Zeolite sorbents for separating hydrocarbon isomers

Description

FIELD OF THE INVENTION

[0001] The invention relates to the field of zeolite adsorbents in the form of agglomerates comprising faujasite-type zeolite, for the separation of gaseous or liquid mixtures of aromatic hydrocarbons, and relates more particularly to processes for the separation of xylenes and in particular processes for the separation of para -xylene with improved productivity.

[0002] The present invention also relates to a process for separating gaseous or liquid mixtures of isomers with improved productivity, and more particularly to a process for separating xylene isomers with improved productivity for the production of para -highly pure xylene from an aromatic hydrocarbon feedstock containing 8-carbon isomers. PRIOR TECHNIQUE

[0003] The use of zeolite adsorbents consisting of Faujasite (FAU) zeolites of type X or Y comprising, in addition to sodium cations, barium, potassium or strontium ions, alone or in mixtures, to selectively adsorb the para -xylene in a mixture of aromatic hydrocarbons, is well known in the prior art.

[0004] Patents US3558730, US3558732, US3626020 and US3663638 show that zeolite adsorbents comprising sodium and barium based aluminosilicates (US3960774) or sodium, barium and potassium based, are effective for the separation of para -xylene present in C8 aromatic cuts (cuts comprising aromatic hydrocarbons with 8 carbon atoms).

[0005] The adsorbents described in patent US3878127 are used as adsorption agents in liquid phase processes, preferably of the simulated countercurrent type, similar to those described in patent US2985589 and which apply, among others, to C8 aromatic cuts.

[0006] The invention aims to improve the productivity of the preparation processes of para -xylene and in particular liquid phase processes, preferably of the simulated counter-current type for the separation of xylene isomers from C8 aromatic feedstocks. It has been surprisingly observed that this productivity can be improved by the judicious choice of the characteristics of the zeolitic adsorbent agglomerates used in this type of process.

[0007] Simulated moving bed separation is understood here in the broad sense, i.e. it can be a simulated counter-current moving bed, a simulated co-current moving bed, or a so-called "Varicol" process. The Varicol process proposed by Ludemann-Hombourger (O. Ludemann-Hombourger, R. Nicoud, 2000) and later developed by the company Novasep, allows for non-synchronized movement of the injection and withdrawal points (Bailly, et al. 2004). The lengths of the four zones can be adjusted during the cycle by limiting the number of beds required to achieve separation.

[0008] The common characteristic of this family of processes is that the zeolite adsorbent agglomerate (or more simply "adsorbent solid") is used in a fixed bed, and that the liquid flows in contact with the adsorbent solid are managed either by means of a set of "on / off" valves, or by means of a single complex valve known as a rotary valve.

[0009] When the active element of the adsorbent solids used as adsorption agents in these processes is a zeolite, the latter, obtained in the form of crystals, is preferably used on an industrial scale in the form of agglomerates. These zeolite adsorbents, agglomerated in the form of platelets, beads or extrudates, are generally made up of zeolite crystals, which constitute the active element in the sense of adsorption and a binder intended to ensure the cohesion of the crystals in the form of agglomerates. This binder also gives the agglomerates sufficient mechanical strength to withstand the mechanical stresses to which they are subjected during their implementation within the units. These mechanical stresses are the cause of the formation of "fines", which induce a deterioration in performance during the operation of the process.

[0010] The process of separating xylenes in a simulated moving bed (SMB) has seen numerous technological improvements, particularly in the fluid distribution trays, but relatively little development concerning the intrinsic characteristics of the adsorbent solid.

[0011] Adsorbents for the separation of xylenes having improved transfer properties for the separation of xylenes are for example described in international application WO2008009845 which describes adsorbents based on zeolite X, with small crystals, of size less than 1.7 µm, with an atomic ratio Si / Al, such that 1.15 < Si / Al ≤ 1.5, exchanged with barium, and possibly with potassium, in international application WO2014090771, which describes agglomerated zeolite adsorbents, with optimized properties, in particular for the separation of para -xylene from C8 aromatic cuts. These adsorbents exhibit maximum selectivity properties towards para-xylene and mass transfer, while presenting maximum mechanical resistance associated with an optimized adsorption capacity.

[0012] International application WO2018002174 proposes zeolite adsorbents in the form of agglomerates with optimized properties for the separation of gaseous or liquid mixtures of isomers and more particularly for the separation of xylenes, in gas phase or in liquid phase, in particular para -xylene of C8 aromatic cuts. The zeolite adsorbents of the invention notably exhibit maximum selectivity properties with respect to the para -xylene and mass transfer, while exhibiting improved strength and high adsorption capacity per adsorbent volume and are particularly suitable for use in a separation process of para -xylene in liquid phase, preferably simulated countercurrent type.

[0013] In particular, this application teaches that it is not desirable to greatly increase the macroporosity and / or mesoporosity, therefore the grain porosity because this porosity does not participate in the adsorption capacity. The optimization of diffusion properties and optimal adsorption capacities were obtained by specifically selecting both the porosity and the tortuosity factor.

[0014] Patent application US2009 / 0326308 describes a separation process using an adsorbent with a low binder content and based on nanometric-sized X-type faujasite crystals, typically with an average size of less than 500 nm. Patent application DE 10 2018 109701 A1 discloses an agglomerated zeolite adsorbent, comprising at least one faujasite zeolite with an Si / Al atomic ratio of between 1.00 and 1.50, characterized in that the grain porosity of said adsorbent is preferably at least 35%; said adsorbent comprises zeolite crystals with a diameter of between 0.1 µm and 20 µm, and is in the form of beads.

[0015] In the process of separation of xylenes by adsorption in a simulated moving bed, the zeolite adsorbent is brought into contact with the liquid feed stream (charge) most often comprising mixtures of C8 hydrocarbons, and generally and most often mixtures of xylene isomers and more particularly mixtures of ortho -xylene, meta -xylene, para -xylene and ethylbenzene.

[0016] By using a zeolite adsorbent based on zeolite with a faujasite structure and a Si / Al ratio of between 1.0 and 1.5 (LSX, MSX, X zeolites) exchanged with barium or exchanged predominantly with barium and to a lesser extent with potassium, the para -xylene is then adsorbed in the micropores of the zeolite preferentially compared to all the other hydrocarbon compounds present in the feed stream. The phase adsorbed in the micropores of the zeolite is then enriched in para-xylene compared to the initial mixture constituting the feed stream. The liquid phase is conversely enriched in compounds such as, ortho -xylene, meta -xylene and ethylbenzene in a greater relative proportion than that characterizing the initial mixture constituting the feed stream.

[0017] The liquid phase is removed from contact with the adsorbent, thus forming a raffinate stream. The adsorbed phase, enriched in para -xylene, is desorbed under the action of a desorbent flow, and removed from contact with the adsorbent, thus forming an extract flow.

[0018] In the process of separating xylenes by simulated moving bed adsorption, the zeolitic adsorbent solid is used in one or two multi-stage columns to be brought into contact with the liquid flow. A multi-stage column is a column consisting of a multiplicity of trays arranged along a substantially vertical axis, each tray supporting a bed of granular solid, and the various successive beds being crossed in series by the fluid(s) used in the column. Between two successive beds is located a fluid distribution device for feeding each bed of granular solid.

[0019] Generally speaking, the operation of a simulated moving bed column can be described as follows: A column has at least four zones, and possibly five or six, each of these zones being made up of a certain number of successive beds, and each zone being defined by its position between a feed point and a draw point. Typically, a CCS unit for the production of para -xylene is fed with at least one feed F to be fractionated (aromatic hydrocarbon feed consisting of isomers with 8 carbon atoms) and a desorbent D, sometimes called eluent (generally para- diethylbenzene or toluene), and at least one raffinate R containing the least selectively adsorbed feed products and desorbent and an extract E containing the most adsorbed feed product and desorbent are withdrawn from said unit.

[0020] Other injection and withdrawal points can be added in order to rinse the distribution circuits, as described for example in patent US7208651. The addition of these additional rinsing flows does not change the operating principle of the CCS in any way, for the sake of brevity, we will not add these additional injection and withdrawal points in the description of the method according to the invention.

[0021] The feed and draw-off points are modified over time, shifted in the same direction by a value corresponding to a bed. The shifts of the different injection or draw-off points can be either simultaneous or non-simultaneous as taught in patent US6136198. The process according to this second mode of operation is called Varicol.

[0022] Conventionally, 4 different chromatographic zones are defined in a column operating in simulated countercurrent (CCS). Zone 1: desorption zone of the most adsorbed feed product, between the injection of desorbent D and the extraction of extract E. Zone 2: desorption zone of the least selectively adsorbed feed products, between the extraction of extract E and the injection of the feed to be fractionated F. Zone 3: adsorption zone of the most adsorbed feed product, between the injection of the feed and the withdrawal of raffinate R. Zone 4: zone located between the withdrawal of raffinate R and the injection of desorbent D.

[0023] To increase the productivity of the separation process, the prior art teaches that one way consists of improving the overall transfer in the zeolite adsorbent agglomerate and in particular by reducing the size of the crystals and / or the average size of said agglomerates.

[0024] Prior art documents describing pharmaceutical separation processes (Gomes et al., (2006), Adsorption, vol. 12, p. 375 sqq.) report liquid chromatographic separation processes using agglomerates from a few tens of micrometers to 100 µm.

[0025] In these processes using very small adsorbents, the pressure drop ΔP is high. In xylene separation processes, such pressure drop levels ΔP are not common. However, it is surprisingly noted that the pressure drop ΔP is not a design criterion. It will have an impact in particular on the thickness of the adsorber walls and on the power of the installations.

[0026] Another characteristic of the zeolite adsorbent agglomerate is the hydration rate of said agglomerate. Maintaining the hydration of the zeolite at the desired value, for example a loss on ignition of 4% to 7.7% for zeolite X, MSX or LSX, when used in the process for separating xylenes by simulated moving bed adsorption, is ensured by adding water to the feed and / or desorbent feed streams. The addition of water required for such loss on ignition levels is such that the water content by weight in the hydrocarbon effluents (the extract or raffinate stream) is most often between 0 ppm and 150 ppm, and more generally between 40 ppm and 150 ppm, when the adsorbent is based on zeolite X, MSX or LSX.

[0027] However, it is still necessary to increase the productivity of the process in general.

[0028] The present invention thus has as its first object to propose a zeolitic adsorbent in the form of agglomerates with optimized properties for the separation of gaseous or liquid mixtures of isomers and more particularly for the separation of xylenes, in gas phase or in liquid phase, in particular for the separation of para -xylene from C8 aromatic cuts. The zeolitic adsorbent agglomerates of the invention notably exhibit maximum selectivity properties with respect to para -xylene and mass transfer, while exhibiting high mechanical strength and adsorption capacity and are particularly suitable for use in a separation process of para -xylene in liquid phase, preferably simulated countercurrent type.

[0029] The present invention proposes for this purpose an agglomerated adsorbent, preferably based on faujasite zeolite with an Si / Al atomic ratio of between 1.00 and 1.50, and whose grain porosity is advantageously between 25% and 45%, allowing the production of para-high purity xylene with improved productivity, while avoiding performance degradation over time.More specifically, the invention relates to a zeolitic agglomerated adsorbent, comprising at least one faujasite zeolite with an Si / Al atomic ratio of between 1.00 and 1.50 inclusive (FAU-X) and preferably comprising barium and optionally potassium, in which on the one hand the grain porosity is between 25% and 45%, preferably between 30% and 45%, more preferably between 32% and 45% and very preferably between 35% and 45%, particularly advantageously between 36% and 45%, inclusive, and on the other hand in that the standard deviation σ of the crystal size distribution in said agglomerate is less than 0.30 µm, preferably between 0.05 µm and 0.30 µm, more preferably between 0.05 µm and 0.28 µm, and most preferably between 0.1 µm and 0.28 µm, most preferably between 0.1 µm and 0.25 µm, inclusive. SUMMARY OF THE INVENTION

[0030] Thus, and according to a first aspect, the invention relates to an agglomerated zeolite adsorbent, comprising at least one faujasite zeolite with an Si / Al atomic ratio of between 1.00 and 1.50 inclusive (FAU-X) and comprising barium and optionally potassium, characterized on the one hand in that the grain porosity of said adsorbent is between 25% and 45%, preferably between 30% and 45%, more preferably between 32% and 45% and very preferably between 35% and 45%, particularly advantageously between 36% and 45%, inclusive, and on the other hand in that the standard deviation σ of the crystal size distribution in said agglomerate is less than 0.30 µm, preferably between 0.05 µm and 0.30 µm, more preferably between 0.05 µm and 0.28 µm, and most preferably between 0.1 µm and 0.28 µm, most preferably between 0.1 µm and 0.25 µm, limits included,said adsorbent comprising zeolite crystals with a number-average diameter of between 100 nm and 1200 nm and the mass fraction of FAU zeolite being greater than or equal to 80% relative to the total weight of adsorbent.,

[0031] According to one embodiment, the agglomerated zeolite adsorbent according to the invention comprises zeolite crystals with a number-average diameter of between 400 nm and 1200 nm, more preferably between 500 nm and 1200 nm, most preferably between 550 nm and 1200 nm, very advantageously between 600 nm and 1200 nm, inclusive.

[0032] According to another embodiment, the agglomerated zeolite adsorbent according to the invention is in the form of beads with an average diameter of between 100 µm and 1000 µm, preferably between 100 µm and 600 µm, more preferably 200 µm and 550 µm, limits included.

[0033] In a preferred embodiment, said at least one FAU-X zeolite of the agglomerated zeolite adsorbent according to the invention has an Si / Al atomic ratio of between 1.05 and 1.50, preferably between 1.05 and 1.40, inclusive, and even more preferably between 1.10 and 1.40 inclusive.

[0034] In another preferred embodiment of the invention, no zeolite structure other than the faujasite structure, preferably no zeolite structure other than the faujasite X structure, is detected by X-ray diffraction, in the agglomerated zeolite adsorbent according to the invention.

[0035] The agglomerated zeolite adsorbent according to the invention comprises one or more alkali or alkaline-earth ion(s), preferably chosen from sodium, barium and potassium.

[0036] According to a preferred embodiment, the barium content, expressed as barium oxide (BaO) in the agglomerated zeolite adsorbent according to the invention is greater than 10%, more preferably greater than 15%, very preferably greater than 20%, even more preferably greater than 23%, or even greater than 33% by weight relative to the total mass of the adsorbent, and advantageously, said 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.

[0037] According to another preferred embodiment, the potassium content, expressed as potassium oxide (K 2 O) in the agglomerated zeolite adsorbent according to the invention is less than 25%, preferably between 0 and 20%, even more preferably between 0 and 15%, limits included, by weight relative to the total mass of the adsorbent.

[0038] In one embodiment of the present invention, the loss on ignition of the agglomerated zeolite adsorbent according to the invention, measured at 900°C according to standard NF EN 196-2, is less than or equal to 7.7%, preferably between 0 and 7.7%, more preferably between 3.0% and 7.7%, more preferably between 3.5% and 6.5% and advantageously between 4.5% and 6%, limits included.

[0039] According to another aspect, the present invention relates to the use of the agglomerated zeolite adsorbent as just described in the methods of: separation of C8 aromatic isomer cuts and in particular xylenes, and more particularly para -xylene, separation of substituted toluene isomers such as nitrotoluene, diethyltoluene, toluenediamine, and others, separation of cresols, separation of polyhydric alcohols.

[0040] Finally, and according to yet another aspect, the present invention relates to the method of separating para -xylene from 8-carbon aromatic isomer cuts, using as adsorption agent para -xylene, an agglomerated zeolite adsorbent as defined previously and more precisely in the remainder of this presentation.

[0041] The process of separation of para -xylene from isomeric cuts of aromatic hydrocarbons containing 8 carbon atoms, of the present invention, is conducted in the gas phase or in the liquid phase, preferably in the liquid phase, by adsorption of the para -xylene in the presence of a desorbent, said desorbent preferably being chosen from toluene and para -diethylbenzene.

[0042] According to a preferred embodiment, the method of separating para- xylene according to the present invention, is a simulated moving bed type process, more preferably of the simulated countercurrent type. DESCRIPTION OF EMBODIMENTS

[0043] The zeolite adsorbent of the invention preferably comprises both macropores, mesopores and micropores. By "macropores" is meant pores whose opening is greater than 50 nm, preferably between 50 nm and 400 nm. By "mesopores" is meant pores whose opening is between 2 nm and 50 nm, limits not included. By "micropores" is meant pores whose opening is less than 2 nm.

[0044] As indicated previously, the adsorbent according to the present invention is in the form of an adsorbent whose grain porosity is between 25% and 45%, preferably between 30% and 45%, more preferably between 32% and 45%, very preferably between 35% and 45%, and particularly advantageously between 36% and 45% inclusive. Furthermore, the standard deviation σ of the crystal size distribution in said adsorbent is less than 0.30 µm, preferably between 0.05 µm and 0.30 µm, more preferably between 0.05 µm and 0.28 µm, and most preferably between 0.10 µm and 0.28 µm, most preferably between 0.10 µm and 0.25 µm, inclusive. Said adsorbent comprises zeolite crystals with a number average diameter of between 100 nm and 1200 nm, and the mass fraction of zeolite FAU is greater than or equal to 80% relative to the total weight of adsorbent.

[0045] Indeed, the inventors surprisingly discovered that when the standard deviation σ of the crystal size distribution in the zeolite adsorbent is greater than 0.30 µm, a drastic drop in productivity is observed in a separation process of para -xylene, particularly in a liquid phase separation process, countercurrent in a simulated moving bed.

[0046] It was also surprisingly observed that this productivity value reaches a maximum for values ​​of standard deviation σ of the crystal size distribution in the zeolite adsorbent agglomerate lower than 0.30 µm. This standard deviation σ value appears to correspond to an optimized grain porosity. Indeed, it was also quite surprisingly observed that the grain porosity is inversely proportional to the standard deviation σ of the crystal size distribution in the zeolite adsorbent agglomerate. Thus, the more the standard deviation σ decreases, the more the grain porosity increases. However, excessive grain porosity leads to completely undesired effects, such as, for example, loss of adsorption capacity, loss of mechanical strength, and others.

[0047] Therefore, the person skilled in the art who wishes to achieve maximum productivity finds, thanks to the present invention, a compromise between the porosity of the grain and the standard deviation σ of the crystal size distribution in the zeolite adsorbent agglomerate. Thanks to the agglomerated adsorbent according to the invention, it is thus possible to achieve maximum productivity in xylenes separation processes.

[0048] Advantageously, the agglomerated zeolite adsorbent is in the form of beads with an average diameter of between 100 µm and 1000 µm, preferably between 100 µm and 600 µm, more preferably 200 µm and 550 µm, limits included.

[0049] Preferably, the faujasite-based zeolite adsorbent according to the invention comprises barium and optionally potassium.

[0050] According to yet another embodiment of the invention, the zeolite adsorbent has a barium content, expressed as barium oxide (BaO) greater than 10%, preferably greater than 15%, very preferably greater than 20%, even more preferably greater than 23%, or even greater than 33% by weight relative to the total mass of the adsorbent. 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.

[0051] According to another embodiment of the invention, the zeolite adsorbent may have a potassium content, expressed as potassium oxide K 2 O, of less than 25%, preferably between 0 and 20%, even more preferably between 0 and 15%, limits included, by weight relative to the total mass of the adsorbent.

[0052] According to another embodiment of the invention, the total content of alkali or alkaline-earth ions other than barium and potassium, expressed as oxides of alkali or alkaline-earth ions other than barium oxide BaO and potassium oxide K 2 O is between 0 and 5%, limits included, relative to the total mass of the adsorbent.

[0053] Preferably, the zeolite adsorbent according to the present invention is an adsorbent based on FAU zeolite(s), generally referred to as type X zeolite. By "zeolite X" is meant a zeolite whose Si / Al atomic ratio is between 1.00 and 1.50 inclusive, preferably between 1.00 and 1.40, inclusive.

[0054] Among the X zeolites, it is now commonly accepted to recognize two subgroups called LSX zeolites and MSX zeolites. LSX zeolites have an atomic ratio of Si / Al equal to about 1, i.e. 1.00 ± 0.05, and MSX zeolites have an atomic ratio of Si / Al between about 1.05 and about 1.15, excluding limits.

[0055] According to a preferred embodiment of the present invention, zeolite X has an Si / Al atomic ratio of between 1.15 and 1.50, inclusive. According to another preferred embodiment, zeolite X is an LSX type zeolite with an Si / Al atomic ratio equal to approximately 1, i.e. 1.00 ± 0.05. It may also be envisaged that the adsorbent contains mixtures of two or more types of zeolites X as just defined.

[0056] According to a preferred embodiment, said at least one FAU zeolite included in the zeolite adsorbent agglomerate of the invention has an Si / Al atomic ratio of between 1.00 and 1.50 inclusive, preferably between 1.05 and 1.40 and even more preferably between 1.10 and 1.40. Preferably, said at least one FAU zeolite is an X zeolite.

[0057] 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 (known to those skilled in the art by the acronym DRX) in the zeolite adsorbent agglomerate of the present invention.

[0058] The mass fraction of FAU zeolite, the FAU zeolite preferably being an X zeolite, is greater than or equal to 80% relative to the total weight of adsorbent of the present invention, the remainder to 100% preferably consisting of non-zeolitic phase.

[0059] The zeolite adsorbent agglomerates according to the present invention may contain a non-zeolitic phase (NZP), i.e. a non-crystalline phase which is essentially inert with respect to adsorption. The degree of crystallinity (mass fraction of zeolite) of the adsorbent according to the invention can be measured by X-ray diffraction analysis, known to those skilled in the art by the acronym DRX.

[0060] The zeolitic adsorbent agglomerate of the invention is in the form of an agglomerate, that is to say that it is made up of crystalline elements (or crystals) of at least one FAU zeolite as defined above, said crystalline elements (or more simply "crystals") having a number-average diameter of between 100 nm and 1200 nm, more preferably between 400 nm and 1200 nm, more preferably between 500 nm and 1200 nm, most preferably between 550 nm and 1200 nm, very advantageously between 600 nm and 1200 nm, limits included. METHODS OF IMPLEMENTATION

[0061] The zeolitic adsorbent agglomerates according to the present invention can be prepared by adapting the operating methods already known to those skilled in the art, and as described for example in the documents WO2014090771, WO2018002174, US2009 / 0326308 previously cited and by selecting and adjusting the synthesis parameters making it possible to obtain the agglomerates having the desired values ​​of grain porosity and standard deviation o.

[0062] A method for synthesizing the zeolite adsorbent agglomerate according to the present invention may, for example, comprise at least the steps of: a) agglomeration of crystals of at least one FAU-X type zeolite, with a binder comprising at least 80% clay or a mixture of zeolithizable clay(s), and with possibly up to 5% additives as well as with the quantity of water which allows the shaping of the agglomerated material; drying of the agglomerates at a temperature between 50°C and 150°C; calcination of the dried agglomerates under oxidizing and / or inert gas sweeping, in particular with gases such as oxygen, nitrogen, air, dry and / or decarbonated air, oxygen-depleted air, possibly dry and / or decarbonated, at a temperature above 150°C, typically between 180°C and 800°C, preferably between 200°C and 650°C, b) zeolitization of all or part of the binder by bringing the agglomerates obtained in step a) into contact with an alkaline basic solution,c) cation exchange(s) of the agglomerates from step a) and / or step b) by contacting with a solution of barium ions and / or potassium ions, d) optional additional cation exchange of the agglomerates from step c) by contacting with a solution of potassium ions, e) washing and drying the agglomerates obtained in steps c) or d), at a temperature between 50°C and 150°C, and f) activation by heating to a temperature generally between 100°C and 400°C, preferably between 200°C and 300°C then recovery of the zeolitic agglomerated adsorbent.

[0063] The zeolite crystals that can be used in step a) of synthesis above can advantageously be synthesized according to the known operating methods available in the scientific literature or the patent literature, as well as on the internet. In particular, the zeolite crystals can be prepared as described in documents CN1191118C, or WO2014090771, or US7812208 B2, US2009326308 and US2007224113.

[0064] The parameters which can make it possible to control the standard deviation σ in the zeolitic adsorbent agglomerate of the present invention are, for example, the very nature of the crystals used in step a), in particular the size and the standard deviation of said crystals, but also the zeolitization conditions of the agglomeration binder, such as, for example, the temperature, the duration, the pH of the alkaline zeolitization solution, or even the duration, the stirring mode, the shear rate, pressure, and others.

[0065] More specifically, by "nature of the crystals used in step a)", we mean in particular the standard deviation of said crystals which can for example be controlled by adjusting the synthesis parameters, and in particular the synthesis temperature, the stirring speed, the shear rate, as indicated for example in documents WO2009081022 or US2009326308.

[0066] The synthesis parameters that can make it possible to control the porosity of the zeolitic adsorbent agglomerate of the invention are also known to those skilled in the art. Generally, these parameters include, but are not limited to, the binder content, the type of agglomeration (by extrusion, atomization, granulation, etc.), the humidity content, the nature of the binder, the zeolitization conditions (temperature, duration, pH of the alkaline zeolitization solution, duration, stirring mode, shear rate, pressure and other).

[0067] According to a preferred embodiment, the synthesis of the zeolitic adsorbent agglomerate of the present invention does not include the addition of a pore-forming agent, the presence of a pore-forming agent being able to lead in particular to a degradation of the crystallinity.

[0068] It is also possible to prepare said crystalline elements by synthesis by seeding and / or by adjusting the operating conditions of synthesis such as the SiO 2 / Al 2 O 3 ratio, the sodium content and the alkalinity of the synthesis mixture.

[0069] The synthesis of FAU type zeolite is generally carried out in a sodium medium (cation Na + < ). The crystalline elements of FAU zeolite thus obtained comprise mainly, or even exclusively, sodium cations. However, it would not be outside the scope of the invention to use crystalline elements having undergone one or more cationic exchanges, between the synthesis in sodium form.

[0070] The size of the FAU zeolite crystals used in step a) and of the FAU zeolite crystalline elements in the agglomerates according to the invention is measured by observation under a scanning electron microscope (SEM). As indicated above, the average diameter of the crystals is between 100 nm and 1200 nm, more preferably between 400 nm and 1200 nm, more preferably between 500 nm and 1200 nm, most preferably between 550 nm and 1200 nm, very advantageously between 600 nm and 1200 nm, inclusive.

[0071] This SEM observation also makes it possible to confirm the presence of a non-zeolitic phase including, for example, residual binder (not converted during the zeolitization step) or any other amorphous phase in the agglomerates.

[0072] In this document, the term "number-average diameter" or "size" is used, particularly for crystalline zeolite elements and for zeolite adsorbents. The method for measuring these quantities is explained later in the description.

[0073] Agglomeration and shaping (step a) can be carried out using any technique known to those skilled in the art, such as extrusion, compaction, agglomeration on a granulating plate, granulating drum, atomization and others.

[0074] The proportions of agglomeration binder (see definition below) and zeolite used are typically those of the prior art, i.e. 5 parts to 20 parts by weight of binder for 95 parts to 80 parts by weight of zeolite.

[0075] The agglomerates resulting from step a), whether in the form of balls, extrudates or others, generally have a number average diameter, or their length (largest dimension when they are not spherical), of between 100 µm and 1000 µm, preferably between 100 µm and 600 µm, more preferably 200 µm and 550 µm, limits included.

[0076] At the end of step a), the finest agglomerates can be removed by cycloning and / or screening and / or the overly coarse agglomerates by screening or crushing, in the case of extrudates, for example.

[0077] The agglomeration binder used in step a) comprises, and preferably consists of, a clay or a mixture of clays. These clays are preferably chosen from kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in any proportions.

[0078] In the case of the zeolitization step, the agglomeration binder used in step a) contains at least 80%, preferably at least 90%, more preferably at least 95%, more particularly at least 96%, by weight, of at least one zeolitizable clay and may also contain other mineral binders such as bentonite, attapulgite, and others. By zeolitizable clay, is meant a clay or a mixture of clays which are capable of being converted into zeolitic material, most often by the action of an alkaline basic solution. The zeolitizable clay generally belongs to the family of kaolins (such as for example kaolinites, nacrites, dickites, halloysites) and / or metakaolins.

[0079] Among the additives possibly used in step a), there may be found a source of silica of any type known to those skilled in the art, specialists in the synthesis of zeolites, for example colloidal silica, diatoms, perlite, calcination ash (“fly ash” in English), sand, or any other form of solid silica.

[0080] In step a), in addition to the FAU zeolite crystalline elements and the binder, other additives may also be added, for example additives intended to facilitate agglomeration or to improve hardening, as well as other additives known to those skilled in the art.

[0081] Particularly if the agglomeration binder contains one or more zeolithizable clays, calcination makes it possible to transform the zeolithizable clay, typically kaolin, into meta-kaolin which can then be converted into zeolite during the zeolitization step (step b)). The principle is explained in "Zeolite Molecular Sieves" by DW Breck, John Wiley and Sons, New York, (1973), pp. 314-315.

[0082] The zeolitization of the agglomeration binder is carried out according to any method now well known to those skilled in the art and can, for example, be carried out by immersing the product resulting from step a) in a basic alkaline solution, generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.

[0083] As a general rule, the concentration of the alkaline zeolitization solution is preferably between 0.5 M and 5 M. Zeolitization is preferably carried out hot, at a temperature above room temperature, and typically at temperatures of the order of 80°C to 100°C. The duration of the zeolitization process is generally between a few tens of minutes and a few hours, preferably between approximately 1 hour and 8 hours.

[0084] Preferably, and in order to ensure complete zeolitization of the binder without altering the crystallinity of the zeolite crystals present, it is preferable to bring the adsorbents into contact with a cold sodium hydroxide solution and then carry out a gradual increase in temperature up to a temperature of 80°C-100°C.

[0085] Similarly, the sodium hydroxide concentration can be maintained at the same concentration or can be increased gradually in order to maintain maximum crystallinity of the initial crystals and ensure maximum conversion of the zeolithizable binder.

[0086] The cation exchange steps c) and d) are carried out according to conventional methods known to those skilled in the art, and most often by bringing the agglomerates resulting from step a) into contact with a barium and / or potassium salt, such as barium chloride (BaCl 2 ) and / or potassium chloride (KCl), in aqueous solution at a temperature between room temperature and 100°C, and preferably between 80°C and 100°C in order to rapidly obtain high barium contents, expressed as barium oxide, i.e. preferably greater than 10%, preferably greater than 15%, very preferably greater than 20%, even more preferably greater than 23%, or even greater than 33% by weight relative to the total mass of the adsorbent.

[0087] Advantageously, the barium content, expressed as barium oxide, is between 23% and 42%, and typically between 30% and 40%, inclusive, 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.

[0088] The possible exchange with potassium (step d) can be carried out before and / or after the exchange with barium (step c). As indicated previously, it is also possible to agglomerate in step a) crystalline elements of FAU zeolite 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, with barium or potassium or barium and potassium ions before step a) and to avoid (or not) steps c) and / or d).

[0089] After the cation exchange step(s), washing is then carried out, generally and preferably with water, followed by drying of the agglomerate thus obtained.

[0090] The activation which follows the drying is carried out in a conventional manner, according to methods known to those skilled in the art, for example at a temperature generally between 100°C and 400°C, preferably between 200°C and 300°C for a duration determined according to the desired water content and loss on ignition, typically from 1 hour to 6 hours. CHARACTERIZATION TECHNIQUES Grain size of zeolite crystals:

[0091] The estimation of the number-average diameter of the elements (i.e. crystals) of FAU-type zeolite used in step a) and of the elements (i.e. crystals) of X zeolite contained in the agglomerates is carried out by observation under a scanning electron microscope (SEM).

[0092] In order to estimate the size of the zeolite particles (i.e. crystals) on the samples, a set of images is taken at a magnification of at least 5000. The diameter of at least 200 particles is then measured using dedicated software, for example the Smile View software from the publisher LoGraMi. The accuracy is of the order of 3%. The measurement of the histogram formed from the said diameter measurements simultaneously allows the determination of the standard deviation σ of its distribution. Chemical analysis of zeolite adsorbent agglomerates - Si / Al ratio and exchange rate:

[0093] An elementary chemical analysis of the final product obtained at the end of steps a) to f) described above can be carried out using various analytical techniques known to those skilled in the art. These techniques include the X-ray fluorescence chemical analysis technique as described in standard NF EN ISO 12677: 2011 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 from Bruker.

[0094] X-ray fluorescence is a non-destructive spectral technique that exploits the photoluminescence of atoms in the X-ray range to establish the elemental composition of a sample. The excitation of atoms, generally by an X-ray beam or by bombardment with electrons, generates specific radiation after returning to the ground state of the atom. 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. A measurement uncertainty of less than 0.4% by weight is typically obtained after calibration for each oxide.

[0095] These elementary chemical analyses make it possible both to verify the Si / Al atomic ratio of the zeolite used in the agglomerate and the Si / Al atomic ratio of the final product obtained at the end of steps a) to f) described previously, and to verify the quality of the ion exchange described in step c) and in the optional step d). In the description of the present invention, the measurement uncertainty of the Si / Al atomic ratio is ± 5%.

[0096] The quality of the ion exchange is related to the number of moles of sodium oxide, Na 2 O, remaining in the zeolite agglomerate after exchange. More precisely, the exchange rate by barium ions is estimated by evaluating the ratio between the number of moles of barium oxide, BaO, and the number of moles of the whole (BaO + Na 2 O). Similarly, the exchange rate by barium and / or potassium ions is estimated by evaluating the ratio between the number of moles of the whole barium oxide + potassium oxide (BaO + K 2 O) and the number of moles of the whole (BaO + K 2 O + Na 2 O). It should be noted that the contents of different oxides are given as a percentage by weight relative to the total weight of the anhydrous zeolite adsorbent. Particle size of zeolite adsorbents:

[0097] The determination of the number-average diameter of the zeolite adsorbents obtained from step a) of agglomeration and shaping is carried out by analyzing the particle size distribution of an agglomerate sample by imaging according to ISO 13322-2:2006, using a conveyor belt allowing the sample to pass in front of the camera lens.

[0098] The number-average diameter is then calculated from the particle size distribution by applying ISO 9276-2:2001. In this document, the term "number-average diameter" or "size" is used for zeolite agglomerates. The accuracy is of the order of 0.01 mm for the agglomerate size range of the invention. Mechanical resistance of zeolite adsorbents:

[0099] The crushing strength of a bed of zeolite adsorbents as described in the present invention is characterized according to the Shell method series SMS1471-74 (Shell Method Series SMS1471-74 “Determination of Bulk Crushing Strength of Catalysts. Compression-Sieve Method”), associated with the “BCS Tester” device marketed by the company Vinci Technologies. This method, initially intended for the characterization of catalysts from 3 mm to 6 mm, is based on the use of a 425 µm sieve which will in particular make it possible to separate the fines created during crushing. The use of a 425 µm sieve remains suitable for particles with a diameter greater than 1.6 mm, but must be adapted according to the particle size of the agglomerates that one seeks to characterize.

[0100] The agglomerates of the present invention, generally in the form of balls or extrudates, generally have a number average diameter or length, i.e. largest dimension in the case of non-spherical agglomerates, of between 0.2 mm and 2 mm, and in particular of between 0.2 mm and 0.8 mm and preferably of between 0.4 mm and 0.65 mm, inclusive. Therefore, a 100 µm sieve is used instead of the 425 µm sieve mentioned in Shell standard method SMS1471-74.

[0101] The measurement protocol is as follows: a 20 cm 3< sample of agglomerated adsorbents, previously sieved with the appropriate sieve (100 µm) and previously dried in an oven for at least 2 hours at 250°C (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 5 cm 3< bed of steel balls in order to better distribute the force exerted by the piston on the adsorbent agglomerates (use of 2 mm diameter balls for spherical particles with a diameter strictly less than 1.6 mm). The fines obtained at the different pressure stages are separated by sieving (appropriate sieve of 100 µm) and weighed.

[0102] Bed crushing strength is determined by the pressure in megapascals (MPa) at 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 to the adsorbent bed and interpolating to 0.5% by mass of cumulative fines. Bed crushing strength is typically between a few hundred kPa and a few tens of MPa and generally between 0.3 MPa and 3.2 MPa. Accuracy is typically less than 0.1 MPa. Non-zeolitic phase of zeolitic adsorbents:

[0103] The rate of non-zeolitic phase PNZ, for example non-zeolitized residual binder or any other amorphous phase, after zeolitization is calculated according to the following equation: PNZ = 100 − ∑ PZ where PZ represents the sum of the quantities of the zeolite fractions X within the meaning of the invention.

[0104] The quantity of zeolite fractions X (crystallinity rate) is measured by X-ray diffraction analysis, known to those skilled in the art by the acronym DRX. This analysis is carried out on a Bruker device, then the quantity of zeolite fractions X is evaluated using Bruker's TOPAS software. Microporous volume:

[0105] The crystallinity of the agglomerates is also assessed by measuring their micropore volume by comparing it to that of an appropriate reference (100% crystalline zeolite under identical cationic treatment conditions or theoretical zeolite). This micropore volume is determined from the measurement of the adsorption isotherm of gas, such as nitrogen, at its liquefaction temperature.

[0106] Prior to adsorption, the zeolite adsorbent is degassed between 300°C and 450°C for a period of between 9 hours and 16 hours, under vacuum (P < 6.7.10 -4< Pa). The measurement of the nitrogen adsorption isotherm at 77 K is then carried out on a Micromeritics ASAP 2020 M type device, taking at least 35 measurement points at relative pressures with a PIPa ratio between 0.002 and 1. Total volume of macropores and mesopores, and grain porosity:

[0107] The macroporous and mesoporous volumes Vma, Vme, grain density dg and porosity ε p, of macroporosity and mesoporosity type, are measured by mercury intrusion porosimetry. A Micromeritics Autopore ®< 9500 mercury porosimeter is used to analyze the distribution of the pore volume contained in the macropores and mesopores.

[0108] The experimental method, described in the operating manual of the device referring to the ASTM D4284-83 standard, consists of placing a sample of adsorbent (zeolite adsorbent in the form of agglomerates to be measured) (of known loss on ignition) previously weighed, in a cell of the porosimeter, then, after a preliminary degassing (evacuation pressure of 30 µm of mercury for at least 10 min), filling the cell with mercury at a given pressure (0.0036 MPa), and then applying an increasing pressure in stages up to 400 MPa in order to gradually penetrate the mercury into the porous network of the sample, taking at least 15 pressure stages up to 0.2 MPa, and then applying increments of 0.1 MPa up to 1 MPa, then 0.5 MPa up to 10 MPa, then 2 MPa up to 30 MPa, then 5 MPa up to 180 MPa, and finally 10 MPa up to 400 MPa.

[0109] The relationship between the applied pressure and the characteristic dimension of the pore inlet threshold (corresponding to an apparent pore diameter) is established using the Laplace-Young equation and assuming a cylindrical pore opening, a contact angle between mercury and the pore wall of 140° and a mercury surface tension of 485 dynes cm -1< . The volume increments ΔVi of mercury introduced at each pressure step Pi are recorded, which then allows the cumulative volume of mercury introduced to be plotted as a function of the applied pressure V(Pi), or as a function of the apparent pore diameter V(li). The value at which mercury fills all intergranular voids is set at 0.2 MPa, and it is assumed that beyond this value, mercury penetrates into the pores of the adsorbent.The grain volume Vg is then calculated by subtracting the cumulative volume of mercury at this pressure (0.2 MPa) from the volume of the porosimeter cell, and dividing this difference by the mass of the equivalent anhydrous adsorbent, i.e. the mass of said material corrected for loss on ignition. The grain density dg is the inverse of the grain volume Vg defined previously.

[0110] The macropore volume Vma of the adsorbent is defined as the cumulative volume of mercury introduced at a pressure between 0.2 MPa and 30 MPa, corresponding to the volume contained in pores with an apparent diameter greater than 50 nm. The mesoporous volume Vme of the adsorbent is defined as the cumulative volume of mercury introduced at a pressure between 30 MPa and 400 MPa. Since the mercury intrusion method of measuring the pore volume does not allow access to the micropore volume, the total pore volume Vtot as measured by mercury intrusion corresponds to the sum of the macropore volumes Vma and mesoporous volumes Vme.

[0111] In this document, the macroporous and mesoporous volumes Vma and Vme, as well as their sum (total pore volume Vtot), of the zeolite adsorbents, expressed in cm 3< g -1< , are thus measured by mercury intrusion porosimetry and reported to the mass of the sample in anhydrous equivalent, i.e. the mass of said adsorbent corrected for the loss on ignition. The grain density dg is expressed in g cm -3< and refers to the mass of the sample in anhydrous equivalent.

[0112] The grain porosity ε p of macroporosity and mesoporosity type, is the product of the grain density dg by the sum of the macroporous and mesoporous volumes Vma and Vme: ε p = dg × Vma + Vme Loss on ignition of zeolite adsorbents:

[0113] The loss on ignition is determined in an oxidizing atmosphere, by calcining the sample in air at a temperature of 900°C ± 25°C, following the procedure described in standard NF EN 196-2 (April 2006). The standard deviation of measurement is less than 0.1%. Examples Example 1: Preparation of agglomerates

[0114] Four adsorbents (Agglomerates 1, 3, 4, according to the invention, and Agglomerate 2, comparative) are prepared as described below, from a powder of faujasite zeolite of type X, the average crystal size of which is 0.6 µm. The respective standard deviations of these crystals are 0.25 µm, 0.30 µm, 0.35 µm and 0.50 µm. Preparation of Agglomerate 1 (according to the invention)

[0115] A homogeneous mixture is prepared and 800 g of zeolite crystals, with a standard deviation of 0.25 µm, are agglomerated with 160 g of kaolin (expressed as calcined equivalent) and 60 g of colloidal silica sold under the trade name Klebosol ™ < 30N50 (containing 30% by weight of SiO 2 and 0.5% by weight of Na 2 O) with the quantity of water which allows the extrusion of the mixture. The extrudates are dried, then calcined at 550°C (firing of the clay) under a stream of nitrogen for 2 hours, and finally crushed so as to recover agglomerates whose number average diameter is equal to 0.5 mm.

[0116] The agglomerates obtained as described above (20 g) are placed in a glass reactor equipped with a double jacket regulated at a temperature of 85°C ± 1°C, then 250 mL of an aqueous sodium hydroxide solution with a concentration of 1 M are added, and the reaction medium is left stirring for a period of 5 hours.

[0117] The agglomerates are then washed in 3 successive water washing operations followed by emptying the reactor. The effectiveness of the washing is ensured by measuring the final pH of the wash water, which is between 10.0 and 10.5.

[0118] The agglomerates are exchanged by contact with a 0.5 M barium chloride solution at 95°C in 4 steps. At each step, the volume ratio of solution to mass of solid is 20 mL / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times to remove excess salt. The agglomerates are then dried at 80°C for 2 hours and finally activated at 250°C for 2 hours under a stream of nitrogen. Preparation of Agglomerate 2 (comparison)

[0119] A homogeneous mixture is prepared and 800 g of zeolite crystals with a standard deviation of 0.50 µm are agglomerated with 145 g of kaolin (expressed as calcined equivalent) and 55 g of colloidal silica sold under the trade name Klebosol ™ < 30N50 (containing 30% by weight of SiO 2 and 0.5% by weight of Na 2 O) with the quantity of water that allows the extrusion of the mixture. The extrudates are dried, then calcined at 550°C (firing of the clay) under a stream of nitrogen for 2 hours, and finally crushed so as to recover agglomerates whose number average diameter is equal to 0.5 mm.

[0120] The agglomerates obtained as described above (20 g) are placed in a glass reactor equipped with a double jacket regulated at a temperature of 95°C ± 1°C, then 250 mL of an aqueous sodium hydroxide solution with a concentration of 1.25 M are added, and the reaction medium is left stirring for a period of 4 hours.

[0121] The agglomerates are then washed in 3 successive water washing operations followed by emptying the reactor. The effectiveness of the washing is ensured by measuring the final pH of the wash water, which is between 10.0 and 10.5.

[0122] The agglomerates are exchanged by contact with a 0.5 M barium chloride solution 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 to remove excess salt. The agglomerates are then dried at 80°C for 2 hours and finally activated at 250°C for 2 hours under a stream of nitrogen. Preparation of Agglomerate 3 (according to the invention)

[0123] A homogeneous mixture is prepared and 800 g of zeolite crystals, with a standard deviation of 0.30 µm, are agglomerated with 160 g of kaolin (expressed as calcined equivalent) and 60 g of colloidal silica sold under the trade name Klebosol ™ < 30N50 (containing 30% by weight of SiO 2 and 0.5% by weight of Na 2 O) with the quantity of water which allows the extrusion of the mixture. The extrudates are dried, then calcined at 550°C (firing of the clay) under a stream of nitrogen for 2 hours, and finally crushed so as to recover agglomerates whose number average diameter is equal to 0.5 mm.

[0124] The agglomerates obtained as described above (20 g) are placed in a glass reactor equipped with a double jacket regulated at a temperature of 90°C ± 1°C, then 250 mL of an aqueous sodium hydroxide solution with a concentration of 0.9 M are added, and the reaction medium is left stirring for a period of 6 hours.

[0125] The agglomerates are then washed in 3 successive water washing operations followed by emptying the reactor. The effectiveness of the washing is ensured by measuring the final pH of the wash water, which is between 10.0 and 10.5.

[0126] The agglomerates are exchanged by contact with a 0.5 M barium chloride solution at 95°C in 4 steps. At each step, the volume ratio of solution to mass of solid is 20 mL / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times to remove excess salt. The agglomerates are then dried at 80°C for 2 hours and finally activated at 250°C for 2 hours under a stream of nitrogen. Preparation of Agglomerate 4 (according to the invention)

[0127] A homogeneous mixture is prepared and 800 g of zeolite crystals, with a standard deviation of 0.35 µm, are agglomerated with 150 g of kaolin (expressed as calcined equivalent) and 58 g of colloidal silica sold under the trade name Klebosol ™ < 30N50 (containing 30% by weight of SiO 2 and 0.5% by weight of Na 2 O) with the quantity of water which allows the extrusion of the mixture. The extrudates are dried, then calcined at 550°C (firing of the clay) under a stream of nitrogen for 2 hours, and finally crushed so as to recover agglomerates whose number average diameter is equal to 0.5 mm.

[0128] The agglomerates obtained as described above (20 g) are placed in a glass reactor equipped with a double jacket regulated at a temperature of 90°C ± 1°C, then 250 mL of an aqueous sodium hydroxide solution with a concentration of 1.15 M are added, and the reaction medium is left stirring for a period of 5 hours.

[0129] The agglomerates are then washed in 3 successive water washing operations followed by emptying the reactor. The effectiveness of the washing is ensured by measuring the final pH of the wash water, which is between 10.0 and 10.5.

[0130] The agglomerates are exchanged by contact with a 0.5 M barium chloride solution at 95°C in 4 steps. At each step, the volume ratio of solution to mass of solid is 20 mL / g and the exchange is continued for 4 hours each time. Between each exchange, the solid is washed several times to remove excess salt. The agglomerates are then dried at 80°C for 2 hours and finally activated at 250°C for 2 hours under a stream of nitrogen. Characteristics of Agglomerates 1 to 4

[0131] The mechanical resistance (REL) of the agglomerates is characterized by the characterization techniques described above, and we thus obtain a value of 3.2 MPa for Agglomerate 1, and a value of 3.1 MPa for Agglomerate 2, a value of 2.9 MPa for Agglomerate 3 and a value of 3.1 MPa for Agglomerate 4.

[0132] The grain porosity values ​​ε p and standard deviations σ of the crystals in the final agglomerates, and as measured for Agglomerates 1 to 4 are given in Table 1 below.

[0133] Agglomerate 1, based on BaX crystals, has an average crystal size measured on the final agglomerate of 0.79 µm, Agglomerate 2, based on BaX crystals, has an average crystal size measured on the final agglomerate of 0.76 µm, Agglomerate 3, based on BaX crystals, has an average crystal size measured on the final agglomerate of 0.77 µm, and Agglomerate 4, based on BaX crystals, has an average crystal size measured on the final agglomerate of 0.76 µm.

[0134] The barium exchange rates of Agglomerates 1 to 4 calculated from elemental analyses of barium and sodium oxides by X-ray fluorescence, as described in the characterization techniques, is 99.0%.

[0135] The BaO content in agglomerates 1 to 4 is 36.2% by weight.

[0136] The loss on ignition measured as described above is 5.2% ± 0.1%. Example 2: implemented in a separation process Implementation of Agglomerates 1, 3 and 4

[0137] Agglomerates 1, 3 and 4 are used for the separation of paraxylene in a simulated moving bed.

[0138] A simulated moving bed unit consisting of 24 beds, 1.1 m long, with a feed injection, a desorbent injection, an extract withdrawal and a raffinate withdrawal is used. The beds are divided into 4 chromatographic zones according to the configuration: 5 / 9 / 7 / 3.

[0139] The filler is composed of 50% para-xylene, 14.5% ortho-xylene, 30.6% meta-xylene and 4.9% ethylbenzene. The desorbent is para- diethylbenzene. The temperature is 175°C, and the pressure is 15 bars. The water content is 95 ppm (weight).

[0140] The productivities obtained are presented in Table 1 below. The linear superficial velocity in zone 3 is 1.63 cm s -1< . Implementation of Agglomerate 2

[0141] Agglomerate 2 is used for the separation of paraxylene in a simulated moving bed.

[0142] A simulated moving bed unit consisting of 24 beds, 1.1 m long, with a feed injection, a desorbent injection, an extract withdrawal and a raffinate withdrawal is used. The beds are divided into 4 chromatographic zones according to the configuration: 5 / 9 / 7 / 3.

[0143] The charge is composed of 50% of para -xylene, 14.5% ortho -xylene, 30.6% of meta -xylene and 4.9% ethylbenzene. The desorbent is para- diethylbenzene. The temperature is 175°C, and the pressure is 15 bars. The water content is 95 ppm (weight).

[0144] Productivity is 186 kg of para -xylene m -3< h -1< . The linear superficial velocity in zone 3 is 1.63 cm s -1< .

[0145] The productivity results of the four agglomerated adsorbents are given in Table 1 below. Table 1 Grain porosity ε p (%) Standard deviation σ (µm) Productivity (kg para-xylene m -3< h -1< ) Agglomerate 1 (according to the invention) 35 0,21 220 Agglomerate 2 (comparative) 24 0,32 186 Agglomerate 3 (according to the invention) 32 0.28 214 Agglomerate 4 (according to the invention) 38 0,15 223

[0146] It is clearly shown that the agglomerates according to the invention make it possible to obtain a significant gain in productivity in the para-xylene production process.

Claims

1. Agglomerated zeolitic adsorbent comprising at least one faujasite FAU-X zeolite of Si / Al atomic ratio between 1.00 and 1.50 limits included and comprising barium and optionally potassium, characterized first in that the particle porosity of said absorbent is between 25% and 45%, preferably between 30% and 45%, more preferably between 32% and 45%, further preferably between 35% and 45%, and particularly advantageously between 36% and 45%, limits included, and secondly in that the standard deviation σ of crystal size distribution in said agglomerate is less than 0.30 µm, preferably between 0.05 µm and 0.30 µm, more preferably between 0.05 µm and 0.28 µm, further preferably between 0.1 µm and 0.28 µm, most preferably between 0.1 µm and 0.25 µm, limits included? said adsorbent comprises zeolite crystals of number-weighted mean diameter between 100 nm and 1200 nm, limits included, the weight fraction of FAU zeolite being higher than or equal to 80% relative to the total weight of the adsorbent, wherein the porosity and the standard deviation of crystal size distribution are measured as described in the specification.

2. The agglomerated zeolitic adsorbent according to claim 1, wherein said adsorbent comprises zeolite crystals of number-weighted mean diameter between 400 nm and 1200 nm, further preferably between 500 nm and 1200 nm, still further preferably between 550 nm and 1200 nm, most advantageously between 600 nm and 1200 nm, limits included.

3. The agglomerated zeolitic adsorbent according to one of claim 1 or 2, characterized in that it is in the form of beads of mean diameter between 100 µm and 1000 µm, preferably between 100 µm and 600 µm, more preferably between 200 µm and 550 µm, limits included.

4. The agglomerated zeolitic adsorbent according to one of claims 1 to 3, wherein said at least one FAU-X zeolite has a Si / Al atomic ratio of between 1.05 and 1.50, preferably between 1.05 and 1.40, limits included and more preferably between 1.10 and 1.40 limits included.

5. The agglomerated zeolitic adsorbent according to one of claims 1 to 4, wherein said adsorbent comprises barium with a content of barium oxide (BaO) higher than 10%, preferably higher than 15%, more preferably higher than 20%, further preferably higher than 23%, even higher than 33% by weight relative to the total weight of the adsorbent, and advantageously the barium content is between 23% and 42%, typically between 30% and 40% by weight, limits included, relative to the total weight of the adsorbent.

6. The agglomerated zeolitic adsorbent according to one of claims 1 to 5, wherein said adsorbent comprises potassium with a content of potassium oxide K2O lower than 25%, preferably between 0 and 20%, more preferably between 0 and 15% by weight limits included, relative to the total weight of the adsorbent.

7. The agglomerated zeolitic adsorbent according to any of the preceding claims, wherein no zeolitic structure other than the faujasite structure, preferably no zeolitic structure other than the faujasite X structure is detected by X-ray diffraction.

8. The adsorbent according to any of the preceding claims wherein the weight fraction of FAU zeolite, the FAU zeolite being zeolite X, is higher than or equal to 80% relative to the total weight of the adsorbent.

9. Use of an adsorbent according to any of claims 1 to 8, in processes: - to separate C8 aromatic isomer fractions, and xylenes in particular; - to separate isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, and others; - to separate cresols; - to separate polyhydric alcohols.

10. The use according to claim 9, for the separation of para-xylene from aromatic isomer fractions having 8 carbon atoms.

11. Process for separating para-xylene from aromatic isomer fractions having 8 carbon atoms, using as para-xylene adsorption agent an agglomerated zeolitic adsorbent according to one of claims 1 to 8, in liquid phase or in gas phase.

12. The process for separating para-xylene from isomer fractions of aromatic hydrocarbons having 8 carbon atoms according to claim 11, in liquid phase by adsorption of para-xylene in the presence of a desorbent preferably selected from among toluene and n para-diethylbenzene.

13. The process according to any of claim 11 or 12 of simulated moving bed type, preferably of simulated counter-current type.