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  • 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
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  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
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  • 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
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28011—Other properties, e.g. density, crush strength
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  • 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
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3028—Granulating, agglomerating or aggregating
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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  • 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
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  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/34—Mechanical properties
  • B01J35/37—Crush or impact strength
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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  • 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
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
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  • 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
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  • 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
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/06—Washing
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • 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
  • C01B39/026—After-treatment
• • 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
  • C01B39/20—Faujasite type, e.g. type X or Y
  • C01B39/24—Type Y
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89

Definitions

• the present invention relates to zeolite materials in the form of agglomerates comprising at least one mesoporous zeolite, and the process for preparing said agglomerated zeolite materials.
• the mesoporous zeolites have a great utility in many industrial fields, both as catalysts, catalyst supports but also as adsorbents, insofar as their large porosity expressed in terms of ratio [surface / volume] allows the molecules with which they are brought into contact to easily access the core of the particles and to react on a large surface, thereby enhancing the catalytic and / or adsorbent properties of these materials.
• mesoporous materials are now well known at the laboratory scale, both in terms of their structure and porous distribution, their modes of synthesis, and their possible applications as catalysts and / or as adsorbents. .
• mesoporous inorganic solids have led to the development of mesoporous zeolites, also called zeolites with hierarchized porosity (or "ZPH"). They can be obtained by various methods, such as for example that described in the article by Feng-Shou Xiao et al. (Hierarchically Structured Porous Materials, (2012), 435-455, Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany 978-3-527-32788-1).
• post-treatments from zeolitic crystals in powder form, initially synthesized.
• These post-treatments are for example steam treatments, followed by acidic and / or basic treatments which lead to dealumination, followed by additional treatments to eliminate extra-network species.
• patent US8486369 and patent applications US20130183229, US20130183231 are examples which illustrate such processes for the preparation of zeolite with a mesoporous structure, in particular of type Y, by various successive treatments with steam and then with acids and in the presence surfactant.
• WO2012 / 084276 discloses a method for preparing a mesoporous Y zeolite by various basic post-treatments but at the expense of microporosity. These treatments also lead, as claimed, to an increase in the Si / Al ratio by dealumination. The thus treated zeolite Y powder is then shaped for use in a hydroconversion catalysis process.
• agglomerated forms of these powders which are more commonly called zeolite agglomerates and which may be in the form of grains, yarns, extrudates or other agglomerates, said forms being obtainable by extrusion, pelletizing, atomization or other agglomeration techniques well known to those skilled in the art.
• zeolite agglomerates which may be in the form of grains, yarns, extrudates or other agglomerates, said forms being obtainable by extrusion, pelletizing, atomization or other agglomeration techniques well known to those skilled in the art.
• agglomerates are generally made of zeolite crystals (s) and a binder, usually inert vis-à-vis the application for which the zeolite is intended, said binder being intended to ensure cohesion crystals of zeolite (s) between them and to confer sufficient mechanical strength and necessary for the industrial application envisaged.
• the present invention thus aims to provide a zeolite material in the form of agglomerate comprising at least one mesoporous zeolite.
• the present invention proposes a zeolite material in the form of an agglomerate comprising at least one mesoporous FAU zeolite, with an Si / Al atomic ratio strictly greater than 1, 4 and which has improved crystallinity properties compared to the materials of the invention. prior art.
• Yet another object is to provide a method for preparing a zeolite material in the form of an agglomerate comprising at least one mesoporous zeolite having an Si / Al atomic ratio strictly greater than 1, 4, said method being easily industrializable, and improved in terms of cost and duration, compared to the production processes of agglomerates known from the prior art, while avoiding degradation of the properties of the mesoporous zeolite (s) present (s) in said material.
• one of the objectives of the present invention is to provide an agglomerated zeolite material maintaining within it the properties of purity, crystallinity and porous distribution of the mesoporous zeolite (s) starting and presenting by Moreover, good mechanical strength and optimized crystallinity, and thus allow an easy and efficient industrial use, for example in the fields of catalysis (catalysts or catalyst support), or in separation processes, adsorption or ion exchange, dynamic or static.
• agglomerated zeolite material which comprises at least one mesoporous zeolite, of which the initial properties of microporosity are maintained, that is to say that the mesoporous zeolite used for producing said agglomerated material retains the integrity of its microporosity within said material.
• the agglomerated material has a high level of crystallinity and is provided with a density and sufficient mechanical properties for use in adsorption processes or ion exchange dynamic or static.
• the proportions indicated are weight proportions, counted for the solid components in calcined equivalents, on the basis of calcination carried out at 950 ° C for 1 hour.
• the present invention relates to an agglomerated zeolite material comprising at least one mesoporous zeolite of Si / Al atomic ratio strictly greater than 1, 4 and less than or equal to 6, and optionally one or more non-mesoporous zeolites, said material having at least the following characteristics:
• a bed crush resistance measured according to the ASTM 7084-04 standard of between 0.5 MPa and 6 MPa, preferably between 0.75 MPa and 4 MPa, for a material of average volume diameter (D50), or a length (larger dimension when the material is not spherical), less than 1 mm, inclusive
• a grain crush strength measured according to ASTM D 4179 (201 1) and ASTM D 6175 (2013), between 0.5 daN and 30 daN, preferably between 1 daN and 20 daN, for a material of medium volume diameter (D50), or a length (larger dimension when the material is not spherical), greater than or equal to 1 mm, inclusive.
• the material of the present invention also has a bulk density of between 0.4 g. cm “3 and 1 " cm “3 , inclusive.
• the agglomerates comprise at least one mesoporous zeolite of the Faujasite type (FAU), with an Si / Al atomic ratio strictly greater than 1, 4 and less than or equal to 6, preferably between 1, 5 and 5, more preferably between 1, 5 and 3 inclusive, said mesoporous zeolite being advantageously selected from mesoporous Y type zeolites.
• FAU Faujasite type
• Said mesoporous zeolite is in the form of crystals whose number average diameter, measured by electron microscopy at scanning (SEM), is less than 20 ⁇ , preferably between 0.1 ⁇ and 20 ⁇ , preferably between 0.1 and 10 ⁇ , preferably between 0.5 ⁇ and ⁇ ⁇ ⁇ , more preferably preferred between 0.5 ⁇ and 5 ⁇ , terminals included.
• the term "mesoporous zeolite” a zeolite having a mesoporous outer surface, defined by the t-plot method described below, of between 40 m 2 . g "1 and 400 m 2, g " 1 , preferably between 60 m 2 .
• a "non-mesoporous zeolite” is a zeolite optionally having a mesoporous outer surface, defined by the t-plot method described below, strictly less than 40 m 2 . g "1 .
• the mesopores of the zeolite adsorbent according to the invention are easily identifiable by observation by means of a transmission electron microscope (TEM or "TEM” in English), as described for example in US7785563.
• TEM transmission electron microscope
• the process according to the invention uses a zeolite adsorbent comprising mesoporous crystals of zeolite Faujasite (FAU), of Si / Al atomic ratio strictly greater than 1, 4 and less than or equal to 6, preferably between 1.5 and 5, more preferably between 1.5 and 3 inclusive, said mesoporous zeolite being advantageously selected from Y-type mesoporous zeolites.
• FAU zeolite Faujasite
• mesoporous is meant zeolite crystals (microporous) which have, together with the microporosity, internal cavities of nanometric size (mesoporosity), easily identifiable by observation by means of a transmission electron microscope (TEM or "TEM” in English), as described for example in US7785563.
• TEM transmission electron microscope
• the adsorbents of the process according to the invention contain an amount greater than or equal to 30%, preferably greater than or equal to 40%, more preferably greater than or equal to 70%, more preferably still greater than or equal to 80%. and advantageously greater than or equal to 90% by number of mesoporous zeolite crystals and not solid crystals, with respect to all the crystals.
• This statistical analysis is advantageously carried out by analysis of at least 50 MET images.
• the crystals of the mesoporous zeolite (s) included in the zeolite material of the invention, alone or mixed with other crystals of non-mesoporous zeolites, are agglomerated with a binder.
• the binder content is as low as possible, in order to optimize the zeolite content (s) of the zeolite material.
• the binder included in the zeolitic agglomerated material of the present invention comprises, and preferably consists of, a clay or a mixture of clays and / or sols of silica or alumina which are then dried or gelled for the harden.
• These clays are preferably chosen from kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in all proportions.
• binder is understood to mean an agglomeration binder which makes it possible to ensure the cohesion of the zeolite crystals (s) in the agglomerated zeolite material of the invention.
• This binder is further distinguished from zeolite crystals in that it does not exhibit a zeolite crystalline structure after calcination, for which reason the binder is often described as inert, and more precisely inert to the adsorption and / or ion exchange.
• the binder present in the agglomerated zeolite material of the invention consists solely of one or more clays, and preferably of a single clay.
• the zeolitic agglomerated material according to the present invention may also comprise one or more other components, in an amount of between 0 and 5%, preferably between 0 and 1%, more preferably between 0 and 0.5%, limits included. , the percentages being expressed by weight relative to the total weight of the zeolitic agglomerated material.
• This or these other component (s) is (are) generally the residues of the additives, and other synthesis aids of said zeolitic agglomerated material, and in particular those which will be described later in the present description.
• Such other components include the ashes of additives after calcination, silica, and others. It should be understood that these other components are generally present in the form of residues or traces and are not used to provide any binding or cohesive character to agglomerated zeolite materials comprising at least one mesoporous zeolite of the invention.
• the agglomerated zeolite material of the present invention may be in various forms such as those well known to those skilled in the art, specialist agglomeration of powders, crystals, including zeolite crystals, and for example and in a nonlimiting manner, the zeolitic agglomerated material of the invention may be in the form of beads, yarns, extrudates or the like.
• the microporous volume decreases sharply when the mesoporous outer surface increases.
• the mesoporosity is created during the synthesis of the crystals (direct synthesis) and it is observed that the microporous volume of the adsorbents remains substantially constant, and this even when the mesoporous outer surface increases .
• zeolitic adsorbents according to the invention have, in contrast to mesoporous zeolite adsorbents of the prior art, both a high mesoporous outer surface and a high microporous volume.
• the present invention also relates to a method for preparing the agglomerated zeolite material described above comprising at least the steps of mixing at least one mesoporous zeolite, optionally with one or more additives, with at least one a binder, in the proportions indicated above, and shaped agglomerated material, according to any method known to those skilled in the art, for example by extrusion, pelletizing, atomization or other agglomeration techniques well known to those skilled in the art .
• the method of the invention comprises at least the steps of:
• a binder comprising at least 80% of clay or a mixture of clays and / or sols of silica or alumina which are then dried or gelled to harden, the clay (s) being optionally zeolonizable (s), and with up to 5% of additives, and optionally one (or more) non-mesoporous zeolite (s), and with the amount of water that allows the shaping of the agglomerated material;
• step b) calcination of the agglomerates of step b) under an oxidizing and / or inert gas scavenging, with in particular gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, depleted air; oxygen, optionally dry and / or decarbonated, at a temperature above 150 ° C, typically between 180 ° C and 800 ° C, preferably between 200 ° C and 650 ° C, for a few hours, for example from 2 to 6 hours ; d) optionally zeolizing the binder by contacting the agglomerates obtained in step c) with an alkaline basic solution;
• gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, depleted air
• oxygen, optionally dry and / or decarbonated at a temperature above 150 ° C, typically between 180 ° C and 800 ° C, preferably between 200 ° C and 650 ° C, for a few hours, for example from 2 to 6
• step e) optionally cationic exchange (s) of the agglomerates of step c) or of step d) by placing in contact with a solution of at least one alkali or alkaline earth metal salt;
• step g) obtaining the agglomerated zeolite material by activating the agglomerates obtained in step f) under the conditions described in step c).
• step e) it would not be outside the scope of the invention if the at least one mesoporous zeolite used in step a) of agglomeration had previously undergone one or cation exchange (s) (s). In this case, step e) therefore becomes unnecessary.
• the powder (zeolite crystals) thus obtained is agglomerated such that, after drying and / or after calcination and / or after ion exchange, by means of an inert binder in the sense of adsorption.
• step a) agglomeration of crystals of a zeolite prepared in the presence of a sacrificial template which is intended to be carried out is carried out. to be removed according to methods known to those skilled in the art, for example by calcination, in order to create a mesoporosity in the zeolite and thus obtain a mesoporous zeolite.
• the sacrificial template used may be of any type known to those skilled in the art and in particular those described in the application WO2007 / 043731.
• the sacrificial template is advantageously chosen from organosilanes and more preferably from [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] hexadecyl dimethylammonium chloride, [3- (trimethoxysilyl) propyl] dodecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] octylammonium chloride, N- [3- (trimethoxysilyl) propyl] aniline, 3- [2- (2-aminoethylamino)] ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysily
• sacrificial templates having a higher molar mass and for example PPDAs (Polymer Poly-DiallyldimethylAmmonium), PVB (PolyVinyl Butyral) and other oligomeric compounds known in the art for increasing the diameter of the mesopores.
• PPDAs Polymer Poly-DiallyldimethylAmmonium
• PVB PolyVinyl Butyral
• the additional step of removing the sacrificial template can be performed at any time during the process for preparing the agglomerated zeolite material of the invention.
• the elimination of said sacrificial template can thus advantageously be carried out by calcination of the zeolite crystals before the agglomeration step a), or also concomitantly with step c).
• the dried crystals are then subjected to calcination, a step necessary to release both the microporosity (elimination of water) and the mesoporosity (elimination of the structuring agent).
• the calcination allows the elimination of the sacrificial template.
• This calcination step may be carried out according to any calcination method known to those skilled in the art and, for example, and in a nonlimiting manner, the calcination of zeolite crystals comprising the sacrificial jig may be carried out under an oxidizing and / or inert gas scavenging.
• gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, oxygen-depleted air, optionally dry and / or decarbonated, at a temperature or temperatures above 150 ° C. typically between 180 ° C and 800 ° C, preferably between 200 ° C and 650 ° C, for a few hours, for example between 2 and 6 hours.
• gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, oxygen-depleted air, optionally dry and / or decarbonated
• the size of the mesoporous zeolite crystals used in step a) and the mesoporous zeolite crystals in the agglomerates is measured by scanning electron microscope (SEM) observation. This observation SEM also makes it possible to confirm the presence of non-zeolite phase comprising for example residual binder (not converted during the zeolitization step) or any other amorphous phase in the agglomerates.
• SEM scanning electron microscope
• Agglomeration and shaping (step a) can be carried out according to all the techniques known to those skilled in the art, such as extrusion, compaction, agglomeration on granulator plate, granulator drum, atomization and others. .
• the proportions of agglomeration binder and zeolites used are between 5 parts and 70 parts by weight of binder for 95 parts to 30 parts by weight of zeolite.
• the agglomerates from step a), whether in the form of beads, extrudates or the like, generally have a volume diameter by number, or a length (larger dimension when they are not spherical), less than or equal to 7 mm, preferably between 0.05 mm and 7 mm, more preferably between 0.2 mm and 5 mm and more preferably between 0.2 mm and 2.5 mm.
• one or more additives may also be added.
• the additives are preferably organic, for example lignin, starch, carboxymethylcellulose, surfactant molecules (cationic, anionic, nonionic or amphoteric), intended to facilitate the handling of the dough zeolite (s) / clay (s) by modifying the rheology and / or stickiness or to give the final agglomerates satisfactory properties, especially macroporosity.
• the additives are introduced in a proportion of 0 to 5%, preferably of 0.1% to 2%.
• the additives may also be a source of liquid and / or solid silica, preferably representing from 1% to 5% of the total mass of said solids.
• the possible source of silica may be of any type known to those skilled in the art, specialist in the synthesis of zeolites, for example colloidal silica, diatoms, perlite, fly ash ash in the language English), sand, or any other form of solid silica.
• the nature of the gases, the ramps of temperature rise and the successive temperature levels, as well as their respective durations, will be adapted according to the nature of the sacrificial template to be eliminated and depending on the nature of the binder used in the agglomeration step a).
• the zeolitization of the agglomeration binder is carried out according to any method now well known to those skilled in the art and may for example be carried out by immersion of the product of step c) in a basic solution alkaline, generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.
• a basic solution alkaline generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.
• agglomerated zeolite materials according to the present invention possess both the characteristics of the mesoporous zeolites, but also in particular the mechanical properties of conventional zeolite agglomerates known from the prior art, that is to say without mesoporous zeolite.
• the agglomerated zeolite materials of the invention show that it is possible to maintain the crystallinity and the mesoporosity of the zeolite within a zeolitic agglomerated material, to obtain a non-degraded and resistant agglomerated zeolite material. mechanically.
• the process for preparing zeolite agglomerated zeolite (s) mesoporous (s) according to the invention is a method of implementation easy, fast and economical and therefore easily industrialized with a minimum of steps.
• the loss on ignition is determined in an oxidizing atmosphere, by calcination of the sample in air at a temperature of 950 ° C ⁇ 25 ° C, as described in the standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%.
• the purity of the zeolite phases in the agglomerates is evaluated by X-ray diffraction analysis, known to those skilled in the art under the acronym DRX. This identification is carried out on a DRX device of the brand Bruker.
• each zeolite structure has a diffraction spectrum (or diffractogram) unique defined by the positioning of the diffraction peaks and their relative intensities.
• the interpretation of the diffraction spectrum (or diffractogram) obtained is carried out under EVA with identification of the phases using the ICCD database PDF-2 release 201 1.
• the amount of zeolite fractions X is measured by XRD analysis. This analysis is carried out on a device of the Bruker brand, then the quantity of the zeolite fractions X is evaluated using the software TOPAS Bruker society.
• each of the zeolite structures has a single diffractogram (or diffraction spectrum) defined by the positioning of the diffraction peaks and by their relative intensities.
• the interpretation of the diffraction spectrum (or diffractogram) obtained is carried out with the EVA software with identification of the phases using the ICDD PDF-2 base, release 201 1, which makes it possible to highlight a phase perfectly crystalline.
• the amount of zeolite fractions, by weight, is measured by XRD analysis, this method is also used to measure the amount of zeolite fractions FAU. This analysis is performed on a Bruker device, then the amount by weight of the zeolite fractions, is evaluated using the TOPAS software from Bruker.
• the measurement of the microporous volume is estimated by conventional methods such as measurements of Dubinin-Raduskevitch volumes (adsorption of liquid nitrogen at 77 K).
• the Dubinin-Raduskevitch volume is determined from the measurement of the nitrogen gas adsorption isotherm at its liquefaction temperature. Prior to adsorption, the zeolite adsorbent is degassed between 300 ° C. and 450 ° C. for a period of between 9 hours and 16 hours under vacuum (P ⁇ 6.7 ⁇ 10 -4 Pa). adsorption is then carried out on an ASAP 2020 Micromeritics-type apparatus, taking at least 35 measuring points at relative pressures of ⁇ / ⁇ 0 ratio of between 0.002 and 1.
• microporous volume is determined according to Dubinin and Rohskevitch from isotherm obtained by applying the ISO 15901 -3 (2007) standard
• the microporous volume evaluated according to the Dubinin and Rohskevitch equation is expressed in cm 3 of liquid adsorbate per gram of zeolite The measurement uncertainty is ⁇ 0.003 cm 3 g -1 .
• Figures 1 and 2 show TEM images obtained at a magnification of x 245000 and x 175000, respectively, of a reference adsorbent ( Figure 1) and the adsorbent according to the invention ( Figure 2).
• the snapshot of Figure 2 allows us to visualize (see for example the box in Figure 2) the presence of mesopores and estimate their diameters.
• the estimation of the number average diameter of the mesoporous zeolite crystals used in step a) and the zeolite crystals contained in the agglomerates is carried out as indicated previously by observation under a scanning electron microscope (SEM).
• a set of images is carried out at a magnification of at least 5000.
• the diameter of at least 200 crystals is then measured using a dedicated software, for example the Smile View software from the LoGraMi editor.
• the accuracy is of the order of 3%.
• the crush resistance of a bed of zeolite adsorbents as described in the present invention is characterized according to the Shell method series SMS1471 -74 (Shell Method Series SMS1471 -74 "Determination of Bulk Crushing Strength of Catalysts. Compression-Sieve Method ”) associated with the" BCS Tester "device marketed by Vinci Technologies.
• This method initially intended for the characterization of catalysts of size between 3 mm and 6 mm, is based on the use of a 425 ⁇ sieve which will allow in particular to separate the fines created during the crash.
• the use of a 425 ⁇ sieve remains suitable for particles with a diameter greater than 1.6 mm but must be adapted according to the particle size of the agglomerates that are to be characterized.
• the mechanical crushing strengths in grains are determined with a device "Grain Crushing Strength” marketed by Vinci Technologies, according to ASTM D 4179 and D 6175 standards.
• the agglomerated zeolite material of the invention was evaluated with respect to the Si / Al atomic ratio by elemental chemical analysis of said agglomerated zeolite material, and more precisely by chemical analysis by X-ray fluorescence as described in the NF EN ISO standard. 12677 (201 1) on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 from Bruker.
• WDXRF wavelength dispersive spectrometer
• a growth gel is prepared by adding 1446 g of colloidal silica (Ludox AM-30 containing 30% by weight of SiO 2 ) at 25 ° C in an aluminate solution containing 184 g of sodium hydroxide (NaOH), 138 g of alumina trihydrate (Al 2 O 3 , 3H 2 O, containing 65.2 % by weight Al 2 O 3 ) and 800 g water at 25 ° C in 25 minutes with a stirring speed of 300 rpm "1 .
• colloidal silica Lidox AM-30 containing 30% by weight of SiO 2
• NaOH sodium hydroxide
• Al 2 O 3 , 3H 2 O containing 65.2 % by weight Al 2 O 3
• 800 g water at 25 ° C in 25 minutes with a stirring speed of 300 rpm "1 .
• the stoichiometry of growth gel is: 2.5 Na 2 0 / AI 2 0 3 / Si0 8.0 2/1 17H 2 0.
• the homogenization of the gel growth is carried out with stirring at 300 tr.min -1 for 25 minutes at 25 ° C.
• nucleating gel (2% by weight) of composition 12 Na 2 0 / AI 2 0 3 / 10 Si0 2/180 H 2 0 prepared by mixing a sodium silicate and sodium aluminate under stirring for 1 hour under stirring at 40 ° C. After 5 minutes of homogenization tr.min 300 "1 , the stirring speed is reduced to 100 r "1 and continued for 30 minutes.
• the stirring speed is lowered to 50 rpm " and the set point of the jacket of the reactor is set at 80.degree. C. so that the reaction medium rises to 75.degree. C. in 80 minutes.
• the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization.
• the solids are recovered on sintered and then washed with deionized water to neutral pH.
• the drying is carried out in an oven at 90 ° C for 8 hours, the loss on ignition of the dried product is 23% by weight.
• the calcination of the dried product necessary to release both the microporosity (water) and the mesoporosity by eliminating the structuring agent is carried out with the following temperature profile: 30 minutes of temperature rise at 200 ° C., then 1 bearing time at 200 ° C, then 3 hours of temperature rise at 550 ° C, and finally 1.5 hours of bearing at 550 ° C.
• a commercial zeolite the CBV100 marketed by Zeolyst International, a non-mesoporous atom having an Si / Al atomic ratio of 2.6, is used.
• the size distribution of the mesopores is calculated by the Density Functional Theory (DFT) method with the cylindrical Pores model.
• DFT Density Functional Theory
• the percentage of crystallinity is calculated using TOPAS software using ICDD PDF-2, release 201 1.
• a homogeneous mixture consisting of 1600 g of anhydrous crystals of mesoporous zeolite Y obtained in Example 1, 350 g of anhydrous kaolin, 130 g of colloidal silica sold under the trade name of Klebosol® 30 is prepared. (Containing 30% by weight of Si0 2 and 0.5% of Na 2 0) as well as the amount of water which allows the extrusion of the mixture. The fire loss of the pulp before extrusion is 44%.
• Extruded shapes 1.6 mm in diameter are formed.
• the extrudates are dried overnight in a ventilated oven at 80 ° C. They are then calcined for 2 hours at 550 ° C. under a nitrogen sweep and then 2 h at 550 ° C. under a decarbonated dry air sweep.
• the mechanical crushing strength on the extrudates of mesoporous zeolite Y is 2.7 daN. Their apparent density is 0.63 g. cm "3 .
• Example 2 The operations of Example 2 are repeated identically by substituting the mesoporous Y zeolite with the non-mesoporous Y zeolite of reference (CBV 100).
• CBV 100 non-mesoporous Y zeolite of reference
• the mechanical crush strength of non-mesoporous Y zeolite extrudates of reference is 1.7 daN.
• Their apparent density is 0.60 gcm- 3 .
• agglomerated zeolite material according to the invention comprising a mesoporous Y zeolite exhibits mechanical characteristics as well as an apparent density comparable to those of an agglomerated zeolite material comprising a non-mesoporous zeolite.
• the present invention makes it possible to have agglomerated zeolite materials combining both the properties of the mesoporous zeolites, the properties related to the microporosity and the mechanical properties of the zeolite agglomerates known hitherto. It is thus possible to envisage without problem using the agglomerated zeolite materials of the invention in all fields of industrial applications such as catalysis, separation, adsorption, and others.
• the agglomerates according to the invention have microporous volumes equivalent to those measured on agglomerates based on non-mesoporous zeolites of the prior art and mesoporous outer surfaces substantially greater than those measured on these same agglomerates based on non-zeolites. mesoporous of the prior art.

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