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    • 专利摘要:
    The present invention relates to a zeolitic adsorbent having an external surface area of between 20 m2.g-1 and 70 m2.g-1, a mesoporous volume (Vmeso) of less than or equal to 0.20 cm3g-1, a content non-zeolitic phase (PNZ) less than or equal to 6%, and at least one of which is greater than or equal to 30 μm. The invention also relates to the process for preparing said zeolite materials in the form of agglomerates and its uses for gas phase or liquid phase separation operations.
    公开号:FR3028429A1
    申请号:FR1460916
    申请日:2014-11-13
    公开日:2016-05-20
    发明作者:Ludivine Bouvier；Cecile Lutz；Sylvie Szendrovics
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of zeolitic adsorbents comprising at least one mesoporous zeolite as well as the process for the preparation of said zeolite adsorbents. [0002] Inorganic mesoporous solids are well known and their synthesis, in particular by surfactant structuring effect, has been described for the first time in US Pat. No. 3,556,725. These mesoporous solids (or even mesoporous zeolites, or zeolites with mesoporous structure) have a great utility in many industrial fields, both as catalysts, catalyst supports but also as adsorbents, insofar as their high porosity expressed in terms of the [surface / volume] ratio 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. [0004] Mobil company, during the nineties, undertook a great deal of work relating to mesoporous inorganic solids, in particular relating to (alumino) silicic compounds, and more particularly to compound MCM 41 (for Mobil Composition Of Matter 41 ) of which a method of synthesis is described in Nature, (1992), vol. 359, pp.710-712, and which have been the subject of numerous patents and subsequent scientific articles. [0005] Thus, these mesoporous materials are now well known at laboratory scale, both in terms of their structure and porous distribution, of their modes of synthesis, and of their possible applications as catalysts and catalysts. or as adsorbents. However, these mesoporous inorganic materials have the major disadvantage of being thermally unstable in the presence of water which greatly limits industrial applications. [0006] The search for mesoporous inorganic solids has led to the development of mesoporous zeolites obtained by various methods, as for example 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). [0007] One of the approaches envisaged is that of post-treatments of zeolite crystals, these post-treatments being able to be, for example, treatments with water vapor, acidic and / or basic treatments which lead to dealumination, treatments Complementary to eliminate extraterrestrial species, all these post-treatments can each or together be operated one or more times, simultaneously or consecutively. [0008] Patent US8486369, patent applications US20130183229, US20130183231, as well as application WO2013106816, are examples which illustrate such processes for the preparation of zeolite with a mesoporous structure by various successive post-treatments with steam and then with acids. and in the presence of surfactant. If such processes tend to create large pore volumes, it is observed in return that they strongly degrade the crystallinity of the initial zeolite powder, up to almost 50% in certain cases. It is also necessary to use complementary cautery treatments to stabilize the zeolite framework, eliminate extra-lattice aluminum atoms in order to make possible the subsequent thermal treatments, especially calcination, required for most uses of zeolite materials as catalysts or adsorbents. Such methods making it possible to create a certain mesoporosity within the zeolite solids are therefore very heavy to implement because of the succession of numerous steps, which are uneconomical and therefore difficult to industrialize. In addition, the multitude of steps tends to weaken the zeolite structure and consequently reduce the intrinsic properties of these zeolites. [0011] For this reason, the synthesis of mesoporous zeolite solids by the direct route and with no post-treatment known as such in the prior art is preferred today. Various publications show the feasibility of synthesis in the laboratory of mesoporous zeolites, and by way of example, applications WO2007043731 and EP2592049 are particularly noteworthy, in which the synthesis of mesoporous zeolites is carried out on the basis of surfactant, and in particular that of the TPOAC type. ([3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride). Still other publications illustrate such works, such as those of R. Ryoo (Nature Materials, 5, (2006), 718 sqq.) Which describe a synthesis of LTA with mesopores, or those of A. Inayat et al. (Angew Chem Int., Ed., (2012), 51, 1962-1965) which describe the synthesis of mesoporous FAU (X) using TPHAC ([3- (trimethoxysilyl) propyl] hexadecyl dimethyl ammonium chloride), as a structuring agent. [0013] However, there is currently no description concerning the preparation of agglomerates based on agglomerated mesoporous zeolites in which the specific properties of these mesoporous zeolites, in particular their microporosity, are preserved. Therefore, it remains that today no industrial application, particularly in the field of the separation of liquids and / or gases, ion exchange or in the field of catalysis, implements such agglomerates zeolites with a high microporosity comprising at least one mesoporous zeolite and whose transfer kinetics are at least comparable to those expected due to the presence of mesoporosity. There remains therefore today a need for zeolitic adsorbents having a high microporosity, that is to say a large adsorption capacity, but also allow optimized transfers, in particular thanks to the presence of mesopores. Thus, the current need of the industrialists goes now to zeolitic adsorbents which combine both an adsorption capacity and an optimal transfer kinetics. It should also be recalled that the industry, and in particular in the fields of application mentioned above, uses zeolite adsorbents in the form of agglomerates. Indeed, synthetic zeolites are most often obtained at the end of a process of nucleation and crystallization of silico-aluminate gels, the size of the crystallites produced is of the order of a micrometer to a few micrometers: of zeolite crystals or zeolite in powder form. These powders are of difficult industrial use because they are difficult to handle because of their poor flowability, they generate significant pressure losses, and a poor distribution of flows in the beds, especially in dynamic processes which involve flowing fluids. The agglomerated forms of these powders, which are more commonly known as zeolite agglomerates or agglomerated zeolite adsorbents and which may be in the form of grains, yarns, extrudates or other agglomerates, are therefore more preferred. be obtained by extrusion, pelletizing, atomization or other agglomeration techniques well known to those skilled in the art. These agglomerates do not have the aforementioned drawbacks inherent to pulverulent materials. These agglomerates are generally made of zeolite crystals (s) and a binder, most often 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 give them sufficient mechanical strength and necessary for the industrial application envisaged. The present invention thus aims to provide a zeolite adsorbent in the form of agglomerate comprising at least one mesoporous zeolite combining both adsorption capacity and mechanical strength appropriate and adapted to the application to which it is destined. According to a preferred aspect, the present invention also aims to provide a zeolite adsorbent in the form of an agglomerate comprising at least one mesoporous zeolite combining both optimal adsorption capacity and transfer kinetics, while offering resistance appropriate mechanical and adapted to the application for which it is intended. Still another object is to provide a process for preparing such a zeolite adsorbent, said process being easily industrializable, and improved in terms of cost and time, compared to the processes for producing adsorbents. known from the prior art, while avoiding degradation of the properties of the mesoporous zeolite (s) present (s) in said material. [0022] More particularly, one of the objectives of the present invention is to provide an agglomerated zeolite adsorbent maintaining within it the properties of purity, crystallinity and porous distribution of the starting mesoporous zeolite (s) and having Moreover, good mechanical strength and optimized crystallinity and transfer kinetics, and thus allow an easy, efficient and further improved industrial use, for example in the fields of catalysis (catalysts or catalyst support), or in the processes dynamic or static ionic separation, adsorption or ion exchange systems for liquid or gaseous fluids. Still other objects will appear in the light of the description of the present invention which follows. The Applicant has discovered that it is possible to achieve, in whole or at least in part, the aforementioned objectives and to manufacture, in an economical and optimized manner, a zeolitic adsorbent with a high degree of crystallinity, and combining at the same time optimal adsorption capacity and optimal transfer kinetics. The zeolitic adsorbent according to the invention has, in addition to a high level of crystallinity, a density and mechanical properties sufficient for use in adsorption processes and ion exchange processes in dynamic or static. [0025] Unless otherwise indicated in the present description, the proportions indicated are weight proportions, counted for solid components in calcined equivalents, based on calcination carried out at 950 ° C. for 1 hour. Thus, and according to a first aspect, the present invention relates to a zeolite adsorbent having the following characteristics: the external surface, measured by nitrogen adsorption, is between 20 m2.g-1, and 70 m2.g-1, preferably between 20 m2.g-1 and 60 m2.g-1, more preferably between 30 m2.g-1 and 60 m2.g-1, more preferably between 40 m2.g- 1, and 60 m2.g-1, limits included, - the mesoporous volume (Vmeso), is such that 0 <Vmeso <0.20 cm3g-1, preferably <Vmeso <0.10 cm3g-1, measured by nitrogen adsorption, - the non-zeolite phase content (PNZ) is such that 0 <PNZ 6%, preferably 0.5% PNZ 6%, more preferably 1% PNZ 6%, more preferably 2% PNZ 6%, advantageously 3% PNZ 6%, by weight relative to the total weight of said adsorbent, and at least one of the dimensions is greater than or equal to 30 μm, preferably greater than or equal to 50 μm, more preferably greater than or equal to 80 μm, each of the measurements being carried out on the zeolite adsorbent in its form exchanged at sodium. According to one embodiment of the invention, the exchangeable cationic sites of the zeolitic adsorbent are occupied by sodium ions, and / or by any ion known to those skilled in the art and which can occupy a site. exchangeable cationic zeolite, and for example the ions of groups IA, IIA, IIIA, IIIB of the periodic table of the elements, the trivalent ions of the elements of the lanthanide series, the zinc ion (II), the copper ion (II), the chromium (III) ion, the iron (III) ion, the ammonium ion, the hydronium ion or mixtures of two or more of them, in all proportions. [0028] Group IA and especially sodium, potassium and lithium ions are preferred; but also Group IIA ions, and in particular magnesium, calcium, strontium and barium ions. Among the IIIA and IIB ions, aluminum, scandium, gallium, indium and yttrium ions are preferred, and among the trivalent ions of the lanthanide series, lanthanum, cerium, praseodymium and neodymium are preferred. According to a very particularly preferred aspect, the cationic exchangeable sites of the zeolite adsorbent are occupied by one or more of the ions selected from hydronium, lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, praseodymium, and lanthanum, more preferably from hydronium, lithium, sodium, potassium, cesium, calcium, barium, and mixtures of two or more of them in all proportions. According to another preferred embodiment, the zeolite adsorbent of the present invention further has, in its sodium-exchanged form, a bulk density of between 0.4 g.cm-3 and 1.0 g. cm-3, preferably between 0.5 g.cm-3 and 0.9 g.cm-3, inclusive. Bulk density is measured as described in DIN 8948 / 7.6. In the present invention, the term zeolitic adsorbent in its sodium-exchanged form, a zeolite adsorbent whose cationic sites are occupied mainly by sodium ions, that is to say that the exchange rate in Sodium ions are typically greater than 90%, preferably greater than 95%. The measurement of the exchange rate is explained further in the description. In the present invention, the adsorbents comprise at least one mesoporous zeolite, said mesoporous zeolite being advantageously chosen from mesoporous zeolites of structure LTA, EMT and FAU with an Si / Al atomic ratio of between 1 and 5, preferably from LTA and FAU structure with an Si / Al atomic ratio of between 1 and 1.4, inclusive, and preferably among the mesoporous zeolites of type X FAU structure, MSX and LSX. By zeolite MSX (Medium Silica X) is meant a zeolite of the FAU type having an Si / Al atomic ratio of between about 1.05 and about 1.15, inclusive. By zeolite LSX (Low Silica X) is meant a zeolite of FAU type having an atomic ratio Si / Al equal to about 1. According to a preferred embodiment, said at least one mesoporous zeolite present in the adsorbent according to The invention is in the form of crystals whose number-average diameter, measured by scanning electron microscope (SEM), is less than 20 μm, preferably between 0.1 μm and 20 μm, preferably between 0 μm. , 1 and 10 μm, preferably between 0.5 μm and 10 μm, more preferably between 0.5 μm and 5 μm, inclusive. In the present invention, the term "mesoporous zeolite" means a zeolite having an external surface, defined by the t-plot method described below, of between 40 m 2 g -1 and 400 m 2. 1, preferably between 40 m2.g-1 and 250 m2.g-1, more preferably between 40 m2.g-1 and 200 m2.g-1, limits included. By extension, in the sense of the present invention, a "non-mesoporous zeolite" is a zeolite possibly having an external surface, defined by the t-plot method described below, strictly less than 40 m 2 g -1. According to a preferred embodiment, the method according to the invention uses a zeolite adsorbent comprising mesoporous zeolite crystals chosen from zeolites LTA, EMT and FAU, and their mixtures of two or more of them in all proportions. Preferably, and preferably the method according to the invention uses a zeolite adsorbent comprising mesoporous crystals of zeolite FAU. The crystals of the mesoporous zeolite (s) included in the zeolite adsorbent of the invention, alone or as a mixture with other crystals of non-mesoporous zeolites. are agglomerated with a zeolitic binder and with up to 5% of additives. Said zeolitic binder is zeolitized so that the content of non-zeolitic phase (PNZ) in the adsorbent is such that 0 <PNZ 6%, preferably 1% PNZ 6%, more preferably 2% PNZ 6%, by weight relative to the total weight of said adsorbent, as indicated above. The zeolitic binder used for the preparation of the adsorbent according to the invention comprises, and preferably consists of, a zeolitizable clay alone or mixed with one or more other zeolitizable or non-zeolizable clays, preferably zeolizable. The 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, and preferably from zeolitizable clays including kaolins, kaolinites, nacrites, dickites, halloysites, illites and metakaolins, as well as mixtures of two or more of them in all proportions. In the present invention, it should be understood that the agglomeration binder undergoes at least one zeolitization step (transformation of the binder into zeolite), this zeolitization of said agglomeration binder not being total so that the The adsorbent of the invention comprises an amount of non-zeolitized (i.e. non-crystalline) zeolitic binder such that the non-zeolite phase (PNZ) content in the adsorbent is such that 0 <PNZ 6%, preferably 0.5% PNZ 6%, more preferably 1% PNZ 6%, more preferably 2% PNZ 6%, advantageously 3% PNZ 6%, by weight relative to the total weight of said adsorbent, as indicated previously. The non-zeolized agglomeration binder 25 makes it possible, inter alia, to ensure the cohesion of the zeolite crystals in the agglomerated zeolite adsorbent of the invention. This binder is further distinguished from zeolite crystals in that it does not exhibit a zeolite crystalline structure after calcination, which is why the non-zeolite binder (or residual binder) is often referred to as inert, and more precisely inert to adsorption and / or ion exchange. According to a particularly preferred aspect, the binder present in the agglomerated zeolite adsorbent of the invention consists solely of one or more clays, and preferably of a single clay, preferably a single zeolitizable clay. The zeolitic adsorbent 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. % inclusive, the percentages being expressed by weight relative to the total weight of said zeolite adsorbent. This or these other component (s) is (are) generally the residues of the additives, and other synthesis aids of said zeolite adsorbent, and in particular those which will be described later in the present description. Examples of such other components include the ashes of additives after calcination, silica, and others. In particular, among the additives optionally used during the production of the adsorbent of the process according to the invention, mention may be made of silica sources of any type known to those skilled in the art of zeolite synthesis, and for example colloidal silica, diatoms, perlites, fly ash, sand, or any other form of solid silica source. [0042] 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 binder or cohesive character to the agglomerated zeolite materials comprising at least one mesoporous zeolite of the invention. The adsorbent of the present invention may be in various forms such as those well known to those skilled in the art of adsorption, and for example and in a nonlimiting manner, the zeolite adsorbent of the invention. may be in the form of beads, yarns, extrudates, but also membranes, films and the like. The zeolitic adsorbent according to the present invention exhibits: a crush resistance in bed (REL) measured according to the ASTM 7084-04 standard of between 1.0 MPa and 3.5 MPa, preferably between 1, 2 MPa and 3.5 MPa, more preferably between 1.5 MPa and 3.0 MPa, for a medium volume diameter material (D50), or a length (larger dimension when the material is not spherical) , less than 1 mm, limit excluded, - a crush resistance, measured in accordance with ASTM D 4179 (2011) and ASTM D 6175 (2013), between 1.5 daN and 30 daN, preferably between 2 daN and 20 daN, for a material of average volume diameter (D50), or a length (greater dimension when the material is not spherical), greater than or equal to 1 mm, terminal included. According to another aspect, the subject of the present invention is also a process for the preparation of the zeolite adsorbent described above comprising at least the steps of mixing at least one mesoporous zeolite, optionally with one or more molecules. several additives, with at least one binder, in the proportions indicated above, and shaping of the agglomerated material, according to any method known to those skilled in the art, for example by extrusion, pelletization, atomization or other well known agglomeration techniques those skilled in the art and zeolitization of the agglomeration binder. According to a preferred embodiment, the method of the invention comprises at least the steps of: a) agglomeration of crystals of at least one mesoporous zeolite with a number average diameter of between 0.1 μm and 20 μm, preferably between 0.1 .mu.m and 20 .mu.m, preferably between 0.1 .mu.m and 10 .mu.m, more preferably between 0.5 .mu.m and 10 .mu.m and still more preferably between 0.5 .mu.m and 5 .mu.m. Atomic Si / Al of between 1 and 1.4, inclusive, and mesoporous outer surface defined by the t-plot method described below, between 40 m2.g-1 and 400 m2.g-1, of preferably between 40 m 2 g -1 and 250 m 2 g -1, more preferably between 40 m 2 g -1 and 200 m 2 g -1, inclusive, with at least one agglomeration binder, optionally one or several additives, as well as with the amount of water that allows the zeolite adsorbent to be shaped; b) drying the agglomerates at a temperature between 50 ° C and 150 ° C; c) calcining the agglomerates of step b) at a temperature above 150 ° C for a few hours; d) zeolitizing at least a portion of the binder binding binder by contacting the agglomerates obtained in step c) with an aqueous alkaline solution, optionally in the presence of at least one structuring agent; e) optional step of eliminating the structuring agent that may be present; F) 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 metal or alkaline earth metal salt; g) then washing and drying the agglomerates obtained in steps d) or e) under the conditions described in step b), and h) obtaining the zeolitic adsorbent by activation of the agglomerates obtained in step f) in the conditions described in step c). The crystals of the at least one mesoporous zeolite used in step a) can be obtained according to various methods known to those skilled in the art and for example according to the syntheses described in the patent application WO2007043731 or else by 35 A Inayat et al (Angew Chem Int.Ed., (2012), 51, 1962-1965). It is also possible to prepare said crystals by seeding synthesis and / or by adjusting the synthesis operating conditions such as the SiO 2 / Al 2 O 3 ratio, the sodium content and the alkalinity of the synthesis mixture or still according to conventional zeolite crystal post-treatment methods known to those skilled in the art. The post-treatment processes generally consist in eliminating atoms of the already formed zeolite network, either by one or more acid treatments which dealuminate the solid, treatment (s) followed by one or more washing (s) to sodium hydroxide (NaOH) in order to remove the aluminum residues formed, as described for example by D. Verboekend et al. (Adv Funct Mater., 22, (2012), pp. 916-928), or again by treatments which combine the action of an acid and that of a structuring agent which improve the efficiency of the acid treatment. , as described for example in the application WO2013 / 106816. The methods of direct synthesis of these zeolites (that is to say, synthetic processes other than post-treatment) are preferred and generally involve one or more structuring agents, also known as sacrificial templates. The sacrificial templates that may be used may be of any type known to those skilled in the art and in particular those described in application WO 2007/043731. According to a preferred embodiment, the sacrificial template is advantageously chosen from organosilanes and more preferably from organosilanes and more preferably from [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl chloride. ] hexadecyldimethylammonium, [3- (trimethoxysilyl) propyl] dodecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] octylammonium chloride, N- [3- (trimethoxysilyl) propyl] aniline, 3- [2- Aminoethylamino) ethylamino] propyltrimethoxysilane, N43- (trimethoxysilyl) propyl] -N '- (4-vinylbenzyl) ethylenediamine, triethoxy-3- (2-imidazolin-1-yl) propylsilane, 1- [3- ( trimethoxysilyl) propyl] urea, N- [3- (trimethoxysilyl) propyl] ethylenediamine, [3- (diethylamino) propyl] trimethoxysilane, (3-glycidyloxypropyl) trimethoxysilane, methacrylate of 3- (trimethoxysilyl) propyl, [ 2- (cyclohexenyl) ethyl] triethoxysilane, dodecyltri ethoxysilane, hexadecyltrimethoxysilane, (3-aminopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, and mixtures of two or more of them in all proportions. Of the sacrificial templates listed above, [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, or TPOAC, is particularly preferred. Sacrificial templates of higher molecular weight can also be used, for example PPDAs (Polymer Poly-DiallyldimethylAmmonium), PVB (PolyVinyl Butyral) and other oligomeric compounds known in the art for increasing the diameter of the mesopores. . According to a preferred embodiment of the process of the present invention, in step a), crystals of at least one mesoporous zeolite, as previously described, are prepared in the presence of a sacrificial template intended to be eliminated. This elimination can be carried out according to the methods known to those skilled in the art, for example by calcination, and in a non-limiting manner, the calcination of the zeolite crystals comprising the sacrificial jig can be carried out under an oxidizing gas sweep and / or or inert, in particular with gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, an 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. The nature of the gases, the ramps of temperature rise and the successive stages of temperatures, their durations will be adapted according to the nature of the sacrificial template. The additional step of eliminating the eventual sacrificial template can be performed at any time during the process for preparing the zeolitic adsorbent 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 else concomitantly with the drying and / or calcination of the adsorbent during steps b) and vs). However, it would not be outside the scope of the invention if the agglomeration of step a) included the agglomeration of several mesoporous zeolites obtained in different modes. The amount of said at least one agglomeration binder can vary in large proportions and is advantageously between 5% and 30%, preferably between 5% and 25%, more preferably between 10% and 20%, by weight of binder relative to the total weight of zeolite (s) and binder, expressed in anhydrous equivalent (weight corrected for loss on ignition). According to a very particularly preferred embodiment, the agglomeration binder comprises at least 80% of a clay or a mixture of zeolitizable clays, that is to say capable of being transformed into a zeolite structure in one or more zeolitization steps. It would not be departing from the scope of the invention if the at least one mesoporous zeolite used in step a) of agglomeration had previously undergone one or more cationic exchange (s). In this case, it is possible to dispense with the ion exchange step f), although this is not preferred. The zeolitization step d) is conducted so that the PNZ value, measured by XRD as indicated below, is as defined above. The agglomerates (step b) can be dried by any method known to those skilled in the art, and advantageously in a drying oven according to methods well known in the prior art and advantageously under gaseous scanning. oxidizing and / or inert, including gases such as oxygen, nitrogen, air, dry air and / or decarbonated, oxygen-depleted air, optionally dry and / or decarbonated, at a temperature greater than 50 ° C, typically between 50 ° C and 150 ° C, preferably between 60 ° C and 80 ° C for a few hours. Stage c) of calcination of the agglomerates is also carried out according to methods well known in the prior art, and advantageously under gaseous, oxidizing and / or inert gas scavenging, with, in particular, gases such as oxygen, carbon dioxide and the like. nitrogen, air, a dry air and / or decarbonated oxygen depleted air, 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. Similarly, the zeolitization step d) is a step now well known to those skilled in the art which can be carried out according to any method described in the prior art, the aqueous alkaline solution used being an aqueous solution. lithium hydroxide, potassium hydroxide, sodium hydroxide, or an aqueous solution of lithium, potassium, sodium salts, in particular halides, advantageously chlorides, the use of sodium hydroxide being very particularly preferred. In general, the concentration of the alkaline zeolitization solution is between 0.5 M and 5 M. The zeolitization is preferably carried out hot, at a temperature above ambient temperature, for example between the ambient temperature (about 20 ° C.) and the boiling temperature of the alkaline solution of zeolitization, and for example at temperatures of the order of 80 ° C. to 100 ° C. The duration of the zeolitization process is generally from a few tens of minutes to a few hours, usually from about 1 hour to 8 hours. According to one embodiment of the process of the present invention, the step d) of zeolization of at least a part of the agglomeration binder can be carried out in the presence of at least one structuring agent or sacrificial template intended to be eliminated according to the methods known to those skilled in the art, for example by calcination, the presence of the structuring agent having the purpose of creating a certain mesoporosity in the agglomerate of the invention thus obtaining an agglomerate zeolitic mesoporous. The amount of structuring agent can vary in large proportions according to the desired degree of mesoporosity, and is advantageously between 0.1% and 50%, preferably between 0.1% and 33%, more preferably between 1% and 30%, advantageously between 5% and 30%, by weight relative to the weight of clay (s). The nature of the structuring agent or sacrificial template may be any type known to those skilled in the art and as described above for the synthesis of mesoporous zeolite. The optional step e) of removing the structuring agent optionally introduced during the zeolitization step d) and aimed at converting a part of the agglomeration binder into a mesoporous zeolite can be carried out by any means. known to those skilled in the art and in particular by heat treatment, generally at a temperature above 150 ° C, typically between 180 ° C and 650 ° C, preferably between 200 ° C and 600 ° C. In this case, the activation step h) carried out at high temperature also makes it possible to eliminate the structuring agent, thus making it possible advantageously not to carry out step e) of eliminating said structuring agent which will in fact be eliminated during activation in step h). Activation step h) is a necessary step to release both the microporosity (elimination of water) and the mesoporosity (elimination of the structuring agent, if it has not been eliminated. during the optional step e)). This activation step may be carried out according to any calcination method known to those skilled in the art and, for example, and without limitation and, as described for step c) under oxidizing and / or inert gas scavenging, with in particular gases such as oxygen, nitrogen, air, dry air and / or decarbonated, oxygen depleted air, optionally dry and / or decarbonated, at a temperature or temperatures above 150 ° C, typically between 180 ° C and 650 ° C, preferably between 200 ° C and 600 ° C, for a few hours, for example between 2 and 6 hours. The nature of the gases, the ramps of temperature rise and the successive stages of temperatures, their durations will be adapted according to the nature of the sacrificial template. The size of the mesoporous zeolite crystals used in step a) and the crystals in the zeolite adsorbents of the invention are advantageously measured by observation under a scanning electron microscope (SEM) which also makes it possible to confirm the presence of a non-zeolite phase comprising, for example, residual binder 5 (not converted during the zeolitization step) or any other amorphous phase in the adsorbents. In the description of the present invention, the term "number average diameter" or "size" is used for zeolite crystals. The method of measuring these quantities is explained later in the description. The agglomeration and the 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 a granulating plate, granulator drum, atomization and other. The proportions of agglomeration binder and zeolites used are typically those of the prior art, that is to say between 5 parts and 30 parts by weight of binder for 95 parts to 70 parts by weight of zeolite . The agglomerates from step 15 a), whether in the form of beads, extrudates or the like, generally have a volume diameter in 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. In step a), in addition to the zeolite crystal (s) and the binder, 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. Mention may be made preferably but not exhaustively of methylcelluloses and their derivatives, lignosulfonates, polycarboxylic acids and carboxylic acid copolymer acids, their amino derivatives and their salts, in particular the alkaline salts and the ammonium salts. The additives are introduced at from 0 to 5%, preferably from 0.1% to 2%. The additives also comprise 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, specialized in the synthesis of zeolites, for example colloidal silica, diatoms, perlites, fly ash in the English language, sand, or any other form of solid silica. According to one embodiment, step a) of the process of the present invention is carried out in the presence of at least one additive which is a silica source chosen from colloidal silica, diatoms, perlites, ashes. calcination, sand, or any other form of solid silica. During the calcination (step c) and step h)), the nature of the gases, the ramps of temperature rise and the successive stages of temperatures, as well as their respective durations, will be adapted according to the nature of the optional structuring agent to be removed and depending on the nature of the binder and any additives used in the synthesis process of the agglomerates of the invention. The zeolitic adsorbent thus obtained presents, quite unexpectedly, optimum properties, combining at the same time: a high degree of crystallinity, characterized by its microporous volume and consequently an optimum capacity, a transfer kinetics optimal, characterized by its mesoporous volume, and optimal mechanical properties for use in adsorption processes and ionic exchange processes in dynamic or static. The mesoporosity of the zeolite adsorbent according to the invention can be visualized by easily identifiable mesopores, for example by observation by means of a transmission electron microscope (TEM or "TEM" in English), as described by US Pat. example in US7785563. The agglomerated zeolite materials according to the present invention possess both the characteristics of the mesoporous zeolites, but also in particular the mechanical properties of the conventional zeolite agglomerates known from the prior art, that is to say, where the zeolite is not -mésoporeuse. [0079] More particularly, the agglomerated zeolite materials of the invention show that it is possible to maintain the crystallinity and the mesoporosity of the zeolite within a zeolite adsorbent, and to obtain a non-degraded agglomerated zeolite adsorbent and mechanically resistant. In addition, the method for preparing the zeolite agglomerated zeolite (s) mesoporous (s) according to the invention is a method of easy implementation, fast and economic and therefore easy to industrialize with a minimum of synthesis steps. Thus, according to yet another aspect, the present invention relates to the use of at least one zeolite adsorbent such as has just been defined or capable of being obtained according to the process described above, in all fields. where zeolites are commonly used and in particular for gas phase or liquid phase separations, and particularly in gas or liquid flow separation processes, pressure swing adsorption processes. in the gas phase, temperature or gas phase modulated adsorption processes, fixed bed adsorption processes without regeneration, simulated moving bed separation methods. The following examples illustrate the object of the invention, and are provided for information only, without however being intended in any way to limit the various embodiments of the present invention. In the following examples, the physical properties of the agglomerates are / o evaluated by methods known to those skilled in the art, the main of which are recalled below. Loss on ignition of zeolitic adsorbents: The loss on ignition is determined in an oxidizing atmosphere by calcining the sample in air at a temperature of 950 ° C. ± 25 ° C., as described in standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%. Measurement of the purity of the crystalline (zeolitic) phases - Qualitative and quantitative analysis by X-ray diffraction: The purity of the zeolitic phases in the adsorbents of the invention is evaluated by X-ray diffraction analysis, known from FIG. skilled in the art under the acronym zo DRX. This identification is carried out on a DRX device of the brand Bruker. This analysis makes it possible to identify the crystalline phases present in the solid analyzed because each of the zeolite structures has a diffraction spectrum (or diffractogram) unique defined by the positioning of the diffraction peaks and their relative intensities. The agglomerated zeolite adsorbents are ground and then spread and smoothed on a sample holder by simple mechanical compression. The acquisition conditions of the diffraction spectrum (or diffractogram) produced on the Brucker D5000 device are the following: Cu tube used at 40 kV-30 mA; - size of the slots (diverging, diffusion and analysis) = 0.6 mm; - filter: Ni; - rotating sample device: 15 rpm; - measuring range: 3 ° <20 <50 °; - not: 0.02 °; - counting time in steps: 2 seconds. The interpretation of the diffraction spectrum (or diffractogram) obtained is carried out with the EVA software with identification of the phases using the ICCD PDF-2 release 2011 database. Mass quantity of the zeolite fractions of the Zeolite adsorbents The mass quantity of the zeolite fractions is measured by X-ray diffraction analysis, known to those skilled in the art under the acronym XRD. This analysis is carried out on a Bruker apparatus, then the quantity of the zeolite fractions is evaluated from the peak intensities of the diffractograms by taking as reference the peak intensities of a suitable reference (zeolite of the same chemical nature assumed 100 crystalline% under cationic treatment conditions identical to those of the adsorbent under consideration). The peaks, making it possible to go back to the crystallinity, are the most intense peaks of the angular zone of between 9 ° and 37 °, for example for the FAU zeolite the peaks observed in the angular ranges of between 11 ° and 13, respectively. °, between 22 ° and 26 ° and between 31 ° and 33 °. The strongest peaks of angular region 20 are available for each zeolite family in "Collection of Simulated XRD Powder Patterns for Zeolites", Editors: M.M.J. Treacy and J. B. Higgins, 4th revised edition, ELSEVIER, (2001). Non zeolite phase (PNZ) of zeolitic adsorbents: [0089] The non-zeolitic phase rate PNZ, for example the level of residual agglomeration binder (ie non-zeolite) and any other possible amorphous phase is calculated according to the equation next: PNZ = 100 - E (PZ), where PZ represents the sum of the amounts of the zeolite fractions within the meaning of the invention.
    [0002] Measurement of Microporous Volume and Mesoporous Volume Measurement of microporous volume is estimated by conventional methods such as measurements of Dubinin-Raduskevitch volumes (adsorption of 77 K liquid nitrogen or 87% liquid argon). K). The Dubinin-Raduskevitch volume is determined from the measurement of the gas adsorption isotherm, such as nitrogen or argon, at its liquefaction temperature, depending on the opening of pores of the zeolite structure: argon for LTA and nitrogen for FAU. Prior to adsorption, the zeolite adsorbent is degassed at 300 ° C. to 450 ° C. for a period of between 9 hours and 16 hours under vacuum (P <6.7 × 10 -4 Pa). Measurement of the adsorption isotherms is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 35 measurement points at relative pressures of P / PO of 0.002 to 1. The volume microporous is determined according to Dubinin and Raduskevich from the obtained isotherm, applying the standard ISO 15901-3 (2007). The microporous volume evaluated according to the Dubinin and Raduskevitch equation is expressed in cm 3 of liquid adsorbate per gram of adsorbent. The measurement uncertainty is ± 0.003 cm3.g-1. The mesoporous volume is determined by the Barrett-Joyner-Halenda method (BJH method, EP Barrett, LG Joyner, PP Halenda, "The Determination of Pore Volume and Area Distributions in Porous Substances." Computations form Nitrogen lsotherms ", J. Am Chem Soc., 73 (1), (1951), 373-380), from the adsorption branch / o of the 77 K nitrogen physisorption isotherm. Measurement of the mesoporous external surface (m2 / g) by the so-called t-plot method: The so-called t-plot calculation method exploits the data of the adsorption isotherm Q ads = f (P / PO) ) and calculates the microporous surface. The outer surface can be deduced by differentiating with the BET surface which calculates the total porous area in m 2 / g (S BET = Microporous surface + Mesoporous outer surface). To calculate the microporous surface by the t-plot method, the curve Q ads (cm3.g-1) is plotted as a function of t = thickness of the layer depending on the partial pressure P / PO which would be formed on a non-porous reference solid (t zo log function (P / PO): Harkins equation and applied Jura: [13,991 (0,034-log (P / PO)) "0,5] In the interval t between 0 At 35 nm and 0.5 nm, a line can be drawn which defines an adsorbed Y intercept which allows the microporous surface to be calculated.If the solid is not microporous the straight line passes through O. Observation of the structure Mesoporous by Transmission Electron Microscopy [0095] After grinding the adsorbents in the mortar, the powder obtained is dispersed in ethanol for 1 minute under ultrasound.A drop of the solution is deposited on a microscopy grid. sample at room temperature [0096] The observation is made with a transmission electron microscope (CM 200 from FEI) under a voltage of 120 kV.
    [0003] Crystallometry of the Crystals: 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). In order to estimate the size of the zeolite crystals on the samples, a set of photographs 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%.
    [0004] Bed Crush Resistance: [0099] The crush strength of a bed of the zeolite adsorbents of the present invention is characterized by the Shell method SMS1471-74 series (Shell Method Series SMS1471-74 "Determination of Bulk Crushing Strength of Catalysts, Compression-Sieve Method ") associated with the" BCS Tester "apparatus marketed by the company Vinci Technologies. This method, initially intended for the characterization of catalysts with a size of between 3 mm and 6 mm, is based on the use of a 425 μm sieve which will make it possible in particular to separate the fines created during the crushing. The use of a 425 μm sieve remains suitable for particles of diameter greater than or equal to 1 mm but must be adapted according to the particle size of the agglomerates that are to be characterized. Resistance to crushing in grains: The mechanical resistance to crushing in grains is determined with a device "Grain Crushing strength" marketed by Vinci Technologies, according to the standards ASTM D 4179 and D 6175.
    [0005] Chemical analysis of zeolitic adsorbents - Si / Al ratio and exchange rate: [0101] A basic chemical analysis of the final product obtained after steps a) to f) described above can be carried out according to various known analytical techniques. of the skilled person. Among these techniques, mention may be made of the technique of chemical analysis by X-ray fluorescence as described in standard NF EN 25 ISO 12677: 2011 on a wavelength dispersive spectrometer (VVDXRF), for example Tiger S8 from the Bruker company. We can also mention the method by ICP. X-ray fluorescence is a non-destructive spectral technique exploiting the photoluminescence of atoms in the X-ray domain, to establish the elemental composition of a sample. The excitation of the atoms generally by an X-ray beam or by electron bombardment generates specific radiations after return to the ground state of the atom. The X-ray fluorescence spectrum has the advantage of relying very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide. Other methods of analysis are for example illustrated by the methods of atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) described in US Pat. standards NF EN ISO 21587-3 or NF EN ISO 21079-3 on a device of the type for example Perkin Elmer 5 4300DV. The X-ray fluorescence spectrum has the advantage of depending very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. After calibration for each oxide SiO 2 and Al 2 O 3 as well as the various oxides (such as those obtained from exchangeable cations, for example sodium), a measurement uncertainty of less than 0.4% by weight is obtained in conventional manner. The ICP-AES method is particularly suitable for measuring the lithium content used to calculate the lithium oxide content. Thus, the elementary chemical analyzes described above make it possible both to verify the Si / Al atomic ratio of the zeolite used within the agglomerate and the Si / Al atomic ratio of the final product obtained at the same time. from steps a) to h) described above, and to check the quality of the optional cation exchange described in step f) but also allows to check the sodium content of the adsorbent in its sodium exchanged form. In the description of the present invention, the measurement uncertainty of the Si / Al atomic ratio is ± 5%. The quality of the ion exchange is related to the number of moles of the cation under consideration in the zeolite agglomerate after exchange. More precisely, the exchange rate by a given cation is estimated by evaluating the ratio between the number of moles of said cation and the number of moles of all the exchangeable cations. The respective amounts of each of the cations are evaluated by chemical analysis of the corresponding cations. For example, the sodium ion exchange rate is estimated by evaluating the ratio of the total Na + cation number to the total number of exchangeable cations (eg Ca 2+, K +, Li +, Ba 2+, Cs +, Na +, etc.). the amount of each of the cations being evaluated by chemical analysis of the corresponding oxides (Na2O, CaO, K2O, BaO, Li2O, 0520, etc.). This calculation method also accounts for any oxides present in the residual binder of the adsorbent. However, the amount of such oxides is considered to be minor compared to the oxides originating from the cations of the exchangeable sites of the zeolite or zeolites of the adsorbent according to the invention. Apparent density [0107] Apparent density is measured as described in DIN 8948 / 7.6. EXAMPLE 1 Synthesis of Type X Mesoporous Zeolite with Addition of Nucleation Gel and Growth Gel with TPOAC / Al 2 O 3 Ratio = 0.04 a) Preparation of the Growth Gel in a Mixed Reactor with Archimedean Screw at 300 rev / min. In a stainless steel reactor equipped with a heating mantle, a temperature probe and a stirrer, a growth gel is prepared by mixing an aluminate solution containing 119 g of sodium hydroxide ( NaOH), 128 g of alumina trihydrate (Al 2 O 3, 3H 2 O, containing 65.2% by weight of Al 2 O 3) and 195.5 g of water at 25 ° C. in 25 minutes with a stirring speed of 300 rpm. 1 in a silicate solution containing 565.3 g of sodium silicate, 55.3 g of NaOH and 1997.5 g of water at 25 ° C. The stoichiometry of the growth gel is as follows: 3.48 Na 2 O / Al 2 O 3 / 3.07 SiO 2/180 H 2 O. Homogenization of the growth gel is carried out with stirring at 300 rpm for 25 minutes at 25 ° C. b) Addition of nucleation gel [0110] 61.2 g of nucleation gel (ie 2% by weight) of composition 12 were added to the growth gel at 25 ° C. with stirring at 300 rpm. Na 2 O / Al 2 O 3/10 SiO 2/180 H 2 O prepared in the same manner as the growth gel, and matured for 1 hour at 40 ° C. After 5 minutes of homogenization at 300 rpm, the stirring speed is decreased to 100 rpm and continued for 30 minutes. C) Introduction into the reaction medium of the structuring agent [0111] 27.3 g of 60% TPOAC solution in methanol (MeOH) are introduced into the reaction medium with a stirring speed of 300 rpm. -1 (TPOAC / A1203 molar ratio = 0.04). A maturation step is carried out at 25 ° C. for 1 hour at 300 rpm, before starting the crystallization. D) Crystallization The stirring rate 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. minutes. After standing for 22 hours at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. E) Filtration / Washing The solids are recovered on sintered material and then washed with deionized water to neutral pH. f) Drying / Calcination [0114] In order to characterize the product, 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. C, then 1 hour of plateau at 200 ° C., then 3 hours of temperature rise at 550 ° C., and finally 1.5 hours of plateau at 550 ° C. There is thus obtained 255 g of anhydrous equivalent solid of XPH zeolite; which represents a yield of 99 mol% relative to the amount of aluminum involved. The Si / Al ratio of the X-ray fluorescence X-mesoporous zeolite (XPH) is 1.24. The characteristics of this XPH prepared in this example 1 are grouped together in the following Table 1: Table 1 - XPH characteristics (Example 1) Synthesis molar ratio TPOAC / Al 2 O 3 0.04 synthesis time (h) 24 Isotherm Microporous volume according to 0.335 adsorption Dubinin-Raduskevitch (cm3.g-1) nitrogen at 77 K Mesoporous outer surface (m2 / g) 105 Mesopore size (nm) 5 to 10 XRD spectrum X crystalline phase pure (diffractogram) X crystallinity (%) 100 MEB crystal size (μm) 1 to 3 [0117] The mesopore size distribution is calculated by the Density Functional Theory (DFT) method with the Cylindrical Pore model. The percent crystallinity is calculated using the TOPAS software using the ICDD PDF-2 base, 2011. Example 2: Preparation of mesoporous zeolite X agglomerates, in the presence of zeolitic binder In the following the masses given are expressed in anhydrous equivalents. A homogeneous mixture consisting of 1600 g crystals of zeolite X zo mesoporous obtained in Example 1, 350 g of kaolin, 130 g of colloidal silica sold under the trade name Klebosol® 30 (containing 30 g % by weight of SiO2 and 0.5% of Na2O) as well as the amount of water which allows the extrusion of the mixture. The fire loss of the pulp before extrusion is 44%. Extrudates of 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 crush strength on the mesoporous X-zeolite X extrudates is 2.6 daN. Their apparent density is 0.64 g.cm-3. The volume of Dubinin-Raduskevich measured from the nitrogen isotherm is 0.269 cm3g-1. The non-zeolite phase content evaluated by XRD is 20% by weight relative to the total weight of the adsorbent. The external surface area measured from the nitrogen adsorption isotherm is 110 m 2 g -1 and the mesoporous volume is 0.18 cm 3 g -1. Example 3 Preparation of Zeolite Adsorbents According to the Invention The extrudates of Example 2 are subjected to a zeolitization treatment. To this end, 200 g of these extrudates are placed in a glass reactor equipped with a controlled double jacket at a temperature of 100 ° C. ± 1 ° C., then 1.5 L of a solution is added. aqueous sodium hydroxide of concentration 1 M and the reaction medium is left stirring for a period of 3 hours. The extrudates are then washed in 3 successive operations of washing with water followed by the emptying of the reactor. The effectiveness of the washing is ensured by measuring the final pH of the wash water, which must be between 10.0 and 10.5. The mechanical resistance to crushing grain extrusions according to the invention is 3.0 daN. Their apparent density is 0.65 g.cm-3. The volume of Dubinin-Raduskevich measured from the nitrogen isotherm is 0.322 cm3g-1. The XRD analysis shows no phase other than the faujasite phase after zeolitization. The non-zeolite phase content evaluated by XRD is 4% by weight relative to the total weight of the adsorbent according to the invention. The external surface area measured from the nitrogen adsorption isotherm is 50 m 2 g -1 and the mesoporous volume is 0.07 cm 3 g -1. It is thus observed that the zeolite material agglomerated according to the invention comprising a mesoporous zeolite X has mechanical and microporous volume characteristics greater than those obtained for non-zeolite adsorbents (see Comparative Example 2, in which the binder has not undergone any zeolitization). It is thus quite remarkable to note that 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 known zeolite agglomerates up to now. It is thus possible to envisage without problem the use of the agglomerated zeolite materials of the invention in all fields of industrial applications such as catalysis, separation, adsorption, and others.
    权利要求:
    Claims (14)
    [0001]
    REVENDICATIONS1. Zeolitic adsorbent having the following characteristics: the external surface, measured by nitrogen adsorption, is between 20 m 2 g -1, and 70 m 2 g -1, preferably between 20 m 2 g -1 and 60 m 2. g-1, more preferably between 30 m2.g-1 and 60 m2.g-1, more preferably between 40 m2.g-1, and 60 m2.g-1, limits included, the mesoporous volume (Vmeso) measured by nitrogen adsorption, is such that 0 <Vmeso <0.20 cm3g-1, preferably 0 <Vmeso <0.10 cm3g-1, / o - the non-zeolitic phase content (PNZ) is such that 0 <PNZ 6%, preferably 0.5% PNZ 6%, more preferably 1% PNZ 6%, more preferably 2% PNZ 6%, preferably 3% PNZ 6%, by weight based on weight total of said adsorbent, and - at least one of the dimensions is greater than or equal to 30 μm, preferably greater than or equal to 50 μm, more preferably greater than or equal to 80 μm, each of the measurements being carried out on the zeolite adsorbent in its form exchanged with sodium.
    [0002]
    Zeolitic adsorbent according to claim 1, the exchangeable cationic sites of which are occupied by the ions of groups IA, IIA, IIIA, IIIB of the periodic table of the elements, the trivalent ions of the elements of the lanthanide series, and the zinc ion. (II), copper (II) ion, chromium (III) ion, iron (III) ion, ammonium ion, hydronium ion or mixtures of two or more all proportions.
    [0003]
    A zeolitic adsorbent according to claim 1 or claim 2, wherein the exchangeable cationic sites are occupied by one or more of the ions selected from hydronium, lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, praseodymium, and lanthanum, more preferably from hydronium, lithium, sodium, potassium, cesium, calcium, barium, and mixtures of two or more of them in all proportions. 30
    [0004]
    A zeolitic adsorbent according to any one of the preceding claims having, in its sodium-exchanged form, a bulk density of between 0.4 gcm-3 and 1.0 gcm-3, preferably between 0. , 5 g.cm-3 and 0.9 g.cm-3 inclusive, said bulk density being measured as described in DIN 8948 / 7.6. 3028429 - 25 -
    [0005]
    5. Zeolitic adsorbent according to any one of the preceding claims, comprising at least one mesoporous zeolite chosen from mesoporous zeolites of structure LTA, EMT and FAU with an Si / Al atomic ratio of between 15 and 5, preferably of structure LTA and FAU. Si / Al atomic ratio between 1 and 1.4 inclusive, and preferably among the mesoporous zeolites of structure FAU type X, MSX and LSX.
    [0006]
    The zeolite adsorbent according to claim 5, wherein said at least one mesoporous zeolite is in the form of crystals whose number-average diameter, measured by scanning electron microscope (SEM), is less than 20 μm, preferably between 0.1 μm and 20 μm, preferably between 0.1 and 10 μm, preferably between 0.5 μm and 10 μm, more preferably between 0.5 μm and 5 μm, inclusive.
    [0007]
    A zeolitic adsorbent according to any one of the preceding claims, wherein the crystals of the zeolite (s) are agglomerated with a binder comprising, and preferably consisting of, a zeolitic clay alone or in admixture with a or several other zeolitizable or non-zeolitizable clays, preferably zo-zeolizable.
    [0008]
    A zeolitic adsorbent according to any one of the preceding claims, wherein the crystals of the zeolite (s) are agglomerated with a binder comprising, and preferably consisting of, a clay selected from kaolin, kaolinites , nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in all proportions, and preferably among kaolins, kaolinites, nacrites, dickites, halloysites, illites and metakaolins, as well as mixtures of two or more of them in all proportions. 30
    [0009]
    A zeolitic adsorbent according to any one of the preceding claims, having: - bed crush strength (REL) measured according to ASTM 7084-04 of between 1.0 MPa and 3.5 MPa, preferably between 1.2 MPa and 3.5 MPa, more preferably between 1.5 MPa and 3.0 MPa, for a medium volume diameter material (D50), or a length (larger dimension when the material is not spherical), less than 1 mm, limit excluded, - a crush resistance in grain, measured in accordance with ASTM D 4179 (2011) and ASTM D 6175 (2013), between 1, 5 daN and 30 daN, preferably between 5 2 daN and 20 daN, for a material of average volume diameter (D50), or a length (greater dimension when the material is not spherical), higher (e) or equal to 1 mm, terminal included.
    [0010]
    10. Process for the preparation of a zeolite adsorbent according to any one of claims 1 to 9, comprising at least the steps of: a) agglomeration of crystals of at least one mesoporous zeolite with a mean diameter in number between 0 , 1 μm and 20 μm, preferably between 0.1 μm and 20 μm, preferably between 0.1 μm and 10 μm, more preferably between 0.5 μm and 10 μm and even more preferably between 0.5 μm and 10 μm. and 5 μm, with an Si / Al atomic ratio of between 1 and 1.4 inclusive, and with a mesoporous outer surface, defined by the t-plot method, of between 40 m 2 g -1 and 400 m 2 g. -1, preferably between 40 m2.get 250 m2.g-1, more preferably between 40 m2.g-1 and 200 m2.g-1, limits included, with at least one agglomeration binder, optionally one or several additives, as well as with the amount of water that allows the zeolite adsorbent to be shaped; b) drying the agglomerates at a temperature between 50 ° C and 150 ° C; c) calcination of the agglomerates of step b) at a temperature above 150 ° C for a few hours; d) zeolitizing at least a portion of the binder binding binder by contacting the agglomerates obtained in step c) with an aqueous alkaline solution, optionally in the presence of at least one structuring agent; e) optional step of eliminating the structuring agent that may be present; f) optionally cationic exchange (s) agglomerates of step c) or step d) by contacting with a solution of at least one salt of alkali metal or alkaline earth metal; g) then washing and drying the agglomerates obtained in steps d) or e) under the conditions described in step b), and h) obtaining the zeolitic adsorbent by activation of the agglomerates obtained in step f) under the conditions described in step c). 3028429 - 27 -
    [0011]
    11. The method of claim 10, wherein the step d) of zeolitization of at least a portion of the agglomeration binder is carried out in the presence of at least one structuring agent. 5
    [0012]
    The process according to claim 11, wherein the structuring agent is [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride.
    [0013]
    13. Process according to any one of claims 10 to 12, in which step a) is carried out in the presence of at least one additive which is a silica source chosen from colloidal silica, diatoms, perlites, calcination ashes. , sand, or any other form of solid silica.
    [0014]
    14. Use of at least one zeolite adsorbent according to any one of claims 1 to 9 or obtainable by the process of any one of claims 10 to 13, for gas phase separations operations. or in the liquid phase, and most particularly in the processes for separating gaseous or liquid streams, gas phase pressure swing adsorption processes, temperature or gas phase modulated adsorption processes, adsorption processes. in a fixed bed without regeneration, the simulated moving bed separation methods.
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    PL3218102T3|2021-06-28|
    CN107073439A|2017-08-18|
    US20180214848A1|2018-08-02|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1460916A|FR3028429B1|2014-11-13|2014-11-13|ZEOLITHIC ADSORBENT BASED ON MESOPOROUS ZEOLITE|FR1460916A| FR3028429B1|2014-11-13|2014-11-13|ZEOLITHIC ADSORBENT BASED ON MESOPOROUS ZEOLITE|
    US15/506,049| US10532342B2|2014-11-13|2015-11-05|Zeolite adsorbent based on mesoporous zeolite|
    PT158055772T| PT3218102T|2014-11-13|2015-11-05|Zeolite adsorbent made from a mesoporous zeolite|
    EP15805577.2A| EP3218102B1|2014-11-13|2015-11-05|Zeolite adsorbent made from a mesoporous zeolite|
    KR1020177005320A| KR101954546B1|2014-11-13|2015-11-05|Zeolite adsorbent made from a mesoporous zeolite|
    PCT/FR2015/052990| WO2016075393A1|2014-11-13|2015-11-05|Zeolite adsorbent made from a mesoporous zeolite|
    PL15805577T| PL3218102T3|2014-11-13|2015-11-05|Zeolite adsorbent made from a mesoporous zeolite|
    ES15805577T| ES2856833T3|2014-11-13|2015-11-05|Zeolitic adsorbent based on mesoporous zeolite|
    JP2017510479A| JP6483242B2|2014-11-13|2015-11-05|Zeolite adsorbent based on mesoporous zeolite|
    CN201580045336.2A| CN107073439B|2014-11-13|2015-11-05|Zeolite adsorbents based on mesoporous zeolites|
    TW104137403A| TWI583444B|2014-11-13|2015-11-12|Zeolite adsorbent based on mesoporous zeolite|
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