and preferably between 3 MPa and 10 MPa. Embodiment 3

[0175] In a third embodiment according to the invention, step a) comprises the following sub-steps:

[0176] i”) a liquid solution is supplied in aqueous or organic phase comprising at least one phosphate precursor, and at least one potassium and / or cesium precursor, and at least one lithium precursor, the preparation temperature being advantageously between 5°C and 80°C, preferably between 10°C and 70°C, the phosphate concentration of the solution being preferably between 50 g / L and 2000 g / L;

[0177] ii”) said solution obtained at the end of step i”) is impregnated on a support containing silica (as a source of silica), the volume of the solution being before typically between 0.9 and 1.1, preferably between 0.8 and 1.05 times the pore volume of the support.

[0178] The impregnation solution of step i”) is preferably prepared by dissolving in an aqueous or organic phase one or more precursors of phosphate, potassium (K) and / or cesium (Cs), and lithium (Li). The impregnation solution can advantageously be prepared by mixing independently introduced phosphorus and alkali metal elements. In this case, the alkali metal precursors Ml and M2 are on the one hand K and / or Cs for the metal Ml and Li for the metal M2. For example, said alkali metal precursors Ml and M2 can be chosen from the salts of carbonate M2CO3, nitrate MNO3, sulfate, formate HCOOM, acetate CH2 COOM, citrate, lactate, chloride MCI, hydroxide MOH and oxide M2O, with M = Ml and / or M2.

[0179] The phosphate precursor(s) may advantageously be chosen, for example, from H3PO4, (NH4)H2PO4, (NH4)2HPO4, (NH4)PO4, P2O5.

[0180] The support supplied in step ii”) advantageously comprises an amorphous SiO2 phase, characterizable by X-ray diffraction. Said support preferably has a specific surface area greater than 5 m2 / g, preferably between 5 and 500 m2 / g, and more preferably between 10 and 450 m2 / g.

[0181] The pore volume of the support is advantageously between 0.05 cmVg and 1.5 cmVg, preferably between 0.2 cmVg and 1.2 cmVg, and more preferably between 0.25 cmVg and 1.1 cmVg.

[0182] The macroporous volume of the support is advantageously between 0.01 cmVg and 0.5 cmVg, preferably between 0.01 cmVg and 0.4 cmVg, and more preferably between 0.01 cmVg and 0.3 cmVg.

[0183] The manufacture of amorphous silicon oxide type supports and their shaping is well known and taught to those skilled in the art, for example in the Handbook of Porous Solids, Wiley-VCH (Volume 3, pages 1543-1590).

[0184] Preferably, the support supplied in step ii”) is in the form of beads, extrudates (preferably cylindrical, trilobed or quadrilobed), pellets, or irregular and non-spherical agglomerates.

[0185] Very advantageously, said support is in the form of balls or extrudates.

[0186] When the support is in the form of balls, the diameter of the balls is generally between 0.5 mm and 10 mm, preferably between 1 mm and 5 mm. When the support is in the form of an extrudate, the length of the extrudate is generally between 2 mm and 10 mm, preferably between 2 mm and 8 mm, and more preferably between 3 mm and 6 mm. When the support is in the form of an extrudate, the extrudates have a diameter generally between 0.5 mm and 10 mm, preferably between 1.0 mm and 2.5 mm and between 1.0 mm and 2.0 mm in length.

[0187] Preferably, the impregnation step ii”) may be preceded by a heat treatment step carried out at a temperature between 80°C and 550°C.

[0188] Preferably, the impregnation step ii”) can be followed, optionally, by other impregnation steps. The impregnation steps following the first can advantageously be carried out after the maturation step b). Step b)

[0189] The preparation process according to the invention comprises a step b) of maturation of the material obtained at the end of step a). Said maturation step is advantageously carried out at a temperature between 0°C and 300°C, preferably between 20°C and 200°C and preferably between 20°C and 150°C, for a duration advantageously between 1 minute and 72 hours, preferably between 30 minutes and 72 hours, preferably between 1 hour and 48 hours and more preferably between 1 hour and 24 hours.

[0190] Preferably, said maturation step is carried out in air and preferably in humid air with a relative humidity between 20% and 100%, and preferably between 70% and 100%. This step allows good hydration of the material limiting the appearance of cracks which are detrimental to the mechanical resistance. At the end of step b), a precursor of matured material is obtained. Step c)

[0191] According to an essential step of the preparation process, the matured material precursor from step b) undergoes a calcination step c) at a temperature between 800°C and 1200°C, preferably between 800°C and 1100°C, and very preferably between 800°C and 900°C. Step c) is carried out for a duration advantageously between 1 hour and 12 hours, preferably between 1 hour and 4 hours. This step is essential for the formation of the cristobalite crystallographic phase. This step also makes it possible to eliminate the organic additives used in order to facilitate the shaping of the material.

[0192] Said calcination step c) is advantageously carried out under a gas flow comprising oxygen, for example preferably the matured material precursor obtained at the end of step b) is calcined under dry air or with different humidity levels or in the presence of a gas mixture comprising an inert gas, preferably nitrogen, and oxygen. The gas mixture used preferably comprises at least 5% by volume, or even preferably at least 10% by volume of oxygen relative to the total volume of said gas mixture.

[0193] At the end of step c), a material is obtained according to an embodiment according to the invention. However, the preparation method may also comprise two additional steps d) and e) to obtain a material according to another embodiment according to the invention. Steps d) and e) are described in detail below. Step d) (optional)

[0194] In one embodiment according to the invention, the material obtained at the end of step c) is brought into contact with at least one second phosphate precursor, and at least one second potassium and / or cesium precursor to obtain a second material precursor.

[0195] Advantageously, step d) comprises the following sub-steps:

[0196] dl) a liquid solution in aqueous or organic phase is prepared comprising at least one second phosphate precursor, and at least one second potassium and / or cesium precursor, at a temperature preferably between 5°C and 80°C, more preferably between 10°C and 70°C;

[0197] d2) the solution prepared in step dl) is impregnated onto the material obtained at the end of step c), the volume of the solution being advantageously between 0.9 and 1.1, preferably between 0.8 and 1.05 times the pore volume of the material obtained at the end of step c);

[0198] d3) optionally, a step of maturation of the second material precursor obtained at the end of step d2),

[0199] d4) optionally, a step of drying the second material precursor matured obtained at the end of step d3).

[0200] Preferably, the phosphate concentration of the solution supplied in step dl) is between either 50 g / L and 2000 g / L.

[0201] The impregnation solution of step dl) is preferably prepared by dissolving in aqueous or organic phase one or more precursors of phosphate and potassium (K) or cesium (Cs) element. The impregnation solution can advantageously be prepared by mixing phosphorus and alkali metal elements introduced independently. In this case, the alkali metal precursor M chosen from K or Cs is chosen for example from one or more of the salts of carbonate M2CO3, nitrate MNO3, sulfate, formate HCOOM, acetate CH2COOM, citrate, lactate, chloride MCI, hydroxide MOH, oxide M2O.

[0202] The phosphate precursor(s) may advantageously be chosen, for example, from H3PO4, (NH4)H2PO4, (NH4)2HPO4, (NH4)PO4, P2O5.

[0203] Preferably, a maturation step d3) is carried out, advantageously at a temperature between 0°C and 300°C, preferably between 20°C and 200°C and preferably between 20°C and 150°C, preferably for a period between 1 minute and 72 hours, preferably between 30 minutes and 72 hours, preferably between 1 hour and 48 hours, and more preferably between 1 hour and 24 hours.

[0204] Preferably, said maturation step is carried out in air and preferably in humid air with a relative humidity between 20 and 100% and preferably between 70 and 100%. This step allows good hydration of the material limiting the appearance of cracks which are detrimental to mechanical resistance.

[0205] Preferably, after the maturation step d3), a drying step is carried out at a temperature below 250°C, preferably between 15°C and 180°C, more preferably between 30°C and 160°C, even more preferably between 50°C and 150°C, and even more preferably between 70°C and 140°C, for a duration typically between 0.5 hours and 12 hours, and more preferably for a duration between 0.5 hours and 5 hours. Longer durations are not excluded, but do not necessarily provide an improvement.

[0206] Preferably, the impregnation step d) can be followed, optionally, by other impregnation steps. Step e) (optional)

[0207] In an embodiment according to the invention, the second material precursor obtained at the end of impregnation step d) undergoes a calcination step e) at a temperature between 300°C and 600°C, preferably between 300°C and 550°C, and very preferably between 300°C and 525°C for a duration advantageously between 1 hour and 12 hours, preferably between 1 hour and 4 hours.

[0208] Said calcination step e) is advantageously carried out under a gas flow comprising oxygen, for example preferably the extrudates are calcined under dry air or with different humidity levels or even treated at temperature in the presence of a gas mixture comprising an inert gas, preferably nitrogen, and oxygen. The gas mixture used preferably comprises at least 5% by volume, or even preferably at least 10% by volume of oxygen.

[0209] At the end of step e), the material is obtained according to another embodiment according to the invention. Transformation process

[0210] The material according to the invention can advantageously be used as a catalyst in a process for dehydrating hydroxypropanoic acid and its derivatives.

[0211] The process for dehydrating hydroxypropanoic acid and its derivatives operates in the presence of the material prepared according to the invention, which is advantageously used as a catalyst at a temperature of between 180°C and 450°C, preferably between 190°C and 430°C, very preferably between 250°C and 420°C and very preferably between 270°C and 420°C, at a pressure of between 0.1 MPa and 12 MPa, preferably between 0.11 MPa and 10 MPa, preferably between 0.13 MPa and 9 MPa and very preferably between 0.15 MPa and 8 MPa, and at a mass flow rate ratio of load on mass of material between 0.01 h 1 and 100 h *, preferably between 0.02 and 50 h 1, more preferably between 0.03 and 30 h 1 and very preferably between 0.05 and 20 h 1.

[0212] Said method makes it possible to selectively obtain a mixture of products comprising acrylic acid.

[0213] During the dehydration of hydroxypropanoic acid and its derivatives into acrylic acid, a mixture of different products, called by-products, is obtained, including in particular propanoic acid, carbon monoxide, carbon dioxide, acetaldehyde, heavy compounds containing more than 3 carbon atoms.

[0214] Said process can advantageously be carried out under a neutral or oxidizing atmosphere.

[0215] Said process is preferably operated continuously, in a fixed bed, preferably at a pressure adjusted so that the products and reactants are in the gas phase, the feed being injected into the process preferentially in the liquid phase. Charge

[0216] The feedstock feeding said process advantageously comprises at least one compound included in the list of hydroxypropanoic acid and its derivatives. Said feedstock advantageously comprises a hydroxypropanoic acid chosen from 2-hydroxypropanoic acid, 3-hydroxypropanoic acid. Preferably, said feedstock comprises 2-hydroxypropanoic acid. Said feedstock comprises between 1% and 99.9% by weight, preferably between 5% and 99.5% by weight, very preferably between 7% and 99% by weight and even more preferably between 8% and 98% by weight of hydroxypropanoic acid and its derivatives.

[0217] Said feedstock may also comprise impurities linked, in particular, to the processes for obtaining hydroxypropanoic acid and its derivatives such as fermentation. The impurity content is preferably less than 10% of the weight of said feedstock. The hydroxypropanoic acid(s) and its derivatives included in said feedstock may be of any origin, chemical, petrochemical or biosourced.

[0218] Said filler comprises between 0.1% and 99% by weight, preferably between 0.5% and 90% by weight, very preferably between 1% and 80% by weight and even more preferably between 2% and 70% by weight of water.

[0219] Said filler comprises between 0.1% and 99% by weight, preferably between 0.5% and 90% by weight, very preferably between 1% and 80% by weight and even more preferably between 2% and 70% by weight of organic solvent, such as for example an alcohol.

[0220] The main products obtained by said process are hydroxypropanoic acids and its unconverted derivatives, acrylic acid resulting from the dehydration reaction.

[0221] The examples below illustrate the invention without limiting its scope. Examples

[0222] In order to exemplify the invention, several methods of preparing materials are described. The contents are expressed in mass percentages.

[0223] Example 1: Preparation of extrudates A based on embodiment 1 in presence of precipitated silica powder (% Li2O = 8.1)

[0224] A precipitated silica powder (Nyasil20; Nyacol®) (41.1%), a source of colloidal silica sol (12.8%), potassium phosphate (KPO3, Aldrich) (27.5%), lithium nitrate (LiNO3, Aldrich) (18.6%) and Méthocel™ (K15M) (3%) are introduced and pre-mixed in a Brabender brand mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The paste obtained is then extruded on an MTS brand piston extruder using a cylindrical die with a diameter of 1.6 mm. The extrudates obtained (extrudates A) are then dried for 16 hours at 120°C in a ventilated oven. Finally, the A extrudates are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours. The extrudates calcined at 450°C are called Al materials (not in accordance with the invention) and the extrudates calcined at 800°C are called A2 materials (in accordance with the invention) [see Table 1 below].

[0225] Example 2: Preparation of extrudates B based on embodiment 2 in presence of a colloidal silica sol (% Li2O = 7.8)

[0226] A source of colloidal silica sol (12.3%), a source of potassium dihydrogen phosphate powder (KH2PO4; Aldrich) (30.4%) ground and sieved to 100 μm are introduced and mixed in the tank of a Thinky brand centrifugal planetary mixer. The rotation speed is set at 1500 rpm for 30 seconds. Then, the suspension obtained, a Méthocel™ (K15M) powder (3%), a lithium nitrate powder (LiNO3, Aldrich) (17.9%) and a precipitated silica powder (Nyasil20; Nyacol®) (39.4%) are introduced and pre-mixed in a Brabender brand mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The resulting paste is then extruded on an MTS piston extruder using a 1.6 mm diameter cylindrical die. The extrudates obtained (extrudates B) are dried for 16 hours at 120°C in a ventilated oven.Finally, the extrudates B are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours. The extrudates calcined at 450°C are called materials B1 (not in accordance with the invention), the extrudates calcined at 800°C are called materials B2 (in accordance with the invention) [see Table 1 below].

[0227] Example 3: Preparation of extrudates B' based on embodiment 2 in presence of a colloidal silica sol (% Li2O = 5.5)

[0228] A source of colloidal silica sol (13.9%), a source of dihydrogeno- potassium phosphate (KH2PO4; Aldrich) (31.5%) ground and sieved to 100 μm are introduced and mixed in the tank of a Thinky brand centrifugal planetary mixer. The rotation speed is set at 1500 rpm for 30 seconds. Then, the suspension obtained, a powder of Méthocel™ (K15M) (3%), a powder of lithium nitrate (LiNO3, Aldrich) (12.8%) and a powder of precipitated silica (Nyasil20; Nyacol®) (41.8%) are introduced and pre-mixed in a Brabender brand mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The paste obtained is then extruded on an MTS brand piston extruder using a cylindrical die with a diameter of 1.6 mm. The extrudates obtained (extrudates B') are dried for 16 hours at 120°C in a ventilated oven. Finally, the extrudates B' are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours.Extrudates calcined at 450°C are called B3 materials (not in accordance with the invention), extrudates calcined at 800°C are called B4 materials (in accordance with the invention) [see Table 1 below].

[0229] Example 4: Preparation of extrudates B” based on embodiment 2 in the presence of a colloidal silica sol (% Li2O = 3.9)

[0230] A source of colloidal silica sol (14.5%), a source of potassium dihydrogen phosphate powder (KH2PO4; Aldrich) (32.9%) ground and sieved to 100 μm are introduced and mixed in the tank of a Thinky brand centrifugal planetary mixer. The rotation speed is set at 1500 rpm for 30 seconds. Then, the suspension obtained, a Méthocel™ (K15M) powder (3%), a lithium nitrate powder (LiNO3, Aldrich) (8.9%) and a precipitated silica powder (Nyasil20; Nyacol®) (43.6%) are introduced and pre-mixed in a Brabender brand mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The resulting paste is then extruded on an MTS piston extruder using a 1.6 mm diameter cylindrical die. The extrudates obtained (extrudates B”) are dried for 16 hours at 120°C in a ventilated oven.Finally, the B” extrudates are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours. The extrudates calcined at 450°C are called B5 materials (not in accordance with the invention), the extrudates calcined at 800°C are called B6 materials (in accordance with the invention) [see Table 1 below].

[0231] Example 5: Preparation of extrudates B”' based on embodiment 2 in presence of a colloidal silica sol (% Li2O = 2.04)

[0232] A source of colloidal silica sol (15.2%), a source of potassium dihydrogen phosphate powder (KH2PO4; Aldrich) (34.5%) ground and sieved to 100 μm are introduced and mixed in the tank of a Thinky brand centrifugal planetary mixer. The rotation speed is set at 1500 rpm for 30 seconds. Then, the suspension obtained, a powder of Méthocel™ (K15M) (3%), a powder of nitrate lithium (LiNO3, Aldrich) (4.7%) and precipitated silica powder (Nyasil20; Nyacol®) (45.6%) are introduced and premixed in a Brabender mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The paste obtained is then extruded on an MTS piston extruder using a cylindrical die with a diameter of 1.6 mm. The extrudates obtained (extrudates B”') are dried for 16 hours at 120°C in a ventilated oven. Finally, the extrudates B'” are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours. The extrudates calcined at 450°C are called B7 materials (not in accordance with the invention), the extrudates calcined at 800°C are called B8 materials (in accordance with the invention) [see Table 1 below].

[0233] Example 6: Preparation of extrudates C based on embodiment 2 in the presence of a zeolite powder (e.g.: %Li2O =7.9)

[0234] A source of colloidal silica sol (12.3%), a source of potassium dihydrogen phosphate powder (KH2PO4; Aldrich) (30.4%) ground and sieved to 100 μm are introduced and mixed in the tank of a Thinky brand centrifugal planetary mixer. The rotation speed is set at 1500 rpm for 30 seconds. The suspension obtained, a methocel powder (K15M) (3%), a lithium nitrate powder (LiNO3, Aldrich) (18.2%) and a ZSM-5 zeolite powder (CBV28014; Zeolyst) (38.6%), are introduced and pre-mixed in a Brabender brand mixer. Water is added dropwise until a paste is obtained and mixing is continued for 20 minutes. The resulting paste is then extruded on an MTS piston extruder using a 1.6 mm diameter cylindrical die. The extrudates are dried for 16 hours at 120°C in a ventilated oven.Finally, the extrudates obtained (extrudates C) are subjected to different calcination temperatures (450°C and 800°C) in a muffle furnace for 3 hours. The extrudates calcined at 450°C are called materials C1 (not in accordance with the invention) and the extrudates calcined at 800°C are called materials C2 (in accordance with the invention) [see Table 1 below].

[0235] For each of the materials obtained (compliant or non-compliant), the structural characteristics (total pore volume, macroporous volume, macroporous median diameter, specific surface area, EGG) and the crystalline phases observed by DRX are indicated in table 1 below.

[0236] [Tables 1] T calcination (°C) Li (% weight measured as Li2O V total (cm3 / g) V macro (cmVg) Dmacro (nm) Sbet (m2 / g) EGG (daN / mm) DRX Al (non-conforming) 450 8.1 0.28 0.28 500 55 Monoclinic KPO3 Amorphous silicic phase Quartz and tridymite A2 (conforming) 800 8.1 0.27 0.17 639 18 4 LiK3P2O7, Lithium tri-potassium di-phosphate with ortho-rhombic structure Li3PO4, Lithio-phosphate with ortho-rhombic structure SiO2 of cristobalite type with tetragonal structure B1 (non-conforming) 450 7.8 0.3 0.3 800 Monoclinic KPO3 Amorphous silicic phase Quartz and tridymite B2 (conform me) 800 7.8 0.26 0.26 2930 <1 1.28 LiK3P2O7, Lithium tri-potassium di-phosphate of ortho-rhombic structure Li3PO4, Lithio-phosphate of ortho-rhombic structure SiO2 of cristobalite type of tetragonal structure B3 (non-conform me) 450 5.5 0.28 0.28 789 <1 Monoclinic KPO3 Amorphous silicic phase Quartz and tridymite B4 (conform me) 800 5.5 0.16 0.16 3396 <1 1.2 LiK3P2O7, Lithium tri-potassium di-phosphate of ortho-rhombic structure KPO3 monoclinic SiO2 of cristobalite type of tetragonal structure B5 (non-conform me) 450 3.9 0.21 0.17 492 <1 KPO3 monoclinic Amorphous silica phase Quartz and tridymite B6 (conformal) 800 3.9 0.3 0.3 2101 <1 1.2 LiK3P2O7, Lithium tri-potassium di-phosphate of ortho-rhombic structure LiPO3, of ortho-rhombic structure SiO2 of cristobalite type of tetragonal structure B7 (non-conformal) 450 2.1 0.24 0.18 422 16 - Monoclinic KPO3 Amorphous silicic phase B8 (conformal) 800 2.1 0.14 0.14 3923 <1 1.1 Monoclinic KPO3 LiPO3, of ortho-rhombic structure SiO2 of cristobalite type of tetragonal structure Cl (non-conformal) 450 1.9 0.16 0.16 450 22 2.2 Zeolite type ZSM-5 + quartz + tridymite KPO3 monoclinic C2 (compliant) 800 1.9 0.04 0.04 2500 <1 2.8 LiK3P2O7, Lithium tri-potassium di-phosphate orthorhombic structure Li3PO4, Lithiophosphate of orthorhombic structure SiO2 of cristobalite type of tetragonal structure

[0237] Example 7: Preparation of PL extradits by impregnation of material B6

[0238] 1.6 grams of potassium hydrogen phosphate (K2HPO4, M= 174 g / mol) and 1.2 g of ammonium hydrogen phosphate ((NH4)2HPO4, M= 132 g / mol) are first dissolved in 4.9 ml of distilled water at room temperature. After complete dissolution, the mixture is added dropwise to 20 grams of material B6. The solid is matured at room temperature for 40 minutes and then dried for 10 hours at 120°C in air. It is then calcined in air at 450°C for 4 hours to obtain the material DI (in accordance with the invention).

[0239] The compositional analysis of the DI material by FX gives a weight content of K of 12% by weight relative to the total weight of the material and of P of 9.5% by weight relative to the total weight of the material. The average equivalent weight content of KPO3 of the D3 material after calcination is 36% by weight relative to the total weight of the material.

[0240] Example 8: Use of catalysts B3. B4. B5. B6. B7. B8 and DI as catalysts for the dehydration of lactic acid into acrylic acid in the gas phase

[0241] The catalysts are tested in the form of extrudates with an Avantium® unit comprising 16 reactors, with an internal diameter of 2 mm and a length of 560 mm. The reaction is carried out in the gas phase, at 375°C and at a total pressure of 10 barg (1 MPa). The feed contains 12% by weight of lactic acid and 88% by weight of water. The gas (N2) and the liquid feed are co-injected and mixed upstream of the reactor head. The evaporation of the feed is carried out in the first part of the reactor with the help of a cord. The PPH of lactic acid is 0.2 h1. The mass of catalyst introduced is around 220 mg. At the unit outlet, all the products are analyzed by gas chromatography. The results are presented in Table 2 below.

[0242] [Tables2] Catalyst KPO3 / (KPO3+SiO2 + Li2O) Li2O / (KPO3+SiO2 + Li2O) Li / K mol / mol Calcination time (°C) Bed height (mm) Yield Acrylic Acid (% molC) B3 (non-compliant) 28 5.5 0.55 450 110 80 B4 (compliant) 28 5.5 0.55 800 93 78 B5 (non-compliant) 30 3.9 0.31 450 96 71 B6 (compliant) 30 3.9 0.31 800 84 66 B7 (non-compliant) 31 2.1 0.17 450 87 70 B8 (compliant) 31 2.1 0.17 800 80 65 DI (Compliant) 36 3.5 0.19 800 80 70 Conversion

[0243] Lactic acid (LA) conversion is calculated using the following formula:

[0244] LA conversion (%) = 100 x ([LA]C feed - [LA]C effluent) / [LA]C feed

[0245] with [AL]C = carbon concentration in AL in gC / L determined by HPLC.

[0246] The carbon yield of acrylic acid (AA) is determined according to the following formula:

[0247] Yield AA (%) = 100 x [AA]C effluent / [AL]C load

[0248] with [AA]C carbon concentration in AA in gC / L determined by HPLC.

[0249] Catalysts B3, B4, B5, B6, B7, B8 and DI convert a lactic acid feedstock into acrylic acid with a carbon yield greater than 60%. After 150 hours under load, the unloading of catalysts B4, B6, B8 and DI is easier than that of catalysts B3, B5, and B7 which are stuck to the reactor walls. The shaped catalysts for which calcination at a temperature greater than 800°C is applied and a cristobalite phase is obtained, are more stable under operating conditions and after a time under load greater than 100 hours, can be easily unloaded.

Claims

Claims

1. A process for preparing a macroporous material comprising an active phase comprising at least one potassium phosphate salt and / or at least one cesium phosphate salt, at least one lithium salt, and a support comprising silica at least partially in the crystalline form cristobalite, comprising at least the following steps: a) at least one source of silica is brought into contact with at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor to obtain a material precursor; b) the material precursor obtained at the end of step a) is allowed to mature for a period of between 1 minute and 72 hours to obtain a matured material precursor; c) the matured material precursor obtained at the end of step b) is calcined at a temperature of between 800°C and 1200°C to obtain said material.

2. A method according to claim 1, wherein in step a) said phosphate, potassium and / or cesium precursors are supplied in the form of at least one potassium phosphate salt and / or at least one cesium phosphate salt.

3. A method according to claim 2, wherein said potassium phosphate salt is selected from: KH2PO4, KH2P20i2, K6P6O7, K3H2P3Oi0, K4H2P40i3, K3P30ç, K4P40i2, K6P60i8, KxP3O24, KioPio030, potassium phosphate (tripotassium) (PO43,3K+), alone or in mixture.

4. A method according to one of claims 2 or 3, wherein said cesium phosphate salt is selected from: CsH2PO4, Cs2H2P3Oi0, Cs4H2P4O i3, Cs3P3O9, Cs4P40i2, Cs6P60i8, Cs8P8O24, (CsPO3), alone or as a mixture.

5. A method according to any one of claims 2 to 4, wherein in step a) said lithium precursor is supplied in the form of at least one lithium salt chosen from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts, in amorphous or crystalline oxide form, taken alone or as a mixture.

6. A method according to claim 5, wherein said lithium salt is selected from lithium phosphate, sulfate, nitrate, carbonate or hydroxide salts from the following list: LiH2PO4, Li2H2P2O7 Li3P3O 9, Li4P4O[2, Li6P60i8, Li8P8O24, Li2SO4, LiNO3, Li2CO3jLiOH, taken alone or in mixture.

7. A method according to one of claims 5 or 6, wherein said lithium salt is selected from lithium nitrate (LiNO3), lithium hydroxide (LiOH), or lithium carbonate (Li2CO3).

8. A method according to any one of claims 5 to 7, wherein said potassium phosphate salt and / or said cesium phosphate salt, and said lithium salt, are supplied in step a) in the form of a powder.

9. Method according to claim 8, wherein prior to their introduction into step a), said powder of at least one potassium and / or cesium phosphate salt and / or said powder of at least one lithium salt are ground and sieved to a grain size of less than 100 μm.

10. Method according to any one of claims 1 to 9, in which step a) comprises the following sub-steps: i) at least one powder of precipitated silica, silica gel or zeolite with a Si / Al ratio >100, at least one colloidal silica sol, at least one powder of at least one potassium and / or cesium phosphate salt and at least one powder of at least one lithium salt are mixed in at least one solvent to obtain a mixture; ii) the mixture obtained at the end of step i) is shaped.

11. Method according to any one of claims 1 to 9, in which step a) comprises the following sub-steps: i') at least one colloidal silica sol is mixed with at least one powder of at least one potassium and / or cesium phosphate salt to obtain a suspension; ii') a powder of at least one precipitated silica, a silica gel, or a zeolite with a Si / Al ratio >100, at least one powder of at least one lithium salt, and at least one solvent are added to said suspension obtained at the end of step i'); iii') the paste obtained at the end of step ii' is shaped.

12. Method according to claim 1, in which step a) comprises the following sub-steps: i”) a liquid solution in aqueous or organic phase is supplied comprising at least one phosphate precursor, at least one potassium and / or cesium precursor, and at least one lithium precursor; ii”) said solution obtained at the end of step i”) is impregnated on a shaped support containing silica as a silica source.

13. A method according to claim 12, wherein the impregnation solution of step i”) comprises a mixture of alkali metal precursors Ml and M2, with Ml selected from K and / or Cs, and M2 being lithium.

14. A method according to claim 13, wherein said alkali metal precursors Ml and M2 are selected from salts of carbonate M2 CO3, nitrate MNO3, sulfate, formate HCOOM, acetate CH2 COOM, citrate, lactate, chloride MCI, hydroxide MOH and oxide M2O, with M = Ml and / or M2.

15. A method according to any one of claims 12 to 14, wherein said phosphate precursor is selected from H3PO4, (NH4)H2PO4, (NH4)2HPO4, (NH4)PO4, and P2O5.

16. Method according to any one of claims 1 to 15, further comprising the following steps: d) bringing said material obtained at the end of step c) into contact with at least one second phosphate precursor, and at least one second potassium and / or cesium precursor to obtain a second material precursor; e) calcining the second material precursor obtained at the end of step d) at a temperature between 300°C and 600°C.