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    • 专利摘要:
    The present invention relates to zeolite X-based agglomerated zeolite adsorbents comprising barium, potassium and sodium. These adsorbents find applications in the separation of C8 aromatic isomer sections and in particular xylenes.
    公开号:FR3038528A1
    申请号:FR1556523
    申请日:2015-07-09
    公开日:2017-01-13
    发明作者:Catherine Laroche；Ludivine Bouvier；Javier Perez-Pellitero
    申请人:IFP Energies Nouvelles IFPEN；Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    ZEOLITHIC ADSORBENTS,
    PREPARATION METHOD AND USES THEREOF
    TECHNICAL FIELD [0001] The invention relates to adsorbents based on agglomerated crystals of zeolite X comprising barium and potassium, their preparation process and their uses.
    These adsorbents may be used more particularly for the production in the liquid phase or gas phase of very pure para-xylene from an aromatic hydrocarbon feed containing isomers containing 8 carbon atoms.
    PREVIOUS TECHNIQUE
    [0003] It is known in the prior art that adsorbents comprising crystalline aluminosilicates can be used to separate certain hydrocarbons from mixtures containing them. In the field of aromatic hydrocarbon separation and in particular the separation of aromatic C8 isomers, it is generally recognized that the use of particular cations in cationic sites of zeolitic crystalline aluminosilicates improves the selectivity of the zeolite for C8-aromatic isomers. This differentiated adsorption within the zeolite allows the separation of the different C8-aromatic isomers, which is used industrially for the production of very pure para-xylene from an aromatic hydrocarbon feed containing 8-atom isomers. carbon.
    Thus, the use of zeolitic adsorbents consisting of X or Y zeolites comprising, besides sodium cations, barium, potassium or strontium ions, alone or in mixtures, for selectively adsorbing the para-xylene in the liquid phase in a liquid phase. mixture of aromatic hydrocarbons, is well known from the prior art.
    No. 3,558,730, US 3,558,732, US 3,626,020, US 3,663,638 and US 3,960,774 show that zeolitic adsorbents comprising aluminosilicates of faujasite structure (FAU) based on sodium and barium. or based on sodium, barium and potassium, are effective for the separation of para-xylene present in C8 aromatic cuts (cuts comprising aromatic hydrocarbons with 8 carbon atoms). The above adsorbents are preferably used as adsorption agents in liquid phase processes, especially of simulated counter-current type, similar to those described in US Pat. No. 2,985,589 and which apply, inter alia, to aromatic cuts in C8.
    However, in general, the adsorption properties of zeolites for aromatic hydrocarbons with 8 carbon atoms (xylenes and ethylbenzene) vary very finely depending on the size and shape of the pores and the position of the cations within the structure that influence both the electrostatic field present inside the zeolite and the shape of the accessible volume in the pores. Other parameters, such as the polarizability of cations and molecules or the flexibility of the structure can also have an influence. It is therefore extremely difficult to predict theoretically and precisely the adsorption characteristics of a zeolite with respect to aromatic hydrocarbons containing 8 carbon atoms.
    To improve the adsorption selectivity of zeolites having the faujasite structure for the C 8 aromatic isomers, numerous studies have mentioned the influence of the Si / Al ratio of the zeolite, the nature of the exchange cations. , as well as their water content. Similarly, it is very difficult to predict the degree of improvement because these factors exert combined actions on the adsorption characteristics of zeolites. In particular, it is difficult to predict the impact of the relative proportion of barium and potassium ions in the case of a zeolite of faujasite structure (FAU) based on barium and potassium, and more specifically in the case of a zeolite of Faujasite structure (FAU) type X, based on barium and potassium.
    Patent FR 2,903,978 teaches that potassium ions may represent up to 1/3 of exchangeable sites occupied by barium and potassium, but this patent does not fill any adsorbent containing potassium and provides no teaching allowing to anticipate the impact of potassium on adsorption selectivities.
    US Pat. No. 8,283,274 and US Pat. No. 8,557,028 describe adsorbents having potassium content by weight of between 0.25% and 0.9% by weight, corresponding to molar ratios K20 / (BaO + K20 + Na 2 O) of between 1.3% and 4.5%. US Pat. No. 8,557,028 claims adsorbents having potassium content by weight of between 0.9 and 1.5%, equivalent to molar ratios K20 / (BaO + K20 + Na2O) of between 4.5% and 7.5%. . The examples of the latter patent show that the productivity is improved with adsorbents having potassium contents of between 0.5% and 0.7% by weight, equivalent to molar ratios K20 / (BaO + K20 + Na2O) of 2 , 5% and 3.5%. CN1267185 describes adsorbents having molar ratios BaO / K20 of between 10 and 40 corresponding to molar ratios K20 / (BaO + K20 + Na2O) of between 2.4% and 9.1%.
    The recent patent US 2015/0105600 describes for its part an adsorbent based on zeolite X, barium and potassium, having a molar ratio K20 / (BaO + K20 + Na2O) of between 15% and 40%.
    The synthesis of zeolites leads to crystals (generally in the form of powder) whose use on an industrial scale is particularly difficult (significant pressure losses during handling). Agglomerated forms of these crystals, in the form of grains, yarns and other agglomerates, are preferred, these forms being able to be obtained by extrusion, pelletizing, and other agglomeration techniques known to those skilled in the art. These agglomerates do not have the disadvantages inherent to the pulverulent materials.
    These agglomerates, whether in the form of platelets, beads, extrudates, and the like, are generally formed of zeolite crystals (s), 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 and to give them sufficient mechanical strength to withstand the vibrations and the movements to which they are subjected during the operations of separating the isomers of the aromatic cuts in C8 . However, the adsorption properties of these agglomerates are obviously reduced compared to the crystal powder, because of 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, the conversion of all or at least part of the agglomeration binder into active zeolite of 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 easily perform this operation, zeolitizable binders are used, most often clays belonging to the family of kaolinite, and preferably previously calcined at temperatures generally between 500 ° C and 700 ° C.
    The patent application FR 2 789 914 describes for example a process for the manufacture of agglomerates of zeolite X, Si / Al ratio between 1.15 and 1.5, containing barium and optionally potassium. The agglomerates thus obtained, after zeolization of the binder, have, from the point of view of the adsorption of the para-xylene contained in the C8 aromatic cuts, improved properties compared with adsorbents prepared from the same amount of zeolite X and binder, but whose binder is not zeolite.
    The important factors that influence the performance of an adsorption separation process include in particular the adsorption selectivity, the adsorption capacity and the material transfer kinetics which defines the adsorption and desorption rates of the different compounds. The adsorbent must therefore have good material transfer properties in order to guarantee a sufficient number of theoretical plates to achieve effective separation of the species in mixture, as Ruthven indicates in the book entitled "Principles of Adsorption and Adsorption Processes" ("Principles of Adsorption and Processes of Adsorption"), 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 addition of the intracrystalline diffusional resistance and diffusional resistance between the crystals. The intracrystalline diffusion resistance is proportional to the square of the crystal rays and inversely proportional to the diffusivity of the intracrystalline molecules.
    The diffusional resistance between the crystals (also called macroporous resistance) is in turn proportional to the square of the rays of the agglomerates and inversely proportional to the diffusivity of the molecules in the macropores. For a given zeolite structure, a given agglomerate size and a given operating temperature, the diffusivities are fixed, and the only way to improve the transfer of material is to reduce the crystal diameter. A gain on the overall transfer will thus be obtained by reducing the size of the crystals.
    Therefore, one skilled in the art expects that agglomerated zeolite adsorbents having both good xylenes adsorption capacity and good selectivity for para-xylene, have very good separation properties. xylenes when they are made from small zeolite crystals in liquid phase processes for separating para-xylene contained in C8 aromatic cuts, for example of simulated countercurrent type. Those skilled in the art are, however, unable to define a priori or theoretically and precisely the adsorption characteristics of a FAU zeolite, especially of type X, having a particular composition of barium and potassium, opposite aromatic hydrocarbons having 8 carbon atoms.
    The present invention aims to provide novel adsorbents based on zeolite X comprising barium, potassium and sodium and having a particular composition of barium, potassium and sodium, optimal to maximize the productivity of the separation process of the invention. para-xylene content in C8 aromatic cuts. The present invention also provides a process for the separation of xylenes using a zeolite X-based adsorbent having a particular composition of barium, potassium and sodium, allowing the production of high purity para-xylene with improved productivity from an aromatic hydrocarbon feed containing isomers containing 8 carbon atoms.
    SUMMARY OF THE INVENTION
    The invention relates to a zeolitic adsorbent comprising crystals of zeolite X and comprising barium, potassium and sodium, wherein the molar ratio K20 / (K20 + BaO + Na2O) (species in the form of oxides). is between 8.0% and 8.6%, preferably between 8.2% and 8.4% inclusive. In an advantageous variant, the molar ratio K20 / (K20 + BaO + Na2O) is equal to 8.3%. In the present invention, the molar ratio K20 / (K20 + BaO + Na2O) is expressed as a percentage of the number of moles of K20 relative to the sum of the number of moles of (K20 + BaO + Na2O).
    The sodium oxide content Na 2 O is advantageously less than 0.3% by weight and preferably less than 0.2% by weight relative to the total mass of the adsorbent.
    The total content of alkali or alkaline earth metal oxides other than barium oxide BaO, potassium oxide K20 and sodium oxide Na20 is advantageously less than 1% by weight, preferably between 0 and 0.5% by weight, and very preferably between 0 and 0.3% by weight, limits included, relative to the total mass of the adsorbent.
    The zeolite crystals X advantageously have an Si / Al atomic ratio of between 1.00 and 1.50, preferably between 1.05 and 1.50 and more preferably between 1.10 and 1.50, terminals included.
    The number average diameter of the zeolite crystals X is less than or equal to 1.5 μm, preferably between 0.1 μm and 1.2 μm, more preferably between 0.1 μm and 1 μm, 0 pm, terminals included.
    The loss on ignition of the adsorbent according to the invention, measured at 950 ° C according to the standard NF EN 196-2 is advantageously between 4.0 and 7.7% and preferably between 4.5 and 6. , 5% and most preferably between 4.8 and 6% by weight, inclusive.
    The average diameter by number of the adsorbent according to the invention may be between 0.2 mm and 2 mm, in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0 mm. , 65 mm, terminals included.
    The invention also relates to a method for preparing an adsorbent as described above, comprising at least the steps of: a) agglomeration of a powder of crystals of zeolite X with a binder, and setting form, then drying and calcination, b) possible zeolization of the binder, c) cationic exchange of the agglomerate by contact with a solution of barium ions, or potassium ions, or barium ions and potassium ions d) cation exchange with potassium when the step c) of exchange is carried out with a solution of barium ions alone, or cation exchange with barium when the step c) of exchange is carried out with a solution of potassium ions only e) then washing and drying the product thus treated, f) activating the zeolitic adsorbent thus obtained.
    Preferably, the process for preparing the adsorbent implements a step b) of zeolitization of the binder.
    Preference or solutions of barium ions, or potassium or barium and potassium steps c) and d) have a concentration between 0.2M and 2M.
    The invention also relates to an adsorbent as described above, obtainable by the preparation method above.
    The invention also relates to the use of said adsorbent according to the invention in the processes of: • separation of C8 aromatic isomer sections and in particular xylenes, • separation of isomers of substituted toluene such as nitrotoluene, diethyltoluene , toluenediamine, and others, • separation of cresols, • separation of polyhydric alcohols, and especially for the separation of para-xylene from cuts of aromatic isomers with 8 carbon atoms.
    The invention also relates to a process for recovering para-xylene from aromatic hydrocarbon isomer cuts containing 8 carbon atoms, in the liquid phase, by adsorption of para-xylene by means of said adsorbent according to US Pat. invention in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
    Said method may be simulated moving bed type, preferably simulated counter current.
    The invention also relates to a process for recovering para-xylene from cuts of isomers of aromatic hydrocarbons containing 8 carbon atoms, in the gas phase, by adsorption of para-xylene by means of said adsorbent according to US Pat. invention in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
    The invention further relates to a process for separating polyhydric alcohols employing said adsorbent according to the invention.
    The invention further relates to a process for separating isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, using said adsorbent according to the invention.
    The invention finally relates to a process for separating cresols using said adsorbent according to the invention.
    In what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this field, especially in the expressions "between" and "ranging from ... to .. . "
    DETAILED DESCRIPTION OF THE INVENTION The present invention thus has as its first object zeolite X-based zeolite adsorbents. These adsorbents are particularly suitable for use in a process for separating para-xylene in the liquid phase, preferably from simulated countercurrent type.
    Thus, the present invention relates to a zeolite adsorbent comprising zeolite X crystals and comprising barium, potassium and sodium, in which the molar ratio K20 / (K20 + BaO + Na2O) is between 8.0% and 8.6%, preferably between 8.2% and 8.4% inclusive, and most preferably 8.3%.
    The adsorbents according to the invention may also comprise a non-zeolitic phase, that is to say a non-crystalline phase which is essentially inert with respect to the adsorption. In the case where the adsorbent according to the invention comprises a non-zeolitic phase, the molar ratio K20 / (K20 + BaO + Na2O) takes into account the oxides included in said non-zeolitic phase.
    The Na 2 sodium oxide content in the adsorbent according to the invention is advantageously less than 0.3% by weight and preferably less than 0.2% by weight relative to the total mass of the adsorbent.
    The total content of oxides of alkaline or alkaline earth ions other than barium oxide BaO, potassium oxide K20 and sodium oxide Na20 in the adsorbent according to the invention is advantageously less than 1% by weight, preferably between 0 and 0.5% by weight, and very preferably between 0 and 0.3% by weight, limits included, relative to the total mass of the adsorbent.
    The zeolitic adsorbent according to the present invention is an adsorbent based on FAU zeolite crystals type X. By "zeolite X" is meant zeolites whose atomic ratio Si / Al is between 1.00 and 1. , 50 terminals included, preferably between 1.05 and 1.50 inclusive, and even more preferably between 1.10 and 1.50 inclusive.
    Among zeolites X, it is now generally accepted to recognize two subgroups called zeolites LSX and zeolites MSX. 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.
    In the zeolite adsorbent of the present invention, and according to a preferred embodiment, the term "zeolite FAU type X" means the zeolites FAU type X defined above, said zeolites being hierarchically porous that is, zeolites of type X with hierarchical porosity (or zeolite XPH), zeolites of MSX type with hierarchical porosity (or MSXPH) and zeolites of LSX type with hierarchical porosity (or LSXPH), and more particularly the FAU zeolites having a hierarchical porosity and an Si / Al atomic ratio of between 1.00 and 1.50 inclusive, preferably between 1.05 and 1.50, more preferably between 1.05 and 1.40, included terminals, and even more preferably, between 1.15 and 1.40 inclusive.
    The invention also comprises zeolitic adsorbents comprising mixtures of two or more FAU zeolites with hierarchical porosity as they have just been defined.
    By "hierarchically porous zeolite" is meant a zeolite having both micropores and mesopores, that is to say a zeolite 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 zeolite crystals are solid zeolite crystals (ie non-mesoporous) or aggregates of crystals solid zeolites 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 a preferred embodiment, the zeolite adsorbent has an Si / Al atomic ratio of between 1.00 and 2.00, preferably between 1.00 and 1.80 inclusive, more preferably between 1.15 and 1.50 inclusive. and 1.80, included terminals and even more preferably between 1.15 and 1.60 inclusive.
    In this document, the term "number average diameter" or "size" is used for zeolite crystals and for zeolite agglomerates. The method of measuring these quantities is explained later in the description. According to a preferred embodiment of the present invention, the number average diameter of the zeolite crystals X is less than or equal to 1.5 μm, preferably between 0.1 μm and 1.2 μm, more preferably included between 0.1 pm and 1.0 pm, inclusive.
    The zeolite adsorbent of the invention is preferably in the form of an agglomerate, that is to say it consists of zeolite crystals (s) and at least one non-zeolite phase which may comprise an agglomeration binder allowing the cohesion of the crystals between them. Thus the zeolitic adsorbent of the invention is often referred to as "agglomerated" in the present disclosure.
    The mass fraction of zeolite X in the adsorbent according to the present invention may be at least 80% by weight relative to the total weight of the adsorbent, preferably at least 90%, this mass fraction being up to 100% and typically up to 99.5% by weight.
    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 of between 4.0% and 7.7%, preferably between 4.5 and 6.5% and advantageously between 4.8 and 6%, limits included.
    The zeolitic adsorbent according to the present invention preferably has a mechanical strength generally greater than or equal to 1.8 MPa, typically greater than or equal to 2.1 MPa. This mechanical resistance is measured by the Shell method SMS1471-74 series suitable for agglomerates of less than 1.6 mm size.
    The adsorption capacity is measured by measuring the microporous volume of the adsorbent evaluated according to the Dubinin-Raduskevitch equation by nitrogen adsorption (N2) at a temperature of 77K, after degassing under vacuum at 300 ° C for 16 hours. The microporous volume of the zeolite adsorbents of the invention was thus measured to be greater than 0.250 cm3 / g, typically in a range of 0.256 cm3 / g to 0.288 cm3 / g.
    According to another aspect, the invention relates to a process for preparing zeolite agglomerates as just defined, which process comprises at least the steps of: a) agglomeration of crystals (powder) of zeolite X with a binder, and shaped agglomerate, then drying and calcination, b) zeolitization of said binder, preferably by the action of an alkaline basic solution, c) cationic exchange of the agglomerate by contacting with a solution of barium ions, or potassium ions, or barium ions and potassium ions, d) potassium cation exchange when the step c) exchange is carried out with a solution of barium ions alone, or cation exchange with barium when the step c) of exchange is carried out with a solution of potassium ions alone, e) then washing and drying of the product thus treated, f) activation of the zeolite agglomerate.
    Preferably, the process for preparing the zeolite agglomerates implements a step b) of zeolitization of the binder.
    Preference or solutions of barium ions, or potassium or barium and potassium steps c) and d) have a concentration between 0.2M and 2M.
    The size of the zeolite X crystals used in step a) is measured by observation under a scanning electron microscope (SEM) or observation by transmission electron microscope (TEM). This observation MEB or MET also confirms the presence of non-zeolite phase comprising for example the binder or the unconverted residual binder during the optional zeolitization step or any other amorphous phase in the agglomerates.
    According to one embodiment, the zeolite X used in step a) comprises, preferably is, an X type FAU zeolite with hierarchical porosity. The X-type 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), 57, 1962-1965).
    It is also possible to prepare said crystals by synthesis by seeding 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 the processes described in US Pat. post-treatment of conventional X-type FAU zeolite crystals 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 else by treatments which combine the action of an acid and that of a structuring agent which improve the efficiency of the acid treatment, as described for example in application WO2013 / 106816.
    Agglomeration and shaping (step a) can be carried out according to all the techniques known to those skilled in the art, such as extrusion, compaction, agglomeration, and others. The proportions of agglomeration binder, optionally zeolitizable (see definition below) and zeolite (s) used are typically those of the prior art, that is to say from 5 parts to 20 parts by weight binder for 95 parts to 80 parts by weight of zeolite. The agglomerates resulting from stage a), whether in the form of beads, extrudates or the like, generally have a number average diameter (or their largest dimension when they are not spherical) between 0.degree. , 2 mm and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0.65 mm inclusive.
    After step a), the finest agglomerated particles can be removed by cycloning and / or sieving and / or excessively large particles by sieving or crushing, in the case of extrudates, for example.
    The agglomeration binder used in step a) may be zeolitizable. It then contains at least 80% preferably, at least 90%, more preferably at least 95%, more particularly at least 96%, by weight, of zeolitic clay and may also contain other inorganic 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 zeolite material (that is to say, active material in the sense of adsorption), most often by action of a basic alkaline solution. Zeolizable clay generally belongs to the family of kaolin, kaolinite, nacrite, dickite, halloysite and / or metakaolin. Kaolin is preferred and most commonly used.
    Other clays such as in particular sepiolite or attapulgite may also be used.
    In all cases, the clays can be used in their raw state or may be previously subjected to one or more treatments, for example selected from calcination, acid treatment, chemical modification, and others.
    The zeolite X powder used in step a) may be derived from the synthesis of zeolite X crystals comprising predominantly, see only sodium cations, for example NaX zeolites, but we would not go outside the box. of the invention using a powder having undergone one or more cationic exchanges, after its synthesis and before its implementation in step a).
    In step a), in addition to the zeolite X powder and the binder, one or more additives may also be added, for example additives intended to facilitate the agglomeration or to improve the hardening of the formed agglomerates such as lignin, starch, carboxymethylcellulose, and other additives known to those skilled in the art. Silica can also be added. The possible source of silica may be of any type known to those skilled in the art, specialist in the synthesis of zeolites, for example colloidal silica, diatoms, perlite, fly ash ash in the language English), sand, or any other form of solid silica.
    After drying in step a), the calcination is conducted at a temperature generally between 500 ° C and 600 ° C. In the case where the shaping is carried out with a zeolitic clay, this step makes it possible to transform the zeolite clay, typically kaolin, into metakaolin which can after being converted into zeolite during the zeolitization step (step b)) . The principle is set forth in D.W. Breck's "Zeolite Molecular Sieves," John Wiley and Sons, New York, (1973), p. 314-315.
    The zeolitization of the agglomeration binder is carried out according to any method known to those skilled in the art and may for example be carried out by immersion of the product of step a) in an alkaline basic solution, generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide.
    As a general rule, the concentration of the alkaline zeolitization solution is preferably between 0.5 M and 5 M. The 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, for example between room temperature (about 20 ° C) and the boiling temperature of the alkaline solution of zeolitization. The duration of the zeolitization process is generally between a few tens of minutes and a few hours, preferably between about 1 hour and 8 hours.
    Steps c) and d) of barium and / or potassium exchange of the zeolite X cations are carried out according to the conventional methods known to those skilled in the art, and most often by contacting the agglomerates from step a) or step b) with a salt, such as barium chloride (BaCl 2) for barium exchange and / or potassium chloride (KCl) for potassium exchange 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 low levels of sodium oxide, ie less than 1%, it is preferred to operate with a large excess of barium and / or potassium ions relative to the cations of the zeolite which it is desired to exchange, typically an excess of the order of 10 to 12, advantageously by proceeding by successive exchanges.
    As indicated above, it is also possible to agglomerate in step a) of the zeolite X powder already containing potassium ions (pre-exchange of the cations present in the starting zeolite X, typically sodium cations, by potassium ions before step a)) and free or not potassium exchanges in steps c) and / or d).
    Then proceed to a washing, usually and preferably with water, and then drying the agglomerate thus obtained.
    The activation which follows drying, is conducted in a conventional manner, according to the methods known to those skilled in the art, for example at a temperature generally between 100 ° C and 400 ° C, preferably between 200 ° C C and 300 ° C. This f) activation step is intended to set the water content and the loss on ignition of the adsorbent optimally for the intended use. In general, thermal activation is carried out preferably between 200 ° C and 300 ° C for a predetermined period depending on the desired water content and loss on fire, typically 1 to 6 hours.
    The present invention also relates to the uses of the zeolite adsorbents described above as adsorption agents that may advantageously replace the adsorption agents described in the literature for the uses listed below: • separation of isomeric cross-sections C8 aromatics and especially xylenes, • separation of isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, and others, • separation of cresols, • separation of polyhydric alcohols, such as sugars.
    The invention relates in particular to a process for recovering para-xylene at high purity from aromatic isomer cuts with 8 carbon atoms comprising using, as para-xylene adsorption agent, a zeolite adsorbent according to the invention, implemented in processes in the liquid phase but also in the gas phase. By para-xylene of high purity, we mean a product suitable for use in the production of terephthalic acid or dimethyl terephthalate, that is to say a purity of at least 99.5% by weight, preferably at at least 99.7% by weight, preferably at least 99.8% by weight and more preferably at least 99.9% by weight. The purity of para-xylene can be determined by chromatographic methods. A gas chromatographic method that can be used both for determining the purity of para-xylene and specific amounts of impurities is ASTM Method D-3798.
    It is thus possible to separate the desired product (para-xylene) by preparative adsorption liquid chromatography (in batch), and advantageously continuously in simulated moving bed, that is to say against the simulated countercurrent or simulated co-current, and more particularly simulated countercurrent.
    The process for recovering para-xylene according to the invention using the adsorbent described according to the invention has the advantage of maximizing productivity, that is to say to maximize the charge rate to be treated. This is particularly true under the following simulated countercurrent industrial adsorption type operating conditions: • number of beds: 6 to 30, • number of zones: at least 4 operating zones, each located between a point and a draw point, • temperature between 100 ° C and 250 ° C, preferably between 150 ° C and 190 ° C, • pressure of the industrial unit between the bubble pressure xylenes at temperature of the process and 3 MPa, • ratio of desorbent / feed rates between 0.7 and 2.5, for example between 0.9 and 1.8 for a single adsorption unit (stand alone) and between 0.7 and 2.5. 1.4 for an adsorption unit combined with a crystallization unit, • recycling rate (ie ratio of the average recycling rate (average of the zone-weighted flow rates of the number of beds per zone) to the charge flow rate) between 2.5 and 12, preferably between 3.5 and 6.
    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.
    The operating conditions of a simulated co-current adsorption industrial unit are generally the same as those operating at 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 4,498,991.
    The desorption solvent may be any desorbent known to those skilled in the art and whose boiling point is lower than that of the filler, such as toluene but also a desorbent whose boiling point is greater than that of the feed, such as para-diethylbenzene (PDEB). The selectivity of the adsorbents according to the invention for the adsorption of para-xylene contained in C8 aromatic cuts is optimal when their loss on ignition measured at 950 ° C. is generally between 4.0% and 7.7%. and preferably between 4.5% and 6.5%, and most preferably between 4.8% and 6.0% inclusive.
    Characterization techniques Granulometry of the crystals: The estimation of the number average diameter of the zeolite X crystals used in step a) and the zeolite X crystals contained in the agglomerates is carried out by observation under a scanning electron microscope ( SEM) or observation by transmission electron microscope (TEM).
    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 a dedicated software, for example the Smile View software from the LoGraMi editor. The accuracy is of the order of 3%.
    Chemical analysis of zeolitic adsorbents - Si / Al and K20 / (K20 + BaO + Na2O) ratio: [0085] An elemental chemical analysis of the final product obtained at the end of steps a) to f) described above can be carried out according to various analytical techniques known to those skilled in the art. Among these techniques, mention may be made of the technique of chemical analysis by X-ray fluorescence as described in standard NF EN ISO 12677: 2011 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 of the company Bruker.
    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. In the present invention, the barium, silicon and aluminum contents are preferably measured by the X-ray fluorescence method described above.
    In contrast, for the elements that are lighter in atomic weight, such as sodium or potassium, present in the adsorbent, it is preferable for the sake of precision the atomic emission spectrometry with inductively coupled plasma (ICP-OES for Inductively Coupled Plasma-Optical Emission Spectroscopy according to the English terminology) according to the UOP 961-12 standard.
    The ICP is a method of analysis by atomic emission spectrometry whose source is a plasma generated by inductive coupling. This method is also commonly used to determine the contents of various elements such as silicon, aluminum, potassium, sodium and barium. In the present invention, the sodium and potassium contents are preferably measured by the ICP method according to the UOP 961-12 standard. In this case, for the sodium, an uncertainty of less than 0.01% is obtained for the content by weight of the sodium oxide in the adsorbent and for potassium an uncertainty on the measurement of less than 0.02% for the content by weight of the potassium oxide in the adsorbent.
    These elementary chemical analyzes make it possible both to verify the Si / Al atomic ratio of the zeolite within the agglomerate, and to verify the quality of the ion exchange described in step c) and in the step d). In the description of the present invention, the measurement uncertainty of the Si / Al atomic ratio is 0.05.
    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. Specifically, the exchange rate by barium ions is determined by the ratio between the number of moles of barium oxide, BaO, and the number of moles of the whole (BaO + K20 + Na20). Similarly, the exchange rate by potassium ions is determined by the ratio between the number of moles of potassium oxide, K20, and the number of moles of the whole (BaO + K20 + Na20). BaO, K20 and Na2O are expressed as oxides. The total exchange rate by barium and potassium ions is estimated from the sum of the two exchange rates described above, corresponding to the ratio between the sum of the number of moles of barium oxide and potassium oxide (BaO + K20) and the number of moles of all (BaO + K20 + 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. In the description of the present invention, the measurement uncertainty on the molar ratio K20 / (K20 + BaO + Na2O) is 0.2%.
    Granulometry of zeolite adsorbents: The determination of the number average diameter of the zeolite adsorbents obtained at the end of step a) of agglomeration and shaping is carried out by analysis of the particle size distribution of a sample of image sintered according to ISO 13322-2: 2006, using a treadmill allowing the sample to pass in front of the camera lens.
    The number average diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard. In this document, the term "average number 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: The technique of characterizing the mechanical resistance representative of the crushing of the adsorbent within a bed or a reactor is the technique of characterization of the mechanical resistance in bed, such as as described in the Shell method serial SMS1471-74 (Shell Method Sereries SMS1471-74 Determination of Bulk Crushing
    Strength of Catalysts. Compression-Sieve Method "), associated with the apparatus" BCS Tester "sold by the company Vinci Technologies.This method, initially intended for the characterization of catalysts from 3 to 6 mm is based on the use of a screen of 425 μηη which will allow to separate the fines created during crushing.The use of a 425 μm sieve remains suitable for particles greater than 1.6 mm in diameter, but must be adapted according to the particle size of the zeolite adsorbents that ASTM D7084-04, which also describes a method for measuring catalyst bed crush strength ("Determination of Bulk Crush Strength of Catalysts and Catalyst Carriers"), defines the passage of the sieve. to be used as being equal to half the diameter of the catalyst particles to be characterized The method provides for a preliminary step of sieving the catalyst sample or adsorban If an amount equal to 10% by weight of the sample passes through the grid, a smaller through screen will be used.
    The agglomerates of the present invention, generally in the form of beads or extrudates, generally have a number average diameter or a length, ie the largest dimension in the case of nonspherical agglomerates, of between 0.2 mm. and 2 mm, and in particular between 0.2 mm and 0.8 mm and preferably between 0.2 mm and 0.65 mm. Therefore, a suitable screen such that less than 10% by weight of the sample passes through the screen during a prior sieving step is used in place of the 425 μm sieve mentioned in the standard Shell method SMS1471-74 .
    The measuring protocol is as follows: a sample of 20 cm 3 of agglomerated adsorbents, previously sieved with the appropriate sieve and previously dried in the 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 bed of 5 cm3 of steel balls in order to better distribute the force exerted by the piston on the agglomerates of adsorbents (use of 2 mm diameter balls for particles of spherical shape with a diameter strictly less than 1.6 mm). The fines obtained at the different pressure levels are separated by sieving (with a suitable sieve) and weighed.
    The crush resistance in bed is determined by the pressure in megaPascal (MPa) for which the amount of cumulative fines passing through the sieve is 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 4 MPa. The accuracy is conventionally less than 0.1 MPa. Determination of zeolite fractions of zeolite adsorbents: The nature and the quantity of the various zeolite fractions are determined by X-ray diffraction analysis, known to those skilled in the art under the acronym XRD. This analysis is carried out on a Bruker brand apparatus, then the quantity of zeolite fractions is evaluated using Bruker's TOPAS software. Microporous Volume: [0098] The crystallinity of the agglomerates is also evaluated by measuring their microporous volume by comparing it with that of a suitable reference (100% crystalline zeolite under identical cationic treatment conditions 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 adsorption, the zeolite adsorbent is degassed at 300 ° C. to 450 ° C. for a period of 9 hours to 16 hours, under vacuum (P <6.7 × 10 -4 Pa). The measurement of the nitrogen adsorption isotherm at 77K is then carried out on a Micromeritics ASAP 2010 M type apparatus, taking at least 35 measurement points at relative pressures with a P / P0 ratio of between 0.002 and 1. The microporous volume is determined according to Dubinin and Raduskevitch from the obtained isotherm, applying the ISO 15901-3: 2007 standard. The microporous volume evaluated according to Dubinin and Raduskevitch is expressed in cm3 of liquid adsorbate per gram of adsorbent. The measurement uncertainty is ± 0.003.
    Loss on ignition of zeolitic 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 the adsorption in liquid phase by drilling: The technique used to characterize the adsorption of molecules in 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 analysis of the dispersion (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 ideally stirred hypothetical reactors (theoretical stages), which is a direct measurement of the axial dispersion and resistance to material transfer of the system.
    Examples
    Preparation of zeolite adsorbents [0100] A homogeneous mixture is prepared and 800 g of NaX zeolite crystals are agglomerated according to the procedure described in patent application FR 2 999 098 (synthesis of Example B) with 105 g of kaolin (expressed as in calcined equivalent) and 45 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 extrudates are dried, crushed so as to recover grains whose number average diameter is equal to 0.5 mm, and then calcined at 550 ° C. under a stream of nitrogen for 2 hours.
    200 g of agglomerates obtained 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. of 2.5 M sodium concentration and the reaction medium is left stirring for a period of 4 hours.
    Then the agglomerates are 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.
    EXAMPLE 1 Cationic Exchange with Barium and Potassium The sodium cations of the agglomerates obtained are exchanged with barium and potassium ions using a 0.5M aqueous solution of potassium chloride and 95% barium chloride. C in 4 steps. The concentrations of potassium chloride and barium chloride in the solution are adapted in order to reach the targeted barium and potassium contents in the adsorbent and therefore the molar ratios K20 / (K20 + BaO + Na20) targeted (Figure 1). . At each step, the volume ratio of solution to mass of solid is 20 ml / g and the exchange is continued for 3 hours each time. Between each exchange, the solid is washed several times in order to rid it of 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.
    The measured loss on ignition, as previously described, is 5.6% ± 0.1% for each sample. The barium-potassium exchange rate of the agglomerates calculated from elemental analyzes of barium and sodium oxides by X-ray fluorescence as described in the characterization techniques is 99.7 ± 0.2%.
    Example 2 Drilling Test [0105] A drilling test (frontal chromatography) is then performed on the agglomerates obtained in Example 1 to evaluate their effectiveness. The amount of adsorbent used for this test is about 30 g.
    The procedure for obtaining the drilling curves is as follows: • Filling of the column by the sieve and setting up in the test bench. • Filling with solvent (toluene) at room temperature. • Gradual increase at the adsorption temperature under a stream of solvent (2 cm3 / min). • Injection of solvent at 2 cm3 / min when the adsorption temperature is reached. • Solvent / charge permutation to inject the charge (2 cm3 / min). • The injection of the charge is then maintained for a time sufficient to reach thermodynamic equilibrium. • Collection of the recipe of the piercing in a single bottle then analysis of the composition of the recipe by GIC.
    The pressure is sufficient for the charge to remain in the liquid phase, ie 1 MPa. The adsorption temperature is 175 ° C. The composition of the filler used for the tests is as follows: • Para-xylene: 18% by weight • Meta-xylene: 18% by weight • Ortho-xylene: 18% by weight • Ethylbenzene: 18% by weight • Para-xylene: 18% by weight diethylbenzene: 18% by weight • Iso-octane: 10% by weight (this one is used as a tracer for the estimation of the non-selective volumes and does not intervene in the separation)
    The selectivities of the compounds in pairs, denoted binary selectivities ai / k are calculated from the adsorbed quantities q, and qk compounds i and k, the latter being determined by material balance from the analysis of the composition. of the recipe of the piercing and the composition of the charae (charge in which the mass fraction of the compounds i and k is y, and yk): the evaluation of the potential of these adsorbents during the implementation against -current simulated, is made based on the theory of equilibrium applied to multi-constituent systems with constant selectivities as described by Mazotti, Storti and Morbidelli in Robust Design of Countercurrent Adsorption Separation Processes: 2.
    Multicomponent Systems, AlChE Journal November 1994 Vol. In particular, reference is made here to equation 8, which describes the conditions to be satisfied on the reduced flow rates m, of the 4 sections (j = 1 to 4) of a counterbalance separation unit. current as schematized in Figure 1 of the cited article to obtain a complete separation.
    Section 1:
    Section 2:
    Section 3:
    (8)
    Section 4:
    This equation 8 refers to the adsorptivity K, of the various constituents, as well as to the parameter δ, of each section j defined by equation 7:
    0 = 1, ..., 4) (7) [0111] It should be noted here that by definition the binary selectivity ai / k between the compounds i and k is equal to the ratio of adsorptivity K, / Kk.
    The reduced flow rate of each section of the unit is defined as the ratio of the flow rate of the liquid phase to the flow rate of the adsorbed phase. Equation 8 indicates which flow rates are reduced for each section. In a 4-section countercurrent separation unit, the charge flow corresponds to the difference between the flow in zone 3 and the flow in zone 2.
    Therefore, when one wants to evaluate the maximum productivity that can be achieved with a given adsorbent, one seeks to evaluate the maximum amount of charge that can be treated, that is to say to evaluate the difference between the maximum flow rate in zone 3 and the minimum flow rate in zone 2. The performance in terms of maximum productivity of two adsorbents can be compared by comparing their maximum reduced flow rate determined from the reduced flow rates of zones 2 and 3, respectively m2 and m3, according to the relationship: max (mCharge) = max (m3) - min (m2).
    If a system with constant selectivities is considered, the composition of the liquid phase which gives the strongest stress in zone 2 and in zone 3 is the composition of the liquid phase at the point of injection of the feed into the unit. Indeed, from this point the concentration of para-xylene, which is the most adsorbed compound, increases in the direction of circulation of the solid in zone 2, and decreases in the direction of circulation of the liquid in zone 3. to approximate the composition of this point to the composition of the load to be treated, and it is this composition that will be used to evaluate the term δ2 and δ3 of equation 8. The terms δ2 and δ3 being defined by equation 7 mentioned above. For each adsorbent, this reduced flow rate max (mCharge) is calculated from the binary selectivity values measured experimentally and represented in FIG. 1 as a function of the molar ratio K20 / (K20 + BaO + Na2O) (FIG. 1). It can be seen that the reduced flow rate max (mcharge) is improved for a molar ratio K20 / (K20 + BaO + Na2O) of between 8.0% and 8.6%.
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    A zeolitic adsorbent comprising zeolite X crystals and comprising barium, potassium and sodium, wherein the molar ratio K20 / (K20 + BaO + Na2O) is between 8.0% and 8.6%.
    [2" id="c-fr-0002]
    2. Adsorbent according to claim 1, further comprising a non-zeolitic phase.
    [3" id="c-fr-0003]
    An adsorbent according to claim 1 or claim 2, wherein the sodium oxide content Na 2 O is less than 0.3% by weight based on the total mass of the adsorbent.
    [4" id="c-fr-0004]
    An adsorbent according to any one of the preceding claims, wherein the total content of alkali or alkaline earth metal oxides other than barium oxide BaO, potassium oxide K20 and sodium oxide Na20, is less than 1% by weight relative to the total mass of the adsorbent.
    [5" id="c-fr-0005]
    An adsorbent according to any one of the preceding claims, wherein the X zeolite crystals have an Si / Al atomic ratio of between 1.00 and 1.50 inclusive.
    [6" id="c-fr-0006]
    6. Adsorbent according to any one of the preceding claims, having a number average diameter of between 0.2 mm and 2 mm inclusive.
    [7" id="c-fr-0007]
    An adsorbent according to any one of the preceding claims, wherein the number average diameter of the zeolite crystals X is less than or equal to 1.5 μm inclusive.
    [8" id="c-fr-0008]
    8. Adsorbent according to any one of the preceding claims, having a loss on ignition, measured at 950 ° C according to the standard NF EN 196-2, between 4.0% and 7.7% by weight.
    [9" id="c-fr-0009]
    9. Adsorbent according to any one of the preceding claims, wherein the mass fraction of zeolite X is at least 80% by weight relative to the total weight of the adsorbent.
    [10" id="c-fr-0010]
    A process for the preparation of an adsorbent according to any one of the preceding claims, comprising at least the steps of: a) agglomeration of zeolite X crystals with a binder, and shaping of agglomerate, followed by drying and calcination, b) possible zeolization of the binder, c) cationic exchange of the agglomerate by contacting with a solution of barium ions, or potassium ions, or barium ions and potassium ions, d) cation exchange with potassium when the exchange step c) is carried out with a solution of barium ions alone, or cation exchange with barium when the step c) of exchange is carried out with a solution of potassium ions alone, e) then washing and drying the product thus treated, and f) activating the zeolite adsorbent thus obtained.
    [11" id="c-fr-0011]
    11. The method of claim 10, wherein the binder used in step a) contains at least 80% by weight of zeolitizable clay and a source of silica, and in that the process comprises a step b) of zeolitization of said zeolitizable binder by the action of an alkaline basic solution, preferably with a concentration solution of between 0.5 M and 5 M and for a duration of between a few tens of minutes and a few hours.
    [12" id="c-fr-0012]
    The method of claim 10 or claim 11, wherein the zeolite X used in step a) comprises, preferably is, a hierarchized porosity X type FAU zeolite.
    [13" id="c-fr-0013]
    13. Adsorbent according to any one of claims 1 to 9, obtainable according to the method of any one of claims 10 to 12.
    [14" id="c-fr-0014]
    14. Use of an adsorbent according to any one of claims 1 to 9, or according to claim 13, in the processes of: • separation of sections of C8 aromatic isomers and in particular xylenes, • separation of isomers from substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, and others, • separation of cresols, • separation of polyhydric alcohols.
    [15" id="c-fr-0015]
    15. Use according to claim 14, for the separation of para-xylene from aromatic isomeric cuts with 8 carbon atoms.
    [16" id="c-fr-0016]
    16. Process for recovering para-xylene from cuts of aromatic hydrocarbon isomers containing 8 carbon atoms, in the liquid phase, by adsorption of para-xylene by means of an adsorbent according to any one of claims 1 at 9 or 13 in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
    [17" id="c-fr-0017]
    17. Process for recovering para-xylene according to claim 16 of simulated moving bed type, preferably simulated countercurrent.
    [18" id="c-fr-0018]
    18. A process for recovering para-xylene from carbon-atom-containing aromatic hydrocarbon isomer sections, by adsorption of para-xylene by means of an adsorbent according to any one of claims 1 to at 9 or 13 in the presence of a desorbent, preferably selected from toluene and para-diethylbenzene.
    [19" id="c-fr-0019]
    19. A process for separating polyhydric alcohols employing an adsorbent according to any one of claims 1 to 9 or 13.
    [20" id="c-fr-0020]
    20. Process for the separation of isomers of substituted toluene, such as nitrotoluene, diethyltoluene, toluenediamine, using an adsorbent according to any one of claims 1 to 9 or 13.
    [21" id="c-fr-0021]
    21. A process for separating cresols, using an adsorbent according to any one of claims 1 to 9 or 13.
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1556523A|FR3038528B1|2015-07-09|2015-07-09|ZEOLITHIC ADSORBANTS, THEIR PREPARATION PROCESS AND THEIR USES|FR1556523A| FR3038528B1|2015-07-09|2015-07-09|ZEOLITHIC ADSORBANTS, THEIR PREPARATION PROCESS AND THEIR USES|
    TW105121713A| TWI702084B|2015-07-09|2016-07-07|Zeolite adsorbents, preparation process therefor and uses thereof|
    US15/742,614| US10913695B2|2015-07-09|2016-07-08|Zeolite adsorbents, preparation process therefor and uses thereof|
    CN201680040332.XA| CN108472625A|2015-07-09|2016-07-08|Zeolite adsorbents, preparation method and its purposes|
    CN202110907011.8A| CN113731354A|2015-07-09|2016-07-08|Zeolite adsorbent, method for the production thereof and use thereof|
    EP16741569.4A| EP3319723B1|2015-07-09|2016-07-08|Zeolitic adsorbents, method for the production thereof, and uses of same|
    PCT/EP2016/066293| WO2017005907A1|2015-07-09|2016-07-08|Zeolitic adsorbents, method for the production thereof, and uses of same|
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