Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28004—Sorbent size or size distribution, e.g. particle size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/28016—Particle form
  • B01J20/28019—Spherical, ellipsoidal or cylindrical
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28078—Pore diameter
  • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/643—Pore diameter less than 2 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/69—Pore distribution bimodal
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Definitions

• the present invention relates to the field of mesostructured aluminosilicate materials with a high aluminum content. It also relates to the preparation of these materials which are obtained by the use of the "EISA" (Evaporation Induced by Self Assembly) process, also known as an evaporation-induced self-assembly process.
• EISA Evaporation Induced by Self Assembly
• the structural and textural properties of the materials according to the invention as well as their acid-base properties make them particularly suitable for applications in the field of refining and petrochemistry.
• This phenomenon of cooperative self-assembly governed, inter alia, by the concentration of structuring agent can be induced by progressive evaporation of a solution of reagents whose concentration of structuring agent is lower than the critical micelle concentration, which leads either to the formation of mesostructured films in the case of a deposit on substrate ("dip-coating" technique), or the formation of a mesostructured powder after atomization (aerosol technique) or draining of the solution.
• 6,387,453 discloses the formation of organic-inorganic hybrid films mesostructured by the "dip-coating" technique, these same authors having the aerosol technique has also been used to develop purely silicic mesostructured materials (CJ Brinker, Y. Lu, A. Sellinger, H. Fan, Adv Mater., 1999, 11, 7).
• the release of the porosity is then obtained by removing the surfactant, which is conventionally carried out by chemical extraction processes or by heat treatment.
• several families of mesostructured materials have been developed.
• the M41S family originally developed by Mobil consisting of mesoporous materials obtained via the use of ionic surfactants such as quaternary ammonium salts, having a generally hexagonal, cubic or lamellar structure, pores of uniform diameter in a range of 1.5 to 10 nm and amorphous walls of the order of 1 to 2 nm thick has been extensively studied.
• the incorporation of the aluminum element into the amorphous silicic framework by direct synthesis or by post methods. Synthesis was particularly looked at, the aluminosilicate materials obtained having a Si / Al molar ratio in a range from 1 to 1000 (S. Kawi, Shen SC, Surf Stud, Sci., Catal., 2000, 129, 227; Kawi, SC Shen, Surf Stud, Sci., Catal., 2000, 129, 219, R. Mokaya, W. Jones, Common Chem., 1997, 2185).
• hydrothermal stability properties and the acid-base properties thus developed by these aluminosilicates did not allow their use at an industrial stage in refining or petrochemical processes, which gradually led to the use of new structuring agents such as block copolymer type amphiphilic macromolecules, the latter leading to mesostructured materials having a generally hexagonal, cubic or lamellar structure, pores of uniform diameter in a range of 4 to 50 nm and amorphous walls of thickness in a range of 3 to 7 nm.
• the materials thus defined are not obtained by a progressive concentration of the inorganic precursors and the structuring agent within the solution where they are present.
• the elementary particles thus obtained do not have a regular shape and are generally characterized by a size greater than 500 nm.
• the mesostructured aluminosilicate materials thus obtained have increased hydrothermal stability properties compared to their homologues synthesized via other structuring agents, their properties of acid-baseicity remaining approximately similar (1 ⁇ Si / Al ⁇ 1000).
• low values of the Si / Al molar ratio are difficult to obtain since it is not easy to incorporate large amounts of aluminum into the material via these particular processes (D. Zaho, J. Feng, Q. Huo , N. Melosh, GH Fredrickson, BF Chmelke, GD Stucky, Science, 1998, 279, 548, Y.-H. Yue, A. Gideon, J. -L. Bonardet, JB d'Espinose, N. Melosh, J Fraissard, Stud Surfing Sci., Catal., 2000, 129, 209).
• the invention relates to a mesostructured aluminosilicate material consisting of at least two elementary spherical particles, each of said spherical particles consisting of a matrix based on silicon oxide and aluminum oxide, said matrix having a pore diameter between 1, 5 and 30 nm, an Si / Al molar ratio of at least 1 and having amorphous walls with a thickness of between 1 and 30 nm, said elementary spherical particles having a diameter D such that 10 ⁇ D ( ⁇ m ⁇ 100.
• the material according to the invention has a high aluminum content and the Si / Al molar ratio is preferably between 1 and 10.
• a process for preparing the material according to the invention comprises: a) mixing in solution at least one surfactant, at least one aluminic precursor and at least one silicic precursor; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 microns; c) drying said droplets, d) grinding the solid product obtained in step c); e) mixing in solution at least one surfactant, at least one aluminic precursor, at least one silicic precursor and at least one fraction of the solid product obtained in step d); f) the aerosol atomization of the suspension obtained in step e) using a spray nozzle leading to the formation of suspension droplets which are precursors of spherical elementary particles having a diameter D such that 10 ⁇ D ( ⁇ m) ⁇ 100 constitutive material according to the invention; g) drying said droplets obtained in step
• the aluminosilicate material according to the invention is a mesostructured material consisting of elementary spherical particles, each of said particles consisting of a matrix based on silicon oxide and aluminum oxide.
• Said matrix is mesostructured and has amorphous walls with a thickness of between 1 and 30 nm, a uniform pore diameter of between 1.5 and 30 nm and an Si / Al molar ratio of at least 1.
• Said spherical elementary particles have a diameter D, expressed in microns, such that 10 ⁇ D ( ⁇ m) ⁇ 100 and preferably D is between 11 and 70 ⁇ m.
• controllable size of these particles resulting from the implementation and control of the "EISA" process by the Applicant, as well as their perfectly spherical shape, allow for better control of the diffusion of the compounds when the material is used.
• catalyst or adsorbent for applications in the field of refining and petrochemistry, compared to materials known in the state of the art being in the form of elementary particles of inhomogeneous form, that is, to say irregular.
• each of said particles of the material according to the invention advantageously has a molar Si / Al ratio of between 1 and 10 and very advantageously between 1 and 5: the material according to the invention has a high aluminum content, which gives the material according to the invention acido-basicity properties of interest for applications in catalysis.
• the material according to the invention is also particularly interesting for the organized porosity it has on the mesopore scale.
• the present invention relates to a mesostructured aluminosilicate material consisting of at least two elementary spherical particles, each of said spherical particles consisting of a mesostructured matrix based on silicon oxide and aluminum oxide, said mesostructured matrix having a pore diameter of between 1.5 and 30 nm, an Si / Al molar ratio of at least 1 and having amorphous walls; of thickness between 1 and 30 nm, said elementary spherical particles having a diameter D greater than 10 microns and less than or equal to 100 microns (10 ⁇ D (microns) ⁇ 100).
• the matrix based on silicon oxide and aluminum oxide constituting each of said spherical particles of the aluminosilicate material according to the invention advantageously comprises a high aluminum content: the Si / Al molar ratio is preferably between 1 and 10 and very preferably between 1 and 5.
• the term "mesostructured material” is intended to mean a material having an organized porosity at the mesopore scale of each of said spherical particles, ie a pore-scale organized porosity having an uniform diameter. between 1.5 and 30 nm and preferably between 1.5 and 10 nm and distributed homogeneously and uniformly in each of said particles (mesostructuring of the material).
• the matrix based on silicon oxide and aluminum oxide, included in each of the spherical particles constituting the material according to the invention, is mesostructured: it has mesopores having a uniform diameter, that is to say identical for each mesopore, between 1.5 and 30 nm and preferably between 1.5 and 10 nm, distributed homogeneously and uniformly in each of the spherical particles.
• the material located between the mesopores of each of said spherical particles of the material according to the invention is amorphous and forms walls, or walls, whose thickness is between 1 and 30 nm.
• the thickness of the walls corresponds to the distance separating a first mesopore from a second mesopore, the second mesopore being the pore closest to the first mesopore.
• the organization of the mesoporosity described above leads to a structuring of the matrix based on silicon oxide and aluminum oxide, which may be hexagonal, hexagonal two-dimensional, vermicular or cubic and preferably vermicular.
• said elementary spherical particles constituting the material according to the invention have a diameter D, expressed in microns, strictly greater than 10 ⁇ m and less than or equal to 100 ⁇ m (10 ⁇ D ( ⁇ m) ⁇ 100).
• the diameter D of said spherical particles is advantageously between 11 and 70 ⁇ m.
• said elementary spherical particles have a diameter D of between 11 and 50 ⁇ m and very preferably between 15 and 50 ⁇ m. More specifically, said elementary spherical particles are present in the material according to the invention in the form of aggregates.
• the material according to the invention advantageously has a specific surface area of between 200 and 1200 m 2 / g and very advantageously between 300 and 1000 m 2 / g.
• the present invention also relates to the process for preparing the material according to the invention.
• a process for the preparation of the material according to the invention called the “main preparation process according to the invention” comprises a) mixing in solution at least one surfactant, at least one aluminum precursor and at least one silicic precursor.
• step b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 microns; c) drying said droplets, d) grinding the solid product obtained in step c); e) mixing in solution at least one surfactant, at least one aluminic precursor, at least one silicic precursor and at least one fraction of the solid product obtained in step d) so as to form a suspension; f) the aerosol atomization of the suspension obtained in step e) using a spray nozzle leading to the formation of suspension droplets, which are precursors of spherical elementary particles having a diameter D such that 10 ⁇ D ( ⁇ m ⁇ 100 constituting the material according to the invention; g) drying said droplets obtained in step f) and h) removing said surfactant introduced in steps a) and e) to obtain a material with mesostructured porosity.
• the fraction of the solid product obtained in step d) and used for the implementation of said step e) represents from 1 to 100% by weight, preferably from 1 to 80%. weight and even more preferably from 5 to 50% by weight of the total amount of solid product ground in step d).
• step c) only part of the solid product from step c) is milled during step d) of the process according to the invention; the unmilled portion is generally not reused.
• step h) of removing the surfactant is carried out before the grinding step according to step d) so that said step d) is carried out on a solid product free of organic surfactants.
• Steps a), b), c), h), d), e) and f) become consecutive in the particular case of said second mode of preparation according to the invention are followed by a new cycle of drying the droplets and removing the surfactant introduced in step e) as described in steps g) and h).
• the material according to the invention consisting of elementary spherical particles having a diameter D between 11 and 50 ⁇ m, preferably between 15 and 50 ⁇ m
• a simplified preparation process called “simplified method of preparation according to the invention "comprising the steps of: a) mixing in solution at least one surfactant, at least one aluminum precursor and at least one silicic precursor; b) the aerosol atomization of the solution obtained in step a) using a spray nozzle which leads to the formation of liquid droplets having a diameter less than or equal to 300 microns; c) drying said droplets, and h) removing said surfactant to obtain a mesostructured porosity material.
• the volume percentage of non-volatile compounds present in the suspension according to step e) of the main preparation process according to the invention and in the solution according to step a) of the simplified method of preparation according to the invention is at least 7%, preferably at least 7.5% and even more preferably at least 10%.
• Said volumetric percentage of non-volatile compounds is defined as the ratio of the volume occupied by the non-volatile inorganic fraction in the form of condensed oxide (s) (SiO 2 and AlIO 5 ) in the solid elementary particle obtained after atomization plus the volume occupied by the non-volatile organic fraction being found in the same solid particle (surfactant) on the total volume, the whole being multiplied by 100.
• inorganic precursors present in step a) of the simplified preparation process according to the invention and p in0rg are on average equal to 2 (approximation valid for an inorganic fraction of the "aluminosilicate network" type. ).
• the silicic and aluminic precursors used in steps a) and e) of the main process according to the invention or in step a) of the simplified process according to the invention are precursors of inorganic oxides well known to those skilled in the art.
• the silicic precursor can also advantageously be a precursor organometallic compound of formula Si (OR) 4 .
• the precursor aluminum is advantageously an inorganic aluminum salt of formula AIX 3 , X being a halogen or the group NO 3 .
• X is chlorine.
• the aluminum precursor may also be an aluminum oxide or hydroxide.
• the surfactant used in steps a) and e) of the main process according to the invention or in step a) of the simplified process according to the invention is an ionic or nonionic surfactant or a mixture of both.
• the ionic surfactant is chosen from phosphonium and ammonium ions and very preferably from quaternary ammonium salts such as cetyltrimethylammonium bromide (CTAB).
• CTAB cetyltrimethylammonium bromide
• the nonionic surfactant may be any copolymer having at least two parts of different polarities conferring properties of amphiphilic macromolecules.
• any copolymer with an amphiphilic character known to those skilled in the art can be used (S. Fôrster, M. Antionnetti, Adv.Mater, 1998, 10, 195-217; Fôrster, T.PIantenberg, Angew.
• a block copolymer consisting of poly (alkylene oxide) chains is preferably used.
• Said block copolymer is preferably a block copolymer having two, three or four blocks, each block consisting of a poly (alkylene oxide) chain.
• one of the blocks consists of a poly (alkylene oxide) chain of hydrophilic nature and the other block consists of a poly (alkylene oxide) chain of a nature hydrophobic.
• the blocks For a copolymer with three blocks, at least one of the blocks consists of a chain of poly (alkylene oxide) hydrophilic nature while at least one of the other blocks consists of a poly ( alkylene oxide) of hydrophobic nature.
• the hydrophilic poly (alkylene oxide) chains are poly (ethylene oxide) chains denoted by (PEO) x and (PEO) 2 and the Poly (alkylene oxide) chains of hydrophobic nature are chains of poly (propylene oxide) denoted (PPO) y , poly (butylene oxide) chains, or mixed chains, each chain of which is a mixture of several alkylene oxide monomers.
• a compound of formula (PEO) x - (PPO) y - (PEO) z where x is between 5 and 300 and y is between 33. and 300 and z is between 5 and 300.
• the values of x and z are the same.
• nonionic surfactants known as Pluronic (BASF), Tetronic (BASF), Triton (Sigma), Tergitol (Union Carbide), Brij (Aldrich) are useful as nonionic surfactants in steps a) and e) the main process according to the invention or in step a) of the simplified process according to the invention.
• Pluronic BASF
• Tetronic BASF
• Triton Sigma
• Tergitol Union Carbide
• Brij Aldrich
• two of the blocks consist of a chain of poly (alkylene oxide) hydrophilic nature and the other two blocks consist of a chain of poly (oxides) of alkylene hydrophobic nature.
• the solution in which at least one silicic precursor, at least one aluminic precursor and at least one surfactant are mixed in accordance with steps a) and e) of the main process according to the invention or in accordance with step a) of the simplified process according to the invention may be acidic, neutral or basic.
• said solution is acidic and has a maximum pH equal to 2, preferably between 0 and 2.
• the acids used to obtain an acid solution of maximum pH equal to 2 are, without limitation, hydrochloric acid, sulfuric acid and nitric acid.
• Said solution may be aqueous or may be a water-organic solvent mixture, the organic solvent preferably being a polar solvent, especially an alcohol, preferably ethanol.
• Said solution may also be substantially organic, preferably substantially alcoholic, the amount of water being such that the hydrolysis of the inorganic precursors is ensured (stoichiometric amount).
• said solution in which at least one silicic precursor, at least one aluminum precursor and at least one surfactant are mixed in accordance with step a) and step e) of the main process of the invention or in accordance with step a) of the simplified process according to the invention is an aquo-organic acid mixture, very preferably an acid-alcohol water mixture.
• Said solution according to step e) of the main process of the invention also comprises at least a fraction of the solid product obtained in step d) of the process of the invention.
• the concentrations of silicic and aluminic precursors are defined by the Si / Al molar ratio of the material according to the invention, said Si / Al molar ratio being at least 1, preferably in the range of 1 to 1000, more specifically in the range of 1 to 10 and very preferably in the range of 1 to 5.
• the initial concentration of surfactant introduced into the mixture according to steps a) and e) of the main process according to the invention or in accordance with step a ) of the simplified method according to the invention is defined by C 0 and C 0 is defined relative to the critical micelle concentration (c mc ) well known to those skilled in the art.
• the ccc is the limit concentration beyond which occurs the phenomenon of self-arrangement of the surfactant molecules in the solution.
• the concentration C 0 can be lower, equal to or greater than the c mc , preferably it is lower than the c mc .
• the concentration C 0 is lower than the c mc and said solution respectively the suspension referred to in step a) respectively in step e) of the main process according to the invention or the solution referred to in step a) of the simplified process according to the invention is an acid-alcohol water mixture.
• the step of atomizing the mixture according to steps b) and f) of the main process according to the invention or the step of atomizing the mixture according to step b) of the simplified process according to the invention produces spherical droplets with a diameter of less than or equal to 300 ⁇ m by the use of a spray nozzle, said nozzle being able to be "mono-fluid” or "bi-fluid” (with control of the pressure of a gas such as air compressed or nitrogen) according to the terms known to those skilled in the art.
• nozzles from Spraying System Emani can be used ("single-fluid" nozzle type N22 ® or "bi-fluid” type SU4 ® for example).
• the size distribution of these droplets is lognormal.
• the atomization of the solution is done in a chamber in which a gas is sent vector, a dry air / nitrogen mixture for smaller plants and nitrogen alone for larger installations.
• said droplets are dried.
• This drying is carried out by the contact of said droplets with the above gas, which leads to the progressive evaporation of the solution respectively of the suspension, for example of the aquo-organic acid solution respectively of the aqueous-organic suspension, obtained during step a) respectively of step e) of the main process for preparing the material according to the invention or the progressive evaporation of the solution obtained during step a) of the simplified process for preparing the material according to the invention, and thus to obtain spherical elementary particles.
• the outlet temperature ensuring the drying in the chamber of the atomizer is in a range of 80 to 450 ° C.
• the distribution of residence time of the droplets or particles in the atomization chamber is of the order of a few seconds .
• step d) of the main process according to the invention the particles are crushed (Netzsch CGS 10 air jet mill for example) and reduced to a few ⁇ m (generally 3 to 5 ⁇ m). Depending on the installation, the particles are collected at the exit of a cyclone or in a bag filter.
• the drying of the particles according to steps c) and g) of the main process according to the invention and according to step c) of the simplified process according to the invention is advantageously followed by a complementary heat treatment at a temperature of between 50 and 300. 0 C before removal of the surfactant in step h) of the main process according to the invention or the simplified process according to the invention to obtain the material according to the invention with mesostructured porosity.
• Said removal of the surfactant introduced in steps a) and e) of the main process according to the invention or in step a) of the simplified process according to the invention is advantageously carried out by chemical extraction processes or by heat treatment and preferably by calcination in air in a temperature range of 300 to 1000 0 C and more specifically in a range of 450 to 600 0 C for a period of 1 to 24 hours and preferably for a period of 2 to 6 hours.
• the mesostructuration of the matrix of the material according to the invention and prepared according to the methods described above is consecutive to a progressive concentration, within each droplet, of the silicic precursor, the aluminum precursor and the surfactant. , up to a concentration of surfactant c> c mc resulting from evaporation of each of the aquo-organic solutions, preferably acidic.
• the increase in the combined concentration of the silicic and aluminic precursors and the surfactant causes the precipitation of the aluminic and silicic precursors around the self-organized surfactant and consequently the structuring of the material according to the invention.
• the use of spray nozzles is particularly advantageous for constraining the reagents present in steps b) and f) of the main process according to the invention or in step b) of the simplified process according to the invention to interact with each other, no loss of material excluding solvents being possible, all the aluminum and silicon elements initially present being thus perfectly preserved throughout the process instead of being eliminated during the filtration and washing steps encountered in conventional synthesis processes known to those skilled in the art.
• the production of droplets with a diameter of less than or equal to 300 ⁇ m leads to evaporation kinetics of the solution or of the aquo-organic suspension all the more slow as the droplet is large (because proportional to the square of the diameter of the the drop to evaporate). If the total evaporation time is slower than the condensation time of the inorganic material at the periphery of the drop, a layer of condensed material is formed. the evaporation interface is an additional barrier to evaporation.
• Vant total volume of solvent, the solvent being consisting of water and optionally an organic solvent, org V p0
• the elements present must then accommodate the mesostructuration to a total volume (defined by the volume inscribed in the rigid crust) higher than the optimal value. If the ratio V pO
• steps b) and f) of the main process according to the invention respectively in step b) of the simplified method according to the invention to limit the volume of solvent to evaporate or in other words, to concentrate the aerosolized solutions in order to work preferentially with a C 0 value close to or greater than the C mc .
• this volume percentage is specific to each system and is limited mainly by three criteria: (i) the lack of stability over time of the solutions obtained in steps a) and e) of the main process of the invention respectively to the step a) of the simplified process according to the invention, (ii) the spontaneous precipitation of the solution with too high concentration (either for lack of solubility of the one or more constituents, or by condensation reaction of the inorganic constituents present in solutions obtained in steps a) and e) of the main process of the invention respectively in step a) of the simplified process according to the invention), and (iii) the rheological properties of the solutions obtained in steps a) and e) of the process main of the invention respectively in step a) of the simplified process according to the invention which may become unsuitable for the formation of droplets by the spray nozzles (viscosity too high for example).
• the mesostructured aluminosilicate material with a high aluminum content of the present invention can be obtained in the form of powder, beads, pellets, granules or extrudates, the shaping operations being carried out using conventional techniques known from the art.
• the mesostructured aluminosilicate material according to the invention is obtained in powder form, which consists of elementary spherical particles having a diameter D such that 10 ⁇ D ( ⁇ m) ⁇ 100 and preferably between 11 and 70 ⁇ m, this which facilitates the control of the possible diffusion of the compounds in the case of the use of the material according to the invention as catalyst or adsorbent in refining or petrochemical applications.
• the mesostructured aluminosilicate material of the invention is characterized by several analysis techniques and in particular by X-ray diffraction at low angles (low angle XRD), nitrogen adsorption isotherm, transmission electron microscopy (TEM). , by Fluorescence X (FX).
• the X-ray diffraction technique at low angles makes it possible to characterize the periodicity at the nanoscale generated by the organized mesoporosity of the mesostructured matrix of the material of the invention.
• the X-ray analysis is carried out on powder with a diffractometer operating in reflection and equipped with a rear monochromator using copper radiation (wavelength of 1.5406 ⁇ ).
• the nitrogen adsorption isothermal analysis corresponding to the physical adsorption of nitrogen molecules in the porosity of the material via a progressive increase in the pressure at constant temperature provides information on the particular textural characteristics of the material according to the invention. In particular, it provides access to the specific surface and the mesoporous distribution of the material.
• specific surface is meant the specific surface B. AND.
• the diameter of the mesospores ⁇ of the given mesostructured matrix corresponds to the average diameter at the nitrogen desorption defined as being a diameter such that all the pores less than this diameter constitute 50% of the pore volume (Vp). measured on the desorption branch of the nitrogen isotherm.
• Vp pore volume
• the shape of the nitrogen adsorption isotherm and the hysteresis loop can provide information on the nature of the mesoporosity.
• the nitrogen adsorption isotherm on the mesostructured aluminosilicate material according to the invention and obtained with the method of the invention when using the particular block copolymer known as poly (ethylene oxide) 20 - Poly (propylene oxide) 70- poly (ethylene oxide) 2 O (PEO 2 O-PPO 7 O-PEO 2 O or Pluronic 123 or P123) is characterized by a Class IV adsorption isotherm and a D-ring. type H1 hysteresis, the associated porous distribution curve being representative of a population of mesopores of uniform diameter centered in a range of 1.5 to 30 nm.
• TEM Transmission electron microscopy
• the morphology and size distribution of the elementary particles were established by SEM photo analysis.
• the structure of the mesostructured matrix constituting each of the particles of the material according to the invention may be cubic, vermicular or hexagonal depending on the nature of the copolymer chosen as structuring agent.
• a mesostructured aluminosilicate material obtained as described above through the use of particular block copolymer known as poly (ethylene oxide) 20 -poly (propylene oxide) 70 -poly (ethylene oxide) 2 o (PE0 2 o-PP0 70 -PE0 2 o or Pluronic 123) has a vermicular structure.
• the present invention relates to the use of the mesostructured aluminosilicate material according to the invention as an adsorbent for the control of pollution or as a molecular sieve for separation.
• the present invention therefore also relates to an adsorbent comprising the mesostructured aluminosilicate material according to the invention. It is also advantageously used as an acid solid to catalyze reactions, for example those involved in the fields of refining and petrochemistry.
• this material When the mesostructured aluminosilicate material according to the invention is used as a catalyst, this material may be associated with an inorganic matrix which may be inert or catalytically active and with a metallic phase.
• the inorganic matrix may be present simply as a binder to hold together the particles of said material in the various known forms of the catalysts (extrudates, pellets, beads, powders) or may be added as a diluent to impose the degree of conversion in a process which otherwise would progress at a rate that is too fast, leading to fouling of the catalyst consequence of a large formation of coke.
• Typical inorganic matrices are, in particular, support materials for catalysts, such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepiolite, attapulgite, fulling earth, synthetic porous materials such as SiO 2 -Al 2 O 3 , SiO 2 -ZrO 2 , SiO 2 -ThO 2 , SiO 2 -BeO, SiO 2 -TiO 2 or any combination of these compounds.
• catalysts such as the various forms of silica, alumina, silica-alumina, magnesia, zirconia, titanium oxides, boron oxides, aluminum phosphates, titanium, zirconium, clays such as kaolin, bentonite, montmorillonite, sepiolite
• the inorganic matrix may be a mixture of different compounds, in particular an inert phase and an active phase.
• Said material of the present invention may also be associated with at least one zeolite and play the role of main active phase or additive.
• the metal phase can be introduced integrally on said material of the invention.
• cations or oxides chosen from the following elements: Cu, Ag, Ga, Mg, Ca, Sr , Zn, Cd, B, Al, Sn, Pb, V, P, Sb 1 Cr, Mo, W, Mn, Re, Fe, Co, Ni, Pt, Pd, Ru, Rh, Os, Ir and all other elements of the periodic table of elements.
• the catalyst compositions comprising the material of the present invention are generally suitable for carrying out the main hydrocarbon conversion processes and organic compound synthesis reactions.
• the catalyst compositions comprising the material of the invention advantageously find their application in isomerization, transalkylation and disproportionation, alkylation and dealkylation, hydration and dehydration, oligomerization and polymerization, cyclization reactions. , aromatization, cracking, reforming, hydrogenation and dehydrogenation, oxidation, halogenation, hydrocracking, hydroconversion, hydrotreatment, hydrodesulfurization and hydrodenitrogenation, catalytic removal nitrogen oxides, said reactions involving fillers comprising saturated and unsaturated aliphatic hydrocarbons, aromatic hydrocarbons, oxygenated organic compounds and organic compounds containing nitrogen and / or sulfur as well as organic compounds containing other functional groups.
• CTAB surfactant
• the volume percentage of non-volatile compounds present in the suspension before the second atomization (step e ) of the main process according to the invention) is equal to 10.4%.
• the solid is characterized by low angle XRD, nitrogen adsorption isotherm, TEM and X-ray fluorescence. MET analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure.
• An SEM image of the spherical elementary particles thus obtained indicates that these particles have a size characterized by a diameter ranging from 15 to 100 microns, the size distribution of these particles being centered around 50 microns.
• 520 g of aluminum trichloride hexahydrate are added to a solution containing 10 kg of ethanol, 51 of water, 36 ml of HCl and 1.4 kg of surfactant P123.
• the whole is left stirring at room temperature until complete dissolution of the aluminum precursor.
• 4.0 kg of tetraethylorthosilicate (TEOS) are then added.
• the whole is atomized using a "single-fluid" spray nozzle in a chamber into which a carrier gas, a dry air / nitrogen mixture, is sent.
• the droplets, obtained by atomization are dried between 100 and 120 ° C.
• step c) of the main process of the invention The particles are collected in a bag filter. Said particles are ground using an air jet mill and reduced to a few ⁇ m (from 3 to 5 ⁇ m). A fraction of 30% by weight of these crushed particles is then reintroduced into a solution of the same formulation as the initial solution and the suspension is again atomized using a "mono-fluid" spray nozzle as above and the droplets dried between 100 and 120 ° C. according to the protocol described in the disclosure of the invention above, in accordance with step g) of the main process of the invention.
• the volume percentage of non-volatile compounds present in the suspension before the second atomization (step e) of main process according to the invention) is equal to 10.4%.
• 520 g of aluminum trichloride hexahydrate are added to a solution containing 10 kg of ethanol, 5 l of water, 36 ml of HCl and 1.4 kg of surfactant P123.
• the whole is left stirring at room temperature until complete dissolution of the aluminum precursor.
• 4.0 kg of tetraethylorthosilicate (TEOS) are then added.
• the whole is atomized using a "single-fluid" spray nozzle in a chamber into which a carrier gas, a dry air / nitrogen mixture, is sent.
• the droplets, obtained by atomization are dried between 100 and 120 ° C.
• the volume percentage of non-volatile compounds present in the solution before the atomization is equal to 10.4%.
• the solid is characterized by low angle XRD, nitrogen adsorption isotherm, TEM and X-ray fluorescence. MET analysis shows that the final material has an organized mesoporosity characterized by a vermicular structure.

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