ZEOLITHIC ADSORBENTS BASED ON LOW BLEED ZEOLITHEX X WITH LOW EXTERNAL SURFACE, PREPARATION METHOD AN

专利摘要:
The invention relates to an adsorbent comprising a zeolite phase and a non-zeolitic phase, said adsorbent having: an external surface area of less than or equal to 30 m 2 g -1, preferably less than or equal to 20 m 2 g -1, zeolite phase comprising at least one X-type FAU structure zeolite, and a pore diameter distribution, determined by mercury intrusion according to ASTM D4284-83 and expressed by the volume distribution dV / dlogDHg, where DHg is the apparent diameter of the pores, and V, the pore volume, whose mode is between 100 nm and 250 nm, limits included. The invention also relates to a process for the preparation of said adsorbent and their uses, in particular for the separation of xylene isomers.
公开号:FR3028431A1
申请号:FR1460955
申请日:2014-11-13
公开日:2016-05-20
发明作者:Ludivine Bouvier；Cecile Lutz；Catherine Laroche
申请人:IFP Energies Nouvelles IFPEN；Carbonisation et Charbons Actifs CECA SA；
IPC主号:

专利说明:

[0001] The present invention relates to zeolitic adsorbents in the form of low binder agglomerates comprising zeolite. The present invention relates to zeolite adsorbents in the form of low binder agglomerates comprising zeolite. DESCRIPTION OF THE INVENTION faujasite for their uses in applications where the transfer of material is an important parameter, said adsorbents having a small external surface, typically less than or equal to 30 m2.g-1, preferably less than or equal to 20 m2.g-1. The present invention also relates to a process for preparing said zeolite adsorbents, and their uses, in particular for the separation of gaseous or liquid mixtures of isomers, more particularly xylenes and especially for the production of very pure paraxylene from an aromatic hydrocarbon feed containing isomers containing 8 carbon atoms. The use of zeolitic adsorbents comprising at least zeolite Faujasite (FAU) type X or Y and comprising, in addition to sodium cations, barium, potassium or strontium ions, alone or in mixtures, for selectively adsorbing the paraxylene in a mixture of aromatic hydrocarbons is well known in the art. US Pat. Nos. 3,558,730, 3,558,732, 3,626,020 and 3,663,638 show that zeolitic adsorbents comprising aluminosilicates based on sodium and barium (US Pat. No. 3,960,774) or on sodium-based aluminosilicates. , barium and potassium, are effective for the separation of paraxylene present in aromatic C8 cuts (cuts comprising aromatic hydrocarbons with 8 carbon atoms). In the patents listed above, the zeolitic adsorbents are in the form of crystals in the form of powder or in the form of agglomerates consisting mainly of zeolite powder and up to 20% by weight of inert binder. The synthesis of FAU zeolites is usually carried out by nucleation and crystallization of silico-aluminate gels. This synthesis leads to crystals (generally in the form of powder) whose use on an industrial scale is particularly difficult (significant losses of loads during handling). The agglomerated forms of these crystals in the form of grains, yarns and other agglomerates are then preferred, these forms being obtainable by extrusion, pelletization, atomization and other agglomeration techniques known to those skilled in the art. These agglomerates do not have the disadvantages inherent to the pulverulent materials. The agglomerates, whether in the form of platelets, beads, extrudates, and the like, generally consist of crystals of zeolite (s), which constitute the active element (within the meaning of the present invention). adsorption) and an agglomeration binder. This agglomeration binder is intended to ensure the cohesion of the crystals with one another in the agglomerated structure, but it must also make it possible to ensure sufficient mechanical strength for said agglomerates in order to avoid, or at least to minimize as much as possible, the risks of fractures, breakage or breakage that could occur during their industrial uses during which the agglomerates are subjected to numerous constraints, such as vibrations, strong and / or frequent variations of pressures, movements and others. [0008] The preparation of these agglomerates is carried out, for example, by pasting zeolite crystals in powder form with a clay paste, in proportions of the order of 80% to 90% by weight of zeolite powder. for 20% to 10% by weight of binder, then shaped into balls, platelets or extrudates, and high temperature heat treatment for clay baking and reactivation of the zeolite, the cationic exchange (s) (s) ( s), such as, for example, the barium and possibly potassium exchange which can be carried out before and / or after the agglomeration of the powdery zeolite with the binder. [0009] Zeolitic bodies whose particle size is a few millimeters or even of the order of a millimeter are obtained, and which, if the choice of the agglomeration binder and the granulation are made according to the rules of the art, present a set of satisfactory properties, in particular porosity, mechanical strength, abrasion resistance. However, the adsorption properties of these agglomerates are obviously reduced relative to the starting active powder due to the presence of agglomeration binder inert with respect to the adsorption. Various means have already been proposed to overcome this disadvantage of the agglomeration binder to be inert with regard to the adsorption performance, among which is the conversion of all or at least part of the agglomeration binder. in active zeolite from the point of view of adsorption. This operation is now well known to those skilled in the art, for example under the name of "zeolitization". To carry out this operation easily, zeolitizable binders are used, most often belonging to the family of kaolinite, and preferably previously calcined at temperatures generally between 500 ° C. and 700 ° C. [0011] Patent FR 2 789 914 describes a process for the production of zeolite X agglomerates with an Si / Al atomic ratio of between 1.15 and 1.5, exchanged with barium and optionally with potassium, by agglomerating crystals. zeolite X with a binder, a source of silica and carboxymethylcellulose, and then zeolizing the binder by immersion of the agglomerate in an alkaline liquor. After exchanging zeolite cations with barium (and optionally potassium) ions and activating, the agglomerates thus obtained exhibit adsorption selectivity results for paraxylene vis-à-vis the other identical C8 aromatic molecules and an increase in the paraxylene adsorption capacity, relative to adsorbents prepared from the same amount of zeolite X and binder, but the binder of which is not zeolite. Patent FR 2 789 914 thus teaches that the zeolitization of the binder allows an increase in the adsorption capacity of paraxylene, without modifying the adsorption selectivity properties. In addition to a high adsorption capacity and good selectivity properties with respect to the species to be separated from the reaction mixture, the adsorbent must have good material transfer properties in order to guarantee a number of theoretical plateaus sufficient to achieve efficient separation of the mixed species, as Ruthven states in the book Principles of Adsorption and Adsorption Processes, John Wiley & Sons, (1984), pages 326 and 407. Ruthven indicates (ibid., P. 243), that in the case of an agglomerated adsorbent, the overall material transfer depends on the sum of the intra-crystalline and inter-crystalline diffusional resistances. crystalline (between the crystals). The intra-crystalline diffusional resistance is proportional to the square of the diameters of the crystals and inversely proportional to the intracrystalline diffusivity of the molecules to be separated. The inter-crystalline diffusion resistance (also called "macroporous resistance") is in turn proportional to the square of the diameters of the agglomerates, inversely proportional to the porosity contained in the macropores and mesopores (that is to say the pores of which the aperture is greater than 2 nm) within the sinter, and inversely proportional to the diffusivity of the molecules to be separated in this porosity. The size of the agglomerates is an important parameter when using the adsorbent in the industrial application, because it determines the pressure drop within the industrial unit and the uniformity of the filling. The particle size distribution of the agglomerates must therefore be narrow, and centered on number average diameters typically between 0.40 mm and 0.65 mm in order to avoid excessive pressure losses. The porosity contained in the macropores and mesopores within the agglomerate (inter-crystalline macroporosity and mesoporosity respectively) can be increased by using porogenic agents, such as, for example, cornstarch, recommended in the document. No. 8,283,274 to improve the transfer of material. However, this porosity does not participate in the adsorption capacity and consequently the improvement of the transfer of macroporous material is then to the detriment of the volume adsorption capacity. Consequently, this pathway for improving the transfer of macroporous material is very limited. To estimate the improvement in transfer kinetics, it is possible to use the plateau theory described by Ruthven in "Principles of Adsorption and Adsorption Processes," ibid., Pp. 248-250. This approach is based on the representation of a column by a finite number of ideally stirred hypothetical reactors (theoretical stages). The equivalent height of theoretical plates is a direct measure of the axial dispersion and resistance to material transfer of the system. For a given zeolite structure, a given adsorbent size and a given operating temperature, the diffusivities are fixed, and one of the means for improving the transfer of material is to reduce the diameter of the crystals. A gain on the global material transfer will thus be obtained by reducing the size of the crystals. Those skilled in the art will therefore seek to reduce as much as possible the diameter of the zeolite crystals in order to improve the transfer of material. CN patent 1,267,185, thus claims adsorbents containing 90% to 95% BaX or BaKX zeolite for the separation of paraxylene, in which the zeolite X crystals are between 0.1 μm and 0, 4 pm and this to improve the material transfer performance. Likewise, the application US 2009/0326308 describes a process for separating xylene isomers whose performance has been improved by the use of adsorbents based on zeolite X crystals less than 0.5 μm in size. However, the Applicant has observed that the synthesis, filtration, handling and agglomeration of zeolite crystals whose size is less than 0.5 pm 25 implement heavy processes, uneconomical and therefore difficult to industrialize. In addition, such adsorbents having crystals smaller than 0.5 pm are also more fragile, and it then becomes necessary to increase the level of agglomeration binder to enhance the cohesion of the crystals between they within the adsorbent. However, the increase in the level of agglomeration binder leads to densification of the adsorbents, causing an increase in the macroporous diffusional resistance. Thus, despite reduced intracrystalline diffusion resistance due to decreasing crystal size, the increase in macroporous diffusional resistance due to densification of the adsorbent does not provide an improvement in overall transfer. Moreover, the increase in the binder content does not make it possible to obtain a good adsorption capacity. It therefore appears difficult to obtain adsorbents with all the following properties combined: a transfer of material within the adsorbent as fast as possible, that is to say a resistance to transfer of the lowest possible material and ideally almost zero, - properties of adsorption selectivity of paraxylene vis-à-vis the other aromatic C8 high molecules to ensure efficient separation, - a maximum adsorption capacity ( ie a zeolite content (active crystalline phase in the sense of adsorption) as large as possible). - optimal mechanical resistance to crushing. The Applicant has developed a zeolitic adsorbent having a compromise between maximum paraxylene adsorption selectivity, maximum adsorption capacity and minimal resistance to transfer of materials, that is to say, transport of the molecules within the fastest adsorbent possible. The applicant has also developed a method for preparing said adsorbents, and in particular a process for preparing said adsorbents which is more economical than the processes described in the prior art which could lead to said adsorbents. The adsorbents according to the present invention are particularly effective for the separation of gaseous or liquid mixtures of isomers, more particularly xylenes and in particular for the separation of very pure paraxylene from a charge of aromatic hydrocarbons containing isomers. to 8 carbon atoms. Adsorbent according to the invention Thus, and according to a first object, the present invention relates to an adsorbent comprising a zeolite phase and a non-zeolitic phase, said adsorbent having: an external surface less than or equal to 30 m 2 1, preferably less than or equal to 20 m 2 g -1, a zeolite phase comprising at least one zeolite of structure FAU type X, and a pore diameter distribution, determined by mercury intrusion according to the ASTM standard. D4284-83 and expressed by the volume distribution cAildlogDFig, where DFig is the apparent diameter of the pores, and V, the pore volume, whose mode is between 100 nm and 250 nm, inclusive. According to a preferred embodiment, the pore diameter distribution of the adsorbent corresponds to a unimodal distribution. By "unimodal distribution" is meant a distribution having only one peak. A unimodal diameter distribution is thus characterized by a single peak, for which the value of the diameter at the peak apex, is called "mode" or "dominant value", and represents the most frequent value of the distribution.
[0002] When a distribution has two peaks separated by a trough, the distribution is said to be bimodal. The invention does not relate to the case of bimodal or even multimodal distributions, that is to say of distribution where there are several areas of concentration values separated by discontinuities. Such distributions are characteristic of the presence of several populations of pores of different diameters. Advantageously, the microporous volume of the adsorbent according to the invention, evaluated by the t-plot method from the nitrogen adsorption isotherm (N2) at a temperature of 77K, is greater than 0.200. cm3.g-1. Said nitrogen adsorption isotherm is measured, after degassing under vacuum (P <6.7 × 10 -4 Pa), at a temperature of between 300 ° C. and 450 ° C. for a duration ranging from 9 hours to 16 hours. preferably at 400 ° C for 10 hours. Advantageously, the adsorbent according to the present invention comprises a non-zeolitic phase in a content of between 2% and 8% by weight relative to the total weight of the adsorbent. According to another preferred embodiment of the invention, the adsorbent zo comprises barium, or barium and potassium. The outer surface of the zeolite adsorbent of the invention is calculated by the t-plot method from the nitrogen adsorption isotherm at a temperature of 77K, after degassing under vacuum (P <6). , 7.10-4 Pa), at a temperature between 300 ° C and 450 ° C for a period of 9 hours to 16 hours, preferably at 400 ° C for 10 hours. The outer surface of the crystals of the FAU zeolite used during agglomeration is measured in the same way. In a preferred aspect, the barium content (Ba) of the zeolite adsorbent of the invention, expressed as barium oxide (BaO), is greater than 10%, preferably greater than 15%, very preferably preferred greater than 20%, even more preferably greater than 23%, or even greater than 33% by weight relative to the total weight of the adsorbent, and advantageously, the barium content is between 23% and 42%, and typically between 30% and 40%, limits included, by weight relative to the total weight of the adsorbent. According to another preferred aspect, the potassium content (K) of the zeolite adsorbent of the invention, expressed as potassium oxide (K 2 O), is less than 25%, preferably between 0 and 20% even more preferably between 0 and 15% and very preferably from 0 to 10%, inclusive, by weight relative to the total weight of the adsorbent. According to yet another preferred embodiment, the total content of alkaline or alkaline-earth ions, other than barium and potassium, expressed as total content of alkaline or alkaline-earth metal oxides other than oxide. BaO barium and potassium oxide K2O is between 0 and 5%, limits included, relative to the total weight of the adsorbent. Advantageously, the zeolitic adsorbent according to the invention has a total volume contained in the macropores and mesopores (sum of the macroporous volume and the mesoporous volume), measured by mercury intrusion according to the ASTM D4284-83 standard. , between 0.15 cm3g-1 and 0.5 cm3g-1, preferably between 0.20 cm3g-1 and 0.40 cm3g-1 and very preferably between 0 , 20 cm3.g-1 and 0.35 cm3.g-1, all these ranges of values including limits included. According to a preferred embodiment of the present invention, the zeolite adsorbent comprises at the same time macropores, mesopores and micropores. "Macropores" means pores whose diameter is strictly greater than 50 nm. By "mesopores" is meant pores whose diameter is between 2 nm and 50 nm, limits included. "Micropores" means pores whose diameter is less than 2 nm. [0037] In addition, the adsorbent of the invention advantageously has a ratio (macroporous volume) / (macroporous volume + mesoporous volume) of between 0.2 and 1, very preferably between 0.6 and 1, terminals included. It is also preferred, in the context of the present invention, a zeolite adsorbent whose microporous volume, evaluated by the t-plot method from the nitrogen adsorption isotherm (N2) at a temperature of 77 K is greater than 0.200 cm3g-1, preferably between 0.205 cm3g-1 and 0.300 cm3g-1 and more preferably between 0.205 cm3g-1 and 0.290 cm3g-1. . In the context of the present invention, the mechanical strength is measured by the Shell method SMS1471-74 series adapted for agglomerates of size less than 1.6 mm. This mechanical resistance, measured for the zeolite adsorbent defined above, is generally between 1.5 MPa and 4 MPa, preferably between 1.7 MPa and 4 MPa, more preferably between 1.8 MPa and 4 MPa and so preferably between 2 MPa and 4 MPa, limits included. [0040] According to yet another preferred embodiment, the zeolitic adsorbent according to the invention has an Si / Al atomic ratio of between 1.00 and 1.50, inclusive, preferably between 1, 05 and 1.50, inclusive terminals and more preferably between 1.15 and 1.50 inclusive. Among the zeolites of structure FAU and type X, it is now generally accepted to recognize among others two subgroups called LSX zeolites and MSX zeolites. The LSX zeolites have an Si / Al atomic ratio equal to about 1 and the MSX zeolites have an Si / Al atomic ratio of between about 1.05 and about 1.15, inclusive. According to a preferred embodiment, the at least one zeolite FAU is a zeolite X of Si / Al atomic ratio of between 1.15 and 1.50 inclusive. According to another preferred embodiment, the at least one zeolite X is an LSX type zeolite of Si / Al atomic ratio equal to about 1. In the zeolite adsorbent of the present invention, and in a preferred embodiment, by "type X FAU zeolite" means the FAU type X zeolites defined above, said zeolites being of hierarchical porosity that is to say, type X zeolites with hierarchical porosity ( or zeolite XPH), zeolites of the MSX type with hierarchical porosity (or MSXPH) and zeolites of the LSX type with hierarchical porosity (or LSXPH), and more particularly the FAU zeolites with hierarchical porosity and Si / Al atomic ratio between 1.00 and 1.50, limits included, preferably between 1.05 and 1.50, more preferably between 1.05 and 1.40 inclusive, and even more preferably between 1.15 and 1 , 40, terminals included. The invention also includes zeolitic adsorbents comprising mixtures of two or more hierarchically porous FAU zeolites as just defined. By "zeolite with hierarchical porosity" is meant a zeolite possessing both micropores and mesopores, in other words a zeolite that is both microporous and mesoporous. By "mesoporous zeolite" is meant a zeolite whose microporous zeolite crystals 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 the English language), as described for example in US Pat. No. 7,785,563: observation by transmission electron microscopy (TEM) makes it possible to verify whether the zeolitic crystals are solid (ie non-mesoporous) zeolite crystals or aggregates of solid zeolite crystals or mesoporous crystals or aggregates of mesoporous crystals. The crystalline structure of the X-type FAU zeolite in the zeolite adsorbent of the present invention is identifiable by X-ray diffraction (known to those skilled in the art under the acronym DRX). According to another preferred embodiment, no zeolite structure other than the FAU structure, preferably no zeolite structure other than the faujasite X structure, is detected by X-ray diffraction in the zeolite adsorbent. of the present invention. By no zeolite structure other than the FAU structure is meant less than 5% by weight inclusive, preferably less than 2% by weight inclusive, of one or more other zeolitic phases other than the FAU structure. . The mass fraction determined by XRD, described below, is expressed relative to the total weight of the adsorbent. The non-zeolite phase (PNZ) comprises inter alia an agglomeration binder used in the method of preparation to ensure the cohesion of the crystals with each other, hence the term "agglomerate" or "zeolite agglomerate" used sometimes in instead and place of the term "zeolite adsorbent" of the invention, as described above. In the present invention, the term "binder" means an agglomeration binder which makes it possible to ensure the cohesion of the zeolite crystals in the zeolite adsorbent (or 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 ion exchange. According to yet another preferred embodiment, the mass fraction of FAU zeolite, the FAU zeolite preferably being a type X zeolite, is greater than or equal to 85%, preferably greater than or equal to 90% relative to to the total weight of adsorbent of the present invention, the 100% complement being preferably constituted of non-zeolitic phase (PNZ). According to a particularly advantageous aspect, the mass fraction of zeolite FAU is between 92% and 98%, preferably between 94% and 98% by weight, limits included, relative to the total weight of adsorbent of the present invention, the 100% complement being preferably constituted of non-zeolitic phase. As already indicated, the mass fraction of zeolite (s) (crystallinity level) of the adsorbent according to the invention can be determined by X-ray diffraction analysis, known to those skilled in the art under the present invention. acronym DRX. According to a preferred embodiment, the zeolitic adsorbent according to the invention has a loss on ignition, measured at 950 ° C. according to the NF EN 196-2 standard, less than or equal to 7.7%, preferably between 0 and 7.7%, preferably between 3.0% and 7.7%, more preferably between 3.5% and 6.5% and advantageously between 4.5% and 6.0%, terminals included. Unless otherwise indicated in the present description, the proportions indicated are weight proportions, counted for the solid components in calcined equivalents, based on calcination carried out at 950 ° C. for 1 hour. Process for the preparation of the adsorbent according to the invention Another subject of the invention relates to a process for preparing the zeolitic adsorbent according to the invention, said process comprising at least the steps of: a) agglomeration of crystals of at least one FAU zeolite, having an external surface, measured by nitrogen adsorption, of greater than 20 m 2 · g -1, preferably of between 20 m 2 · g -1 and 200 m 2 · g -1, inclusive more preferably from 40 m 2 g -1 to 150 m 2 g -1, inclusive, with a binder preferably comprising at least 80% clay or a mixture of clays and with 5% of additives as well as with the amount of water which allows shaping of the agglomerated material, then drying and calcination of the agglomerates; b) zeolitization of all or part of the binder by contacting the agglomerates obtained in step a) with an aqueous basic solution, optionally in the presence of at least one structuring agent; c) optional elimination of the structuring agent that may be present; d) cationic exchange (s) of the agglomerates of step b) or c) by placing in contact with a solution of barium ions or barium ions and potassium ions; E) additional optional cation exchange of the agglomerates of step d) by contacting with a solution of potassium ions; f) washing and drying the agglomerates obtained in steps d) or e), at a temperature between 50 ° C and 150 ° C; and g) obtaining the zeolite adsorbent according to the invention by activating the agglomerates obtained in step f) under oxidizing and / or inert gaseous flushing, with in particular gases such as oxygen, nitrogen, air, a dry air and / or decarbonated oxygen-depleted air, optionally dry and / or decarbonated, at a temperature between 100 ° C and 400 ° C, preferably between 200 ° C and 300 ° C. In a preferred embodiment of the process for preparing the zeolite adsorbent of the present invention, the drying of the agglomerates in step a) above is generally carried out at a temperature of between 50.degree. C. and 150.degree. ° C, and the calcination of the dried agglomerates is generally carried out under oxidizing and / or inert gas scavenging, with in particular gases such as oxygen, nitrogen, air, dry 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, by example from 2 hours to 6 hours. According to one embodiment of the present invention, the FAU zeolite crystals used during the agglomeration step (step a) have a number average diameter of between 1 μm and 20 μm, inclusive limits, of more preferably between 1.5 pm and 20 pm inclusive, more preferably between 1.8 pm and 10 pm inclusive, more preferably between 2 pm and 10 pm inclusive, and more preferably between 2 pm and 8 pm pm, terminals included. [0057] In the present document, the term "number average diameter" or "size" is used interchangeably, in particular for zeolite crystals. The method of measuring these quantities is explained later in the description. According to a preferred embodiment, the zeolite with structure FAU is as defined and advantageously has an atomic ratio Si / Al preferably of between 1.00 and 1.50, preferably between 1.05 and 1.50. more preferably between 1.05 and 1.40, more preferably between 1.10 and 1.40 and even more preferably between 1.15 and 1.40, inclusive. As indicated above, the external surface of the crystals used in step a) of the process described above is calculated by the t-plot method from the nitrogen adsorption isotherm at a 77 K, after degassing under vacuum (P <6.7 x 10 -4 Pa), at a temperature between 300 ° C and 450 ° C for a period of 9 hours to 16 hours, preferably at 400 ° C for 10 hours. According to a preferred embodiment, the zeolite FAU used in step a) is a zeolite FAU hierarchically porous. The FAU zeolite crystals with a hierarchical porosity having a large external surface can be obtained according to various methods known to those skilled in the art and for example according to the synthesis described by 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 according to conventional FAU zeolite crystal post-treatment processes known to those skilled in the art. The post-treatment processes generally consist in removing atoms from 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 eliminate 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 associate the action of an acid with 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, methods of synthesis other than post-treatment) are preferred and generally involve one or more structuring agents or 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 [3- (trimethoxysilyl) propyl] octadecyldimethylammonium chloride, [3- (trimethoxysilyl) propyl] hexadecyldimethylammonium chloride, chloride [3- (trimethoxysilyl) propyl] dodecyldimethylammonium, [3- (trimethoxysilyl) propyl] octylammonium chloride, N- [3- (trimethoxysilyl) propyl] aniline, 3- [2- (2-amino) -2- ethylamino) ethylamino] propyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl] -N '- (4-vinylbenzyl) ethylenediamine, triethoxy-3- (2-imidazolin-1-yl) propylsilane, [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, dodecyltriethoxysilane, hexadecyltrimethoxysilane (3-aminopropyl) trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-chloropropyl) trimethoxysilane, as well as 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. It is also possible to use 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. According to a preferred embodiment of the process of the present invention, in step a), the crystals of at least one hierarchized porosity FAU zeolite, as described previously, prepared in presence of a sacrificial template 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 template can be carried out under oxidizing gas scavenging and / or or inert, in particular with gases such as oxygen, nitrogen, air, dry air and / or decarbonated air, oxygen-depleted air, optionally dry and / or decarbonated, with one or more 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 removing the optional sacrificial template can be performed at any time during the process for preparing the zeolite 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 calcination of the adsorbent during step a). However, it is not beyond the scope of the invention if the agglomeration of step a) included the agglomeration of several FAU zeolites with hierarchical porosity obtained in different modes. The synthesis of zeolite FAU type is generally in sodium medium (sodium hydroxide and therefore Na cation). The FAU zeolite crystals thus obtained comprise mainly, or even exclusively, sodium cations. However, it is not beyond the scope of the invention to use crystals which have undergone one or more cationic exchanges, between the synthesis in Na form, before or after the possible elimination of the sacrificial template if this step is performed before the implementation. in step 20 a). In this case, step d) and possibly step e) of exchange become (nen) t therefore possibly unnecessary (s). The size of the FAU zeolite crystals used in step a) and the FAU zeolite crystals in the adsorbents according to the invention is measured by observation under a scanning electron microscope (SEM). The agglomeration and the shaping (step a) can be carried out according to all the techniques known to those skilled in the art, and in particular according to one or more of the techniques chosen from extrusion, compacting, agglomeration on granulator plate, granulator drum, atomization and others. The proportions of agglomeration binder (see definition below) and zeolite 30 used are from 8 parts to 15 parts by weight of binder for 92 parts to 85 parts by weight of zeolite. After step a), the finest agglomerated adsorbents can be removed by cycloning and / or sieving and / or agglomerates too large by sieving or crushing, in the case of extruded, for example . The adsorbents thus obtained, whether in the form of beads, extrudates or the like, preferably have a volume average diameter, or a length thereof (larger dimension when not spherical), including 3028431 - 14 - between 0.2 mm and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.40 mm and 0.65 mm, inclusive. The binder used in the context of the present invention may therefore be chosen from conventional binders known to those skilled in the art, and preferably chosen from clays and clay mixtures. The clays are preferably chosen from: kaolin, kaolinite, nacrite, dickite, halloysites, attapulgite, sepiolite, montmorillonite, bentonite, illite and metakaolin, as well as mixtures of two or more of them in all proportions. Preferably, the agglomeration binder used in step a) contains at least one zeolitizable clay, preferably chosen from the family of kaolins, kaolinites, nacrites, dickites, halloysites and metakaolins, and mixtures thereof. . Kaolin is preferred and most commonly used. The agglomeration binder used in step a) may also contain other inorganic binders such as bentonite, attapulgite, and others.
[0003] Zeolizable clay is understood to mean a clay or a mixture of clays which are capable of being converted into zeolitic material, most often by the action of an aqueous basic solution. Among the additives optionally used in step a), there can be found a silica source of any type known to those skilled in the art, specialized in the synthesis of zeolites, for example colloidal silica, diatoms, perlite, fly ash, sand, or any other form of solid silica. In step a), in addition to the zeolite crystal (s), the binder may also comprise one or more additives. The additives are preferably organic, for example lignin, starch, carboxymethylcellulose, surface-active molecules (cationic, anionic, nonionic or amphoteric), intended to facilitate the handling of the zeolite paste (s). / Clay (s) by modifying the rheology and / or stickiness or to give the final adsorbents satisfactory properties, including macroporosity. Mention may be made preferably but not exhaustively of methylcelluloses and their derivatives, lignosulphonates, polycarboxylic acids and carboxylic acid copolymer acids, their amino derivatives and their salts, especially alkaline salts and sodium salts. 'ammonium. The additives are introduced at from 0 to 5%, preferably from 0.1% to 2%, by weight relative to the total weight of the adsorbent. The SEM observation of the zeolitic adsorbent makes it possible to confirm the presence of a non-zeolitic phase comprising, for example, agglomeration binder or any other amorphous phase in the adsorbents. For the calcination included in stage a), the nature of the gases, the temperature ramps and the successive temperature stages, as well as their respective durations, will be adapted in particular according to the nature of the gases. sacrificial template to be eliminated and depending on the nature of the binder used in the agglomeration step a). Similarly, the zeolitization step b) 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. sodium hydroxide or potassium hydroxide, the use of sodium hydroxide being very particularly preferred. As a general rule, the concentration of the alkaline alkaline solution of zeolitization is between 0.5 M 10 and 5 M. The zeolitization is preferably carried out hot, at a temperature greater than ambient temperature, for example included between room temperature (about 20 ° C) and the boiling temperature of the alkaline zeolite solution, and for example at temperatures of the order of 80 ° C to 100 ° C. The duration of the zeolite 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, step b) of zeolization of at least a portion of the agglomeration binder can be carried out in the presence of at least one structuring agent or sacrificial template intended for to be eliminated according to the methods known to those skilled in the art, for example by calcination, the presence of the structuring agent for the purpose of creating a certain mesoporosity in the sinter of the invention thus to obtain a mesoporous zeolite agglomerate. The nature of the structuring agent or sacrificial template may be of any type known to those skilled in the art and in particular chosen from those described above for the synthesis of zeolite with hierarchical porosity. The amount of structuring agent, when it is present during the zeolitization step, may vary in large proportions depending on 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). Step c) possible elimination of the structuring agent optionally introduced during the zeolitization step b) and aimed at converting a portion of the agglomeration binder to a mesoporous zeolite, can be carried out by any known means. 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 g) performed at high temperature also allows the removal of the structuring agent, thus making it possible advantageously not to carry out the step e) of eliminating said structuring agent which will in fact be eliminated during activation in step g). The cationic exchange (s) stages (d) and (e) described above are carried out according to the conventional methods known to those skilled in the art, and most often by contacting the adsorbents of step a) with a barium salt, such as barium chloride (BaCl 2) and / or potassium (KCl) and / or barium and potassium, in aqueous solution at a temperature between room temperature and 100 ° C, and preferably between 80 ° C and 100 ° C to rapidly obtain high levels of barium, ie levels preferably of greater than 10%, preferably greater than 15%, very preferably higher at 20%, even more preferably greater than 23%, or even greater than 33%, expressed by weight of barium oxide relative to the total mass of the adsorbent. Advantageously, the barium content expressed as barium oxide is between 23% and 42%, and typically between 30% and 40%, limits included, by weight relative to the total weight of the adsorbent. It is preferred to operate with a large excess of barium ions relative to the cations of the zeolite that it is desired to exchange, typically an excess of the order of 10 to 12, advantageously by proceeding by successive exchanges. Potential exchange with potassium in step e) can be practiced before and / or after the barium exchange (step b). It is also possible to agglomerate in step a) 20 FAU zeolite crystals already containing barium or potassium or barium and potassium ions (pre-exchange of the cations present in the starting FAU type zeolite, typically sodium cations, by barium or potassium ions or barium and potassium before step a) and overcome (or not) steps d) and / or e). Surprisingly, the Applicant has observed that the cation exchange step, which can be delicate because of the relative fragility of the zeolite crystal structure with hierarchical porosity, does not affect the intrinsic properties of the surface. external and microporous volume (returned to the mass of the adsorbent once exchanged) said zeolite crystals with hierarchical porosity. After the cationic exchange step (s), the product is then washed, generally and preferably with water, followed by drying of the adsorbent thus obtained. The activation which follows the drying is carried out in a conventional manner, according to the methods known to those skilled in the art, for example at a temperature in general of between 100 ° C. and 400 ° C., preferably between 200 ° C. and 300 ° C. ° C. The activation is carried out for a determined duration depending on the desired loss on fire. This time is generally between a few minutes and a few hours, typically 1 to 6 hours. The present invention also relates to the uses of the zeolitic adsorbents described above as adsorption agents that may advantageously replace the adsorption agents described in the literature, based on the above-described adsorbents. Conventional zeolite crystals of the FAU type, and in particular in the uses listed below: separation of C 8 aromatic isomer fractions and in particular xylenes; separation of isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluene diamine, and others, 10 - separation of cresols, - separation of polyhydric alcohols, such as sugars. According to another object, the present invention relates to a process for separating xylene isomers in the gas phase or in the liquid phase using at least one zeolite adsorbent as defined above. The invention relates in particular to a process for separating paraxylene from a feedstock to be treated with cuts of aromatic isomers containing 8 carbon atoms, using, as adsorbent for paraxylene, a zeolite adsorbent such as previously defined. It is thus possible to separate the desired product (paraxylene) by preparative adsorption liquid chromatography (in batch), and advantageously continuously in a simulated moving bed, that is to say, against the simulated countercurrent or at the same time. simulated current, and more particularly simulated countercurrent. The operating conditions of a simulated moving bed adsorption industrial unit operating against the current are in general the following: 25 - number of beds: 4 to 24, - number of zones: at least 4 operating zones each being located between a feed point (feed flow to be treated or desorbent flow) and a draw point (raffinate flow or extract flow); temperature between 100 ° C. and 250 ° C., preferably between 140 ° C. and 190 ° C., pressure of the industrial unit lying between the bubble pressure of xylenes (or toluene when toluene is chosen as the desorbent) ) at the process temperature and 3 MPa, desorbent / charge flow ratio between 0.7 and 2.5, preferably between 0.7 and 2.0, for example between 0.9 and 1.8 for a adsorption unit alone (so-called "stand alone") and between 0.7 and 1.4 for an adsorption unit combined with a crystallization unit, 3028431 - 18 - recycling rate between 2 and 12 preferably between 2.5 and 6, - cycle time, corresponding to the time between two injections of desorbent on a given bed: advantageously between 4 and 25 min. On this subject, reference may be made to the teaching of patents US 2,985,589, US 5,284,992 and US 5,629,467. [0101] The operating conditions of an industrial unit for co-current adsorption simulated are generally the same as those operating against simulated countercurrent, with the exception of the recycling rate which is generally between 0.8 and 7. On this aspect, reference may be made to US Pat. Nos. 4,402,832 and US Pat. 4,498,991. The desorbent is a desorption solvent whose boiling point is lower than that of the feed, such as toluene or greater than that of the feedstock, such as paradiethylbenzene (PDEB). Advantageously, the desorbent is toluene or paradiethylbenzene. The selectivity of the adsorbents according to the invention for the adsorption of paraxylene contained in C8 aromatic cuts is optimal when their loss on ignition measured at 950 ° C. is preferably less than or equal to 7.7%, of preferably between 0 and 7.7%, very preferably between 3.0% and 7.7%, more preferably between 3.5% and 6.5% and even more preferably between 4.5%. and 6%, limits included. The water content in the incoming flows consisting of the feed and / or desorbent flows is preferably adjusted between 20 ppm and 150 ppm, for example by adding water to the feed streams and / or desorbent. The zeolitic adsorbents of the invention exhibit improved material transfer properties while maintaining optimum properties of paraxylene selectivity, maximum adsorption capacity, and maintaining high mechanical strength for use in a process. separating the paraxylene in the liquid phase, preferably of the simulated countercurrent type. It has been very particularly observed that the zeolitic adsorbents according to the present invention have a combined index IC greater than 14, and in general greater than 30 to 15, which is quite remarkable with respect to the IC values observed with the adsorbents of the prior art. The IC number is defined by the following formula: IC - selectivity x HEPT capacity in which: - the "selectivity" parameter represents the selectivity between paraxylene and metaxylene, - the "capacity" parameter represents the adsorption capacity of xylenes expressed in% (cm3 of C8-aromatics adsorbed per cm3 of column) 5 - the "HEPT" parameter represents the equivalent height of theoretical plates measured on paraxylene relative to the column length (expressed in% ). The various parameters are determined by the so-called liquid phase drilling technique in a test carried out under the following conditions: the adsorption temperature is 175 ° C., the superficial velocity (flow rate / section of the column) ) of circulation of the liquid at the test temperature is 1.3 cm.s-1, - the desorption solvent used is para-diethylbenzene, - the composition of the filler is the following: - Paraxylene: 45% weight 15 - Metaxylene: 45% weight - lso-octane: 10% by weight (it is used as a tracer for the estimation of non-selective volumes and does not intervene in the separation); According to yet another aspect, the present invention relates to the use of at least one zeolite adsorbent having a combined index IC greater than 14, and preferably greater than 15, in the processes for separating isomers of xylenes from gas phase or in the liquid phase, such as those defined above. In this use, said at least one zeolitic adsorbent has a mechanical strength advantageously greater than 1.5 MPa, preferably between 1.7 MPa and 4 MPa, more preferably between 1.8 MPa and 4 MPa, and thus Most preferably between 2 MPa and 4 MPa, inclusive. In the context of the present invention, the mechanical strength is measured by the Shell method SMS1471-74 series adapted for agglomerates smaller than 1.6 mm. CHARACTERIZATION TECHNIQUES Granulometry of Zeolite Crystals The estimation of the number average diameter of the zeolite crystals FAU used during step a) of agglomeration and of the crystals contained in the zeolite adsorbents according to the invention is carried out by observation by scanning electron microscope (M EB). In order to estimate the size of the zeolite crystals on the samples, 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 dedicated software. The accuracy is of the order of 3%. Chemical analysis of zeolitic adsorbents - Si / Al ratio and exchange rate: A basic chemical analysis of the final product obtained after the steps a) to e) described above, can be carried out according to different analytical techniques known to those skilled in the art. Among these techniques, mention may be made of the X-ray fluorescence chemical analysis technique as described in standard NF EN ISO 12677: 2011 on a wavelength dispersive spectrometer (VVDXRF), for example Tiger S8 from the Bruker company. [0114] 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 bombardment with electrons, 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. These elementary chemical analyzes make it possible both to verify the Si / Al atomic ratio of the zeolite used during the preparation of the adsorbent, as well as the Si / Al atomic ratio of the adsorbent and to verify the quality of the the ion exchange described in step c) and in optional step d). 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 sodium oxide, Na 2 O, remaining in the zeolite adsorbent after exchange. More specifically, the exchange rate by barium ions is estimated by evaluating the ratio between the number of 25 moles of barium oxide, BaO, and the number of moles of the whole (BaO + Na2O + K2O). Similarly, the exchange rate by potassium ions is estimated by evaluating the ratio between the number of moles of potassium oxide K2O and the number of moles of the whole (BaO + K2O + Na2O). It should be noted that the contents of various oxides are given in percentage by weight relative to the total weight of the anhydrous zeolite adsorbent. Zeolite adsorbent particle size distribution: The determination of the volume average diameter of the zeolite adsorbents obtained at the stage of the agglomerating and shaping step a) is carried out by analysis of the particle size distribution of a sample of zeolitic adsorbents. image adsorbent according to ISO 13322-2: 2006, using a treadmill allowing the sample to pass in front of the camera lens. The volume mean diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard. In this document, the term "volume mean diameter" or "size" is used for zeolite adsorbents. The accuracy is of the order of 0.01 mm for the adsorbent size range of the invention. Mechanical resistance of zeolite adsorbents: The crush resistance of a bed of zeolite adsorbents as described in the present invention is characterized according to 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 device marketed by Vinci Technologies. This method, initially intended for the characterization of catalysts from 3 mm to 6 mm is based on the use of a sieve of 425 pm which will allow in particular to separate the fines created during the crash. The use of a 425 μm sieve remains suitable for particles of diameter greater than 1.6 mm, but must be adapted according to the particle size of the adsorbents that are to be characterized. The adsorbents of the present invention, generally in the form of beads or extrudates, generally have a mean diameter by volume or a length, ie the largest dimension in the case of non-spherical adsorbents, of between 0.2 mm. and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.40 mm and 0.65 mm inclusive. Therefore, a 100 μm sieve is used in place of the 425 μm sieve mentioned in the standard Shell method SMS1471-74. The measurement protocol is as follows: a sample of 20 cm 3 of agglomerated adsorbents, previously sieved with the appropriate sieve (100 μm) and previously oven-dried for at least 2 hours at 250 ° C. (at room temperature). instead of 300 ° C mentioned in the standard Shell method SMS1471-74), is placed in a metal cylinder of known internal section. An increasing force is imposed in stages on this sample by means of a piston, through a bed of 5 cm3 of steel balls in order to better distribute the force exerted by the piston on the agglomerated adsorbents (use of 2 mm diameter for particles of spherical shape of diameter strictly less than 1.6 mm). The fines obtained at the different pressure levels are separated by sieving (100 μm sieve) and weighed. The crush resistance in the bed is determined by the pressure in megaPascal (MPa) for which the amount of cumulative fines passing through the sieve amounts to 0.5% by weight of the sample. This value is obtained by plotting the mass of fines obtained as a function of the force applied on the adsorbent bed and by interpolating at 0.5% by mass of cumulated fines. The mechanical resistance to crushing in a bed is typically between a few hundred kPa and a few tens of MPa and generally between 0.3 MPa and 3.2 MPa. The accuracy is conventionally less than 0.1 MPa.
[0004] Non-Zeolite Phase of Zeolite Adsorbents: The non-zeolitic phase content PNZ, for example the level of agglomeration binder and any other amorphous phase, is calculated according to the following equation: PNZ = 100-E (PZ) where PZ is the sum of the amounts of the zeolite fractions X in the sense of the invention. Mass Quantity of Zeolite Fractions of Zeolite Adsorbents The identification of the zeolite fractions contained in the adsorbent is carried out by X-ray diffraction analysis (XRD). This analysis is carried out on a device of the Bruker brand. The identification of the crystalline phases present in the zeolite adsorbent is carried out by comparison with the sheets of the ICDD database. For example, the presence of the X-type zeolite exchanged with barium will be confirmed by comparison of the lines of the diffractogram obtained with the ICDD sheet No. 38-0234 ("Zeolite X, (Ba)"). The mass quantity of the zeolite fractions is evaluated from the peak intensities of the diffractograms by taking as reference zo the peak intensities of a suitable reference (zeolite of the same chemical nature assumed to be 100% crystalline under cationic treatment conditions identical to those of adsorbent considered). The peaks, allowing to go back to the crystallinity, are the most intense peaks of the angular zone between 9 ° and 37 °, namely the peaks observed in the angular ranges of between 11 ° and 13 ° respectively, 22 ° and 26 ° and between 31 ° and 33 °. Microporous Volume, External Surface The crystallinity of the zeolitic crystals and adsorbents of the invention is also evaluated by measuring their microporous volume by comparing it with that of a suitable reference (100% crystalline zeolite under treatment conditions. identical cationic or theoretical zeolite). This microporous volume is determined from the measurement of the gas adsorption isotherm, such as nitrogen, at its liquefaction temperature. Prior to the adsorption, the zeolite sample (whether adsorbent or crystals) 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). The measurement of the nitrogen adsorption isotherm at 77K is then carried out on an ASAP 2020 M type apparatus of Micromeritics, taking at least 35 measurement points at relative pressures of ratio P / Po included. between 0.002 and 1. The microporous volume as well as the external surface are determined from the isotherm obtained by the t-plot method by applying the ISO 15901-3: 2007 and 5 standard by calculating the thickness statistic t by the Harkins-Jura equation. The microporous volume and the external surface are obtained by linear regression on the points of the t-plot between 0.45 nm and 0.57 nm, respectively from the ordinate at the origin and the slope of the linear regression. . The microporous volume evaluated is expressed in cm 3 of liquid adsorbate per gram of anhydrous adsorbent. The external surface is expressed in m2 per gram of anhydrous adsorbent. Macroporous and Mesoporous Volume, Mercury Intrusion Pore Diameter Distribution, and Grain Density Macroporous and mesoporous volumes as well as grain density are measured by mercury intrusion porosimetry. A Micromeritics Autopore® 9500 mercury porosimeter is used to analyze the distribution of the pore volume contained in macropores and mesopores. The experimental method, described in the operating manual of the apparatus referring to the ASTM D4284-83 standard, consists of placing a sample of adsorbent (zeolite granular material to be measured) (known fire loss) 20 beforehand. weighed, in a cell of the porosimeter, then, after a prior degassing (discharge pressure of 30 pm Hg for at least 10 min), to fill the cell with mercury at a given pressure (0.0036 MPa), and then to apply increasing pressure stepwise up to 400 MPa in order to gradually penetrate the mercury into the porous network of the sample. The pore volume increment dV into which the mercury enters at each pressure level is recorded. The pressure bearing number is typically about 0.0036 MPa to 0.2 MPa, and about 90 to 0.2 MPa to 400 MPa. The relationship between the applied pressure and the apparent diameter of the DFig pores is established assuming cylindrical pores, a mercury-pore wall contact angle of 140 ° and a mercury surface tension of 485 dynes. / cm. The cumulative amount of mercury introduced as a function of the applied pressure is recorded. The value at which the mercury fills all the inter-granular voids is fixed at 0.2 MPa, and it is considered that, beyond this, the mercury penetrates into the pores of the granular material. The grain volume (Vg) is then calculated by subtracting the cumulative volume of mercury at this pressure (0.2 MPa) from the cell volume of the porosimeter, and dividing this difference by the mass of the granular material. anhydrous equivalent, that is to say the mass of said material corrected for loss on ignition. The grain density is the inverse of the grain volume (Vg), and is expressed in grams of anhydrous adsorbent per cm3. The macroporous volume of the granular material is defined as the accumulated volume of mercury introduced at a pressure of between 0.2 MPa and 30 MPa, corresponding to the volume contained in the pores with an apparent diameter greater than 50 nm. The mesoporous volume of the granular material is defined as the cumulative volume of mercury introduced at a pressure of between 30 MPa and 400 MPa. In this document, the macroporous and mesoporous volumes of the zeolite adsorbents, expressed in cm3.g-1, are thus measured by mercury intrusion and reported to the mass of the sample in anhydrous equivalents, that is, that is, the mass of said material corrected for loss on ignition. The pore diameter distribution determined by mercury intrusion is expressed by the volume distribution cA // dlogDFig shown as a function of the apparent pore diameter of the DFig pores. DVidlogDFig values are calculated from the porous volume increment dV in which the mercury enters at each pressure level relative to the corresponding apparent pore diameter difference. Loss on ignition of zeolite adsorbents: 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 standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%. Characterization of liquid phase adsorption by drilling: The technique used to characterize the adsorption of molecules in the liquid phase on a porous solid is the so-called drilling technique, described by Ruthven in "Principles of Adsorption and Adsorption Processes". "(Chapters 8 and 9, John Wiley & Sons, 1984) which defines the technique of breakthrough curves as the study of the response to the injection of a step of adsorbable constituents. The analysis of the average time of exit (first moment) of the drilling curves provides information on the adsorbed quantities and also makes it possible to evaluate the selectivities, that is to say the separation factor, between two adsorbable constituents. The injection of a non-adsorbable component used as a tracer is recommended for the estimation of non-selective volumes. The dispersion analysis (second moment) of the drilling curves makes it possible to evaluate the equivalent height of theoretical plates, based on the representation of a column by a finite number of hypothetical reactors ideally stirred (stages). theoretical), which is a direct measure of the axial dispersion and resistance to material transfer of the system. EXAMPLES Example A Synthesis of Hierarchized Porosity FAU Zeolite The high surface area FAU zeolite is synthesized directly from Inayat et al. (Angew Chem Int.Ed., (2012), 51, 1962-1965). Step 1): Preparation of the growth gel in stirred reactor with Archimedes screw at 300 rpm. 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) at 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.degree. Step 2): Introduction into the reaction medium of the structuring agent 27.3 g of 60% TPOAC solution in MeOH are introduced into the reaction medium with a stirring speed of 300 rpm. 1 (TPOAC / Al 2 O 3 molar ratio = 0.04). After 5 minutes of homogenization, the stirring speed is lowered to 50 rpm. Step 3): Ripening phase The stirred reaction medium is maintained at 50 rpm at 25 ° C for 22 hours and then the crystallization is started. Step 4): Crystallization [0143] The stirring speed is maintained at 50 rpm and the set point of the jacket of the reactor is set at 80 ° C. so that the reaction medium rises to 75 ° C. in 80 minutes. After 72 hours of residence at 75 ° C., the reaction medium is cooled by circulating cold water in the jacket to stop the crystallization. Step 5): Filtration / washing The solids are recovered on sintered and then washed with deionized water until neutral pH. Step 6): Drying / calcination [0145] 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 22% 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 rise at 200 ° C., then 1 hour of bearing at 200 ° C, then 3 hours of rise at 550 ° C, and finally 1.5 hours of bearing at 550 ° C. The crystals obtained are identified by X-ray diffraction (XRD analysis) as being faujasite crystals. Chemical analysis of the solid gives an atomic ratio Si / Al = 1.24. The average number-average crystal diameter of the mesoporous zeolite (or with hierarchical porosity) thus obtained is 4.5 μm. The microporous volume and the external surface measured according to the t-plot 10 method from the isothermal nitrogen adsorption at 77K after degassing under vacuum at 400 ° C for 10 hours are respectively 0.260 cm3g-1 and 90 m2.g-1 expressed per gram of dry adsorbent. Example B: Synthesis of crystals of non-mesoporous zeolite X, Si / Al = 1.25 atomic ratio, number average diameter of 1.0 μm and Na / Al = 1 atomic ratio [0149] A gel was prepared of molar composition 3.5 Na 2 O - 2.8 SiO 2 - Al 2 O 3 - 130 H 2 O, by mixing the following reagents: sodium silicate, sodium aluminate and water. The gel is cured at 35 ° C for 20 hours and crystallized for 4 hours at 100 ° C. The crystals obtained after filtration and washing are identified by X-ray diffraction (XRD analysis) as faujasite crystals. Chemical analysis of the solid gives an atomic ratio Si / Al = 1.25. The number average diameter of the zeolite crystals is 1.0 μm. The microporous volume and the external surface measured by the t-plot method from the nitrogen adsorption isotherm at 77K after degassing under vacuum at 400 ° C. for 10 hours are respectively 0.345 cm3g -1 and 2 m2.g-1. expressed per gram of dry adsorbent. Preparation of Zeolite Adsorbents A homogeneous mixture is prepared and 1600 g of NaX zeolite crystals prepared according to the procedures described in Examples A or B are agglomerated with 350 g of kaolin (expressed as calcined equivalent) and 130 g of colloidal silica sold under the trade name Klebosol® 30 (containing 30% by weight of SiO2 and 0.5% of Na2O) with the amount of water which allows the extrusion of the mixture. The fire loss of the pulp before extrusion is 44%. Extrudates 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, then 2 hours at 550 ° C. under a decarbonated dry air sweep and then crushed to recover grains of equivalent diameter. is equal to 0.4 mm. Example 1 (Comparative) Preparation of zeolite adsorbent in crushed form with X-type zeolite, zeolite crystal size of 1.0 μm and non-zeolitic kaolin binder [0152] Granules (200 g) ) obtained from the powder synthesized in Example B are exchanged with a solution of 0.5 M barium chloride at 95 ° C in 4 steps. At each step, the solution volume to solid mass ratio is 20 mL / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times in order to rid it of excess salt. It is then activated at a temperature of 250 ° C. for 2 hours under a stream of nitrogen. The barium exchange rate is 97% and the loss on ignition is 5.4%. The microporous volume and the external surface measured by the t-plot method from the nitrogen adsorption isotherm at 77 K after vacuum degassing at 400 ° C. for 10 hours are respectively 0.226 cm3 .g-1 and 16.7 m2.gi. The total volume of macropores and mesopores measured by mercury porosimetry is 0.32 cm3g-1. The volume fraction of macropores on the total volume of macropores and mesopores is equal to 0.87. The pore diameter distribution is determined from the mercury intrusion analysis performed on the adsorbent and represented by the volume distribution cAildlogDFig, as a function of the apparent pore diameter DFig. The distribution has a distinct peak in the macropore domain corresponding to a unimodal distribution around a mode equal to about 350 nm. [0156] The mechanical strength is also measured according to the method presented in the description of the invention. The pressure necessary to obtain 0.5% of fines is 2.2 MPa. Example 2 (Comparative) Preparation of zeolite adsorbent in the form of crushed with type X zeolite, 1.0 μm zeolite crystal size and zeolite kaolin binder [0157] Granules (200 g) obtained from the powder synthesized in Example B 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 an aqueous solution is added. of sodium hydroxide of concentration 1 M and the reaction medium is left stirring for a period of 3 hours. The agglomerates 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 washings between 10.0 and 10.5. These agglomerates are exchanged with a solution of 0.5 M barium chloride at 95 ° C in 4 steps. At each step, the volume ratio of solution to mass of solid is 20 mL.g-1 and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times in order to rid it of excess salt. It is then activated at a temperature of 250 ° C. for 2 hours under a stream of nitrogen. [0160] The barium exchange rate is 97% and the loss on ignition is 5.3%. The microporous volume and the external surface measured by the t-plot method from the nitrogen adsorption isotherm at 77 K after vacuum degassing at 400 ° C. for 10 hours are respectively 0.249 cm3g-1 and 5 m2.gi. The total volume of macropores and mesopores measured by mercury porosimetry is 0.29 cm3g-1. The volume fraction of macropores on the total volume of macropores and mesopores is equal to 0.97. The pore diameter distribution is determined from the mercury intrusion analysis carried out on the adsorbent and represented by the volume distribution cAildlogDFig, as a function of the apparent diameter of the DFig pores (see FIG. 1). The distribution 20 has a distinct peak in the macropore domain corresponding to a unimodal distribution around a mode equal to about 360 nm. The non-zeolitic phase content is equal to 5% by weight, as measured by XRD, using as reference the crystals of the starting zeolite having undergone the same barium exchange. [0164] The mechanical strength is also measured according to the method presented in the description of the invention. The pressure required to obtain 0.5% of fines is 2.5 MPa. Example 3 (Comparative) Preparation of zeolitic adsorbent in crushed form with XPH type zeolite, size of 4.5 μm zeolite crystals and non-zeolitized kaolin binder. Granules (200 g) obtained from the powder synthesized in Example A are exchanged with a solution of 0.7 M barium chloride at 95 ° C in 4 steps.
[0005] At each step, the solution volume to solid mass ratio is 20 mL / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times to rid it of excess salt. It is then activated at a temperature of 250 ° C. for 2 hours under a stream of nitrogen. The barium exchange rate is 97% and the loss on ignition is 5.5%. The microporous volume and the external surface measured by the t-plot method from the nitrogen adsorption isotherm at 77 K after vacuum degassing at 400 ° C. for 10 hours are respectively 0.192 cm 3 .g -1 and 70 m2.g-1. The total volume of macropores and mesopores measured by mercury porosimetry is 0.33 cm3g-1. The fraction of volume of macropores on the total volume of macropores and mesopores is equal to 0.6. [0168] The mechanical strength is also measured according to the method presented in the description of the invention. The pressure necessary to obtain 0.5% of fines is 2.1 MPa. The pore diameter distribution is determined from the mercury intrusion analysis performed on the adsorbent and represented by the volume distribution cAildlogDFig, as a function of the apparent pore diameter DFig in FIG. has a peak and a shoulder in the macropore domain, describing a bimodal distribution with a first mode around 140 nm and a second in the very small macropore domains, at about 55 nm. Example 4 (according to the invention): zo Preparation of a zeolitic adsorbent in the form of crushed with 4.5 μm size XPH crystals and a zeolite kaolin binder [0170] Granules (200 g) obtained from of the powder synthesized in Example A 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 an aqueous solution of hydroxide is added. 1 M concentration of sodium and the reaction medium is left stirring for a period of 3 hours. The agglomerates 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 washings between 10.0 and 10.5. These agglomerates are exchanged with a solution of 0.5 M barium chloride at 95 ° C in 4 steps. At each step, the volume ratio of solution to mass of solid is 20 mL.g-1 and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times in order to rid it of excess salt. It is then activated at a temperature of 250 ° C. for 2 hours under a stream of nitrogen. The barium exchange rate is 96% and the loss on ignition is 5.3%. The microporous volume and the external surface measured by the t-plot method from the nitrogen adsorption isotherm at 77 K after vacuum degassing at 400 ° C. for 10 hours are respectively 0.260 cm3g-1 and 12 m2.g-1. [0174] The total volume of macropores and mesopores measured by mercury porosimetry is 0.29 cm3g-1. The volume fraction of macropores on the total volume of macropores and mesopores is equal to 0.9. The pore diameter distribution is determined from the mercury intrusion analysis carried out on the adsorbent and represented by the volume distribution / o cAlldlogDFig, as a function of the apparent diameter of the pores DFig in FIG. distribution has a distinct peak in the macropore domain corresponding to a unimodal distribution around a mode equal to about 190 nm. [0176] FIG. 1 represents the pore diameter distribution curves determined from the mercury intrusion analysis carried out on the adsorbents of Examples 2 to 4. The non-zeolitic phase content is equal to 5. % weight, as measured by XRD, using as a reference, the crystals of the starting zeolite having undergone the same barium exchange. [0178] The mechanical strength is also measured according to the method presented in the description of the invention. The pressure required to obtain 0.5% of fines is 2.5 MPa. Example 5: A drilling test (frontal chromatography) is then performed on these adsorbents to evaluate their effectiveness. The amount of adsorbent used for this test is about 34 g. The procedure for obtaining the drilling curves is as follows: filling the column with the sieve and placing it in the test bench, filling with the desorption solvent at ambient temperature, gradually rising to the adsorption temperature under a stream of solvent (5 cm3 / min), 30 - injection of solvent at 30 cm3 / min when the adsorption temperature is reached, - solvent / charge permutation to inject the charge (30 cm3.min-1) ), the charge injection is then maintained for a time sufficient to reach thermodynamic equilibrium (that is to say until the solvent concentration in the effluent is zero), and 35 - collection and analysis of the drilling effluent. The desorption solvent used is para-diethylbenzene. The composition of the filler is the following: - Paraxylene: 45% by weight - Metaxylene: 45% by weight 5 - Iso-octane: 10% by weight (it is used as a tracer for the estimation of non-selective volumes and not involved in the separation) [0182] The test is carried out with an adsorption temperature of 175 ° C. The pressure is sufficient for the charge to remain in the liquid phase, ie 1.5 MPa. The superficial velocity (flow rate / section of the column) of liquid flow at the test temperature is about 1.3 cm.s-1 for all tests. The selectivity of paraxylene relative to metaxylene is calculated by material balance. The results of the drilling are shown in Table 1 below: Table 1 Adsorbent PX / MX selectivity Capacity HEPT IC Adsorption resistance (%) mechanical r / o) Example 1 3.35 14.2 6, 3 7.6 2.2 (Comparative) Example 2 3.52 17.4 8.4 7.3 2.5 (Comparative) Example 3 2.66 13.4 2.6 13.7 2.1 (comparative) Example 4 3.19 17.6 3.7 15.2 2.5 (invention) Legend - PX = ParaXylene; MX = MetaXylene - Adsorption capacity expressed in% (cm3 adsorbed C8-aromatics per cm3 of column) zo - HEPT = Equivalent Height of Theoretical Plateaux measured on paraxylene expressed in% of column length - IC selectivity x HEPT capacity [ 0184] Compared to the results obtained with the adsorbent of Examples 1 and 2, there is a clear improvement in the material transfer on the adsorbent of Example 4, translated by the equivalent height of theoretical plates significantly decreased. Compared to the results obtained with the adsorbent of Example 3, it is found, for the adsorbent of Example 4, a marked increase in the selectivity of paraxylene vis-à-vis the metaxylene (+ 17%) and a clear increase in the adsorption capacity. The IC index combining all these parameters, capacity, selectivity and 5 HEPT, makes it possible to evaluate the impact of the compromise between selectivity, capacity and material transfer: the higher the index, the better the compromise. It is noted that the IC numbers calculated on the adsorbents based on XPH crystals, namely on the adsorbents of Examples 3 and 4 (Example 4 being according to the invention) are very clearly greater than the indices calculated on the adsorbents of Examples 1 and 2. 2. / o [0187] The highest calculated IC number is obtained on the adsorbent of Example 4, according to the invention, and therefore this adsorbent will be the most efficient for the separation of paraxylene. The zeolitic adsorbent according to the invention combines a good mechanical resistance, a good selectivity of adsorption of paraxylene, a high adsorption capacity and a transport of the molecules within the fast adsorbent.

权利要求:
Claims (18)
[0001]
REVENDICATIONS1. Adsorbent comprising a zeolite phase and a non-zeolitic phase, said adsorbent having: an external surface less than or equal to 30 m 2 g -1, preferably less than or equal to 20 m 2 g -1, a zeolitic phase comprising at least an X-type FAU structure zeolite; and a pore diameter distribution, determined by mercury intrusion according to ASTM D4284-83 and expressed by the volume distribution cAildlogDFig, where DFig is the apparent diameter of the pores, and V , the pore volume, whose mode is between 100 nm and 250 nm, limits included. / 5
[0002]
An adsorbent according to claim 1, wherein the pore diameter distribution corresponds to a unimodal distribution.
[0003]
3. Adsorbent according to claim 1 or 2, whose microporous volume, evaluated by the t-plot method from the nitrogen adsorption isotherm (N2) at a temperature of zo 77K, is greater than 0.200 cm3. 1g-1, preferably between 0.205 cm3g-1 and 0.300 cm3g-1 and more preferably between 0.205 cm3g-1 and 0.290 cm3g-1.
[0004]
4. Adsorbent according to any one of the preceding claims comprising a non-zeolitic phase in a content of between 2% and 8% by weight relative to the total weight of the adsorbent.
[0005]
An adsorbent according to any one of the preceding claims comprising barium or barium and potassium. 30
[0006]
6. Adsorbent according to any one of the preceding claims having a total volume contained in the macropores and mesopores (sum of macroporous volume and mesoporous volume) measured by mercury intrusion according to ASTM D4284-83, between 0.15 cm3.g-1 and 0.5 cm3.g-1 terminals included. 3028431 - 34 -
[0007]
7. Adsorbent according to any one of the preceding claims having a ratio (macroporous volume) / (macroporous volume + mesoporous volume) between 0.2 and 1 included terminals. 5
[0008]
8. Adsorbent according to any one of the preceding claims having an Si / Al atomic ratio of between 1.00 and 1.50 inclusive.
[0009]
9. A process for the preparation of the adsorbent according to claims 1 to 8, comprising at least the steps of: a) agglomerating crystals of at least one FAU zeolite, having an external surface, measured by nitrogen adsorption, greater at 20 m2.g-1, preferably between 20 m2.g-1 and 200 m2.g-1, limits included, more preferably between 40 m2.g-1 and 150 m2.g-1, limits included with a binder preferably comprising at least 80% clay or a mixture of clays and up to 5% of additives and with the amount of water which allows the shaping of the agglomerated material then drying and calcining agglomerates; b) zeolitization of all or part of the binder by contacting the agglomerates obtained in step a) with an aqueous basic solution, optionally in the presence of at least one structuring agent; c) optional elimination of the structuring agent that may be present; d) cationic exchange (s) of the agglomerates of step b) or c) by placing in contact with a solution of barium ions or barium ions and potassium ions; e) additional cationic exchange of the agglomerates of step d) by contacting with a solution of potassium ions; f) washing and drying the agglomerates obtained in steps d) or e), at a temperature between 50 ° C and 150 ° C; and g) obtaining the zeolite adsorbent according to the invention by activating the agglomerates obtained in step f) under oxidizing and / or inert gaseous flushing, with in particular gases such as oxygen, nitrogen, air , a dry air and / or decarbonated oxygen-depleted air, optionally dry and / or decarbonated, at a temperature between 100 ° C and 400 ° C, preferably between 200 ° C and 300 ° C.
[0010]
10. The method of claim 9, wherein the agglomeration binder used in step a) contains at least one zeolitic clay, preferably selected from the family of kaolin, kaolinites, nacrites, dickites, halloysites and metakaolins, and their mixtures. 3028431 - 35 -
[0011]
The process according to claim 9 or 10, wherein the FAU zeolite crystals used in the agglomeration step (step a) have a number average diameter of between 1 μm and 20 μm, inclusive, and preferably between 1.5 pm and 20 pm inclusive, more preferably between 1.8 pm and 10 pm inclusive, more preferably between 2 pm and 10 pm inclusive, and more preferably between 2 pm and 8 pm , terminals included.
[0012]
12. A process according to any one of claims 9 to 11, wherein the FAU zeolite used in step a) is a hierarchically porous FAU zeolite.
[0013]
13. Use of an adsorbent according to any one of claims 1 to 8 or prepared according to one of claims 9 to 12, as adsorption agent in: - the separation of C8 aromatic isomer sections and in particular of xylenes, - the separation of isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, and others, - the separation of cresols, - the separation of polyhydric alcohols, such as sugars. 20
[0014]
14. Process for separating the isomers of xylenes in the gas phase or in the liquid phase using at least one adsorbent according to any one of claims 1 to 8 or prepared according to one of claims 9 to 12.
[0015]
15. The separation process according to claim 14, which is a process for separating paraxylene from a feedstock to be treated with cuts of aromatic isomers with 8 carbon atoms, using as paraxylene adsorption agent a adsorbent according to any one of claims 1 to 8 or prepared according to one of claims 9 to 12. 30
[0016]
16. The method of claim 15 implemented in a simulated moving bed adsorption unit countercurrent simulated under the operating conditions: - number of beds: 4 to 24; - number of zones: at least 4 operating zones, each located between a feed point and a draw point; Temperature ranging from 100 to 250 ° C; Pressure between the bubble pressure of the xylenes (or toluene when toluene is chosen as the desorbent) at the process temperature and 3 M Pa; - Desorbent flow rate report on charge to be treated: 0.7 to 2.5; recycling rate between 2 and 12, preferably between 2.5 and 6.5 cycle times, corresponding to the time between two injections of desorbent on a given bed: between 4 and 25 min.
[0017]
17. The process according to claim 16, wherein the desorbent is toluene or para-diethylbenzene.
[0018]
18. The method of claim 16 or claim 17, wherein the water content in the incoming streams consisting of charge and / or desorbent streams is adjusted between 20 ppm and 150 ppm. 10

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优先权:

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申请号 | 申请日 | 专利标题

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FR1460955A|FR3028431B1|2014-11-13|2014-11-13|ZEOLITHIC ADSORBENTS BASED ON LOW BLEED ZEOLITHEX X WITH LOW EXTERNAL SURFACE, PREPARATION METHOD AND USES THEREOF|FR1460955A| FR3028431B1|2014-11-13|2014-11-13|ZEOLITHIC ADSORBENTS BASED ON LOW BLEED ZEOLITHEX X WITH LOW EXTERNAL SURFACE, PREPARATION METHOD AND USES THEREOF|

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US15/526,081| US10112173B2|2014-11-13|2015-11-13|Zeolite-based adsorbents based on zeolite X with a low binder content and a low outer surface area, process for preparing them and uses thereof|

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TW104137611A| TWI589353B|2014-11-13|2015-11-13|Zeolite-based adsorbents based on zeolite x with a low binder content and a low outer surface area, process for preparing them and uses thereof|

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KR1020177015925A| KR20170083116A|2014-11-13|2015-11-13|Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof|

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EP15797923.8A| EP3218100B1|2014-11-13|2015-11-13|Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof|

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JP2017525947A| JP6660386B2|2014-11-13|2015-11-13|Zeolite-based adsorbent material containing zeolite X as a main component having a low binder content and a small external surface area, method for preparing zeolite-based adsorbent material, and use of zeolite-based adsorbent material|

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PCT/EP2015/076531| WO2016075280A1|2014-11-13|2015-11-13|Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof|

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CN201580061488.1A| CN107107026B|2014-11-13|2015-11-13|Zeolite adsorbents made from X zeolite with low binder content and low external surface area, method for the production thereof and use thereof|