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    • 专利摘要:
    The present invention relates to the use, for gas separation, of at least one zeolitic adsorbent material comprising at least one FAU-type zeolite, said adsorbent having an external surface greater than 20 m 2 g -1, a phase content non-zeolitic (PNZ) such that 0 <PNZ ≤ 30%, and Si / Al atomic ratio between 1 and 2.5. The invention also relates to a zeolitic adsorbent material having an Si / Al ratio such that 1 ≤ Si / Al <2.5, a mesoporous volume of between 0.08 cm3g-1 to 0.25 cm3g-1, a ratio (Vmicro-Vmeso) / Vmicro between -0.5 and 1.0, terminals not included, and a non-zeolitic phase (PNZ) content, such that 0 <PNZ ≤ 30%.
    公开号:FR3032130A1
    申请号:FR1550781
    申请日:2015-02-02
    公开日:2016-08-05
    发明作者:Cecile Lutz；Ludivine Bouvier；Serge Nicolas；Jullian Vittenet；Sylvie Szendrovics；Quitterie Persillon
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to the use of zeolitic adsorbent materials in the form of agglomerates comprising at least one zeolite of the faujasite type, the said adsorbents exhibiting a high concentration of zeolite. a large external surface characterized by nitrogen adsorption, and a high microporous volume, for separation in the gas phase, in particular in pressure-modulated processes, either of the PSA type (pressure swing adsorption or "pressure swing adsorption" in the English) either of the type VSA (Vacuum Swing Adsorption in the English language), or of the VPSA type (hybrid process of the two previous ones), or of the RPSA type ("Rapid Pressure Swing Adsorption" in English), in temperature modulated methods of the type TSA (Temperature Swing Adsorption or "Temperature Swing Adsorption" in / 5 English language) and / o u in pressure and temperature modulated processes of the PTSA (Pressure and Temperature Swing Adsorption) type. The present invention also relates to a gas separation and purification process using said zeolite adsorbents having a large zo external surface. The invention also relates to zeolitic adsorbent materials used in the context of the present invention having a large external surface and comprising lithium and / or calcium and / or sodium. [0004] The use of this type of agglomerate is particularly advantageous in applications where the kinetics of transfer, the adsorption volume capacity, parameters determining the efficiency and the overall productivity of the process, as well as low losses. load are sought. In adsorption separation technologies, much effort has been made in recent years to increase the hourly productivity of the adsorbent beds, in particular by increasing the frequency of the adsorption / desorption cycles, which means that the adsorbent used, in addition to its thermodynamic adsorption properties, must be able to saturate by adsorption and restore desorption adsorbed gas in times of shorter and shorter periods. The adsorbents must therefore be designed so as to have the most efficient mass transfer possible, that is, so that the gases to be separated or purified reach the sites as quickly as possible. adsorption and also be desorbed as quickly as possible. Several tracks have been explored to achieve this goal. The first method proposed by the literature consists in reducing the size of the adsorbent particles. It is generally accepted that this has the effect of allowing a faster diffusion of the gases in the macroporous network, the material transfer kinetic constant being inversely proportional to the square of the particle diameter (or equivalent dimension, according to the morphology of the adsorbents). For example, the article "Adsorbent particle size effects in the separation of air adsorption" by E. Alpay et al., Chemical Engineering Science, 49 (18), 3059-3075, (1994). WO2008 / 152319 describes the preparation, by atomization, mechanically resistant adsorbents of small sizes, which are for example used in portable medical oxygen concentrators, as shown in US2013 / 0216627. The main drawback of the reduction in the size of the adsorbent particles is the increase in the pressure losses in the adsorbers and the significant energy consumption associated therewith. This is particularly unacceptable in industrial gas production adsorption processes. The second method is to improve the ability to intra-granular transfer zo adsorbents, without changing their size. International Applications WO99 / 43415, WO99 / 43416, WO99 / 43418, WO2002 / 049742, WO2003 / 004135 describe adsorbents with improved kinetics obtained by zeolitic active material conversion of the agglomeration binder and the associated gas separation processes, more effective than with conventional particles. [0009] WO2008 / 051904 proposes a process for the extrusion / spheronization process of zeolite adsorbent beads based on LiX zeolite with improved diffusion. WO2008 / 109882 describes the preparation of adsorbents with high mechanical strength and improved mass transfer from LiX or LiLSX zeolites and less than 15% of colloidal introduced silicic binder. The application EP1240939 proposes to select for uses in the PSA or VSA process adsorbents having a ratio between their kinetic constants for transporting the adsorbable compounds in the gas phase and in the solid phase. US6328786 defines a minimum strength threshold and a kinetic coefficient above which adsorbents are preferred for use in the PSA process. EP1048345 discloses high macroporosity adsorbents made by a spheronization and lyophilization technique. A third method is to improve access to the adsorbent using different shaping geometries combining both reduced thicknesses of active material and fluid passage sections large enough to allow a flow with losses. limited loads. Adsorbent sheets and fabrics, monoliths of the honeycomb type, foams or others may be mentioned. Document FR2794993 proposes to use heterogeneous beads, with a thin adsorbent peripheral layer encapsulating an inert core: the diffusion distance is reduced, without increasing the loss of charge. This system has the defect of being of low volume efficiency: a substantial part of the adsorber is occupied by inert material in the sense of adsorption, which has a significant impact in terms of the dimensions of the installations and therefore investments, or even weight, which can be inconvenient, in the case of portable purification / separation apparatus, such as for example the medical oxygen concentrators. US2012 / 0093715 and US2013 / 0052126 patent applications teach that one can form monolithic zeolite structures with a hierarchical structure, by adding a polymer to the synthesis reaction medium: as for the sheets and the adsorbent tissues the solids obtained have a macroporous volume and a very large mesoporous volume, these solids are therefore very sparse and their volume efficiency is low, because of their low capacity for adsorption volume. Thus, all these adsorbent geometries of various natures pose relatively complex implementation problems, mechanical resistance to fatigue or attrition and low volume efficiency, since the content of active ingredient is often reduced to the benefit. inert binders or other mechanical reinforcing fibers or since the materials obtained are very sparse. There remains a need for zeolite adsorbents useful for the separation and purification of gases having good transfer properties that do not have the disadvantages associated with the use of the adsorbents of the prior art. In particular, there remains a need for a zeolitic adsorbent having greater adsorption capacities and better adsorption / desorption kinetics, allowing in particular a more intensive use of processes, including PSA processes, TSA or VPSA. The inventors have now discovered that the above objectives can be achieved in whole or at least in part through the adsorbents specifically dedicated to the uses of separation and purification of gases as they will be described now. Thus, and according to a first aspect, the invention relates to the use for the separation of gases, of at least one zeolitic adsorbent material comprising at least one type of zeolite FAU, said adsorbent having: - a external surface, measured by nitrogen adsorption and expressed in m2 per gram of adsorbent, greater than 20 m 2 · g -1, and preferably between 20 m 2 · g -1 and 300 m 2 · g -1, and preferably still between 30 m2.g-1 and 250 m2.g-1 and even more preferably between 40 m2. g-1 and 200 m2.g-1, and especially between 50 m2.g-1 and 200 m2.g-1, a non-zeolite phase content (PNZ), such that 0 <PNZ 30%, preferably 3% PNZ 25%, more preferably 3% PNZ 20%, advantageously 5% PNZ 20%, more preferably 7% PNZ 18%, measured by XRD (X-Ray Diffraction), by weight by relative to the total weight of the adsorbent, and of the Si / Al atomic ratio of the adsorbent between 1 and 2.5, preferably between 1 and 2.0, more preferably between 1 and 1.8, and most preferably between 1 and 1.6, all measurements being performed on the adsorbent material exchanged at least 95% sodium. In the present description, the term "FAU type zeolite" designates a faujasite type zeolite, advantageously a mesoporous faujasite zeolite chosen from LSX type zeolites, MSX, X, Y and mixtures thereof. According to one embodiment, the zeolitic adsorbent material may also comprise one or more other zeolites chosen from zeolites of type FAU (LSX, MSX, X, Y), type LTA, type CHA (Chabazite). , of the HEU type (Clinoptilolite), and mixtures of two or more of them, and more preferably of the zeolites LSX, MSX, X, and mixtures of two or more of them. Other zeolites may be present in minor amounts in the adsorbents of the invention or used in the process of the invention. These zeolites can be considered as pollutants, in particular because they do not contribute to the adsorption of the gases, in other words they are inert with respect to the adsorption of the gases. These zeolites include, by way of nonlimiting examples, sodalite, hydroxysodalite, zeolite P and other zeolites inert with respect to the adsorption of gases. The different types of zeolites present in the zeolite adsorbent material are determined by XRD. The amount of zeolites is also measured by XRD and is expressed in% by weight relative to the total weight of the adsorbent material. As a corollary, in the present invention, the term "non-zeolite phase" (or "PNZ") refers to any phase present in the adsorbent material, other than the zeolite (s) defined herein. above, referred to as "zeolitic phase" or "PZ". The amount of non-zeolitic phase is expressed by the complement at 100% of the zeolite phase of the adsorbent, that is: c / oPNZ = 100-% PZ, where c / oPNZ is the weight percent of PNZ and% PZ the percentage by weight of zeolite phase, relative to the total weight of the adsorbent. By "adsorbent exchanged at least 95% sodium" means that at least 95% of the cationic exchangeable sites of the zeolite phase are occupied by sodium cations. This zeolitic adsorbent material exchanged at least 95% sodium can be obtained and is preferably obtained according to the following protocol: the zeolitic adsorbent material to be exchanged with sodium is introduced into a solution of sodium chloride at / 1 mole of NaCl per liter, at 90 ° C, for 3 hours, with a liquid to solid ratio of 10 mL. The operation is repeated n times, n being at least 1, preferably at least 2, preferably at least 3, more preferably at least 4. [0024] Solids from Exchange n-1 and n are successively four times washed by immersing in water at a rate of 20 ml / g to remove the excess salt, and then dried for 12 hours at 80 ° C. in air, before drying. be analyzed by X-ray fluorescence. If the weight percentage of sodium oxide of the zeolite adsorbent material, between the exchange operations n-1 and n, is stable to ± 1%, said zeolite adsorbent material is considered to be "in its form exchanged at least 95% sodium ". If necessary, additional exchanges are carried out as described above until a stability of the weight percentage of sodium oxide of ± 1% is obtained. In particular, successive batch cation exchanges with a large excess of sodium chloride may be carried out until the sodium oxide mass content of the zeolitic adsorbent material, determined by chemical analysis of X-ray fluorescence type, be stable at ± 1%. This measurement method is explained later in the description. Alternatively, the zeolitic adsorbent material can already be intrinsically in its sodium-exchanged form after the synthesis step when the latter is carried out exclusively in sodium alkaline medium. [0026] The Si / Al atomic ratio of the zeolitic adsorbent material is measured by elemental chemical analysis in X-ray fluorescence, a technique well known to those skilled in the art and explained further in the description. If necessary, the sodium exchange is carried out before analysis according to the detailed procedure above. By "Vmicro" is meant the microporous volume of the zeolitic adsorbent material whose measurement technique is explained below. By "Vmeso" is meant the mesoporous volume of the zeolite adsorbent material whose measurement technique is explained below. According to a preferred embodiment, said at least one zeolitic adsorbent material that can be used in the context of the present invention has a mesoporous volume (Vmeso) of between 0.08 cm3g-1 and 0.25 cm3. 1, preferably between 0.08 cm3g-1 and 0.22 cm3g-1, and more preferably between 0.09 cm3g-1 and 0.20 cm3g-1, more preferably between 0.10 cm3g-1 and 0.20 cm3g-1, limits included, measured on the adsorbent material exchanged at least 95% sodium. According to another preferred embodiment, said at least one zeolitic adsorbent material that can be used in the context of the present invention has a (Vmicro-Vmeso) / Vmicro ratio between -0.5 and 1.0, terminals not included. , preferably between -0.1 and 0.9, terminals not included, preferably between 0 and 0.9, terminals not included, more preferably between 0.2 and 0.8, terminals not included, preferably between 0.4 and 0.8, bounds not included, preferably between 0.6 and 0.8, limits not included, where Vmicro is the microporous volume measured by the Dubinin-Raduskevitch method and Vmeso is the mesoporous volume determined by the Barrett-Joyner-Halenda method (BJH), all measurements being performed on the adsorbent material exchanged at least 95% sodium. According to yet another embodiment, said at least one zeolitic adsorbent material has a microporous volume (Vmicro, or Dubinin-Raduskevitch volume), expressed in cm 3 per gram of adsorbent material, between 0.210 cm 3. 1 and 0.360 cm3g-1, preferably between 0.230 cm3g-1 and 0.350 cm3g-1, preferably between 0.240 cm3g-1 and 0.350 cm3g-1, more preferably 0.250 cm3g. -1 and 0.350 cm3g-1, measured on the adsorbent material exchanged at least 95% sodium. From the microporous volume according to Dubinin-Raduskevich measured on the zeolitic adsorbent material exchanged with sodium, it is also possible to calculate an overall Dubinin-Raduskevitch volume of zeolite (s) FAU, weighted PNZ. The total volume of macro- and meso-pores zeolitic adsorbent materials used in the context of the present invention, measured by mercury intrusion, is advantageously between 0.15 cm3g-1 and 0.5 cm3. g-1, preferably between 0.20 cm3.g-1 and 0.40 cm3g-1 and very preferably between -7- 0.20 cm3.g-1 and 0.35 cm3.g -1, the measurements being made on the adsorbent material exchanged at least 95% sodium. The volume fraction of the macropores of the zeolitic adsorbent material that can be used in the context of the present invention is preferably between 0.2 and 1.0 of the total volume of the macro- and meso-pores, very preferably between 0.4 and 0.8, and even more preferably between 0.45 and 0.65 inclusive, the measurements being made on the zeolite adsorbent material exchanged at least 95% sodium. [0034] The zeolitic adsorbent materials that can be used in the context of the present invention are either known or can be prepared from known procedures, or are new and, as such, form an integral part of the present invention. According to another preferred embodiment, the use according to the invention uses a zeolitic adsorbent material comprising at least one mesoporous FAU 15 type zeolite. By "mesoporous" is meant a zeolite which, together with the microporosity inherent in the structure of the zeolite, presents internal cavities of nanometric size (mesoporosity), easily identifiable by observation by means of a transmission electron microscope (TEM or "TEM" in English), as described for example in US7785563. More precisely, said zeolite FAU of the zeolitic adsorbent material is a mesoporous FAU zeolite, that is to say a zeolite having an external surface, defined by the t-plot method described below, of between 40 m.sup.2. .g-1 and 400 m2.g-1, preferably between 60 m2.g-1 and 200 m2.g-1, limits included. By extension, in the sense of the present invention, a "non-mesoporous zeolite" is a zeolite possibly having an external surface, defined by the t-plot method described below, strictly less than 40 m 2 g -1. In particular, the zeolitic adsorbent materials that can be used in the context of the present invention comprise at least one FAU-type zeolite, said at least one FAU-type zeolite has a Si / Al ratio corresponding to the 1 Si / Al inequation. <1.5, preferably 1 Si / Al 1.4, and more preferably an Si / Al atomic ratio equal to 1.00 + -0.05, said Si / Al ratio being measured by Nuclear Magnetic Resonance. (NMR) solid silicon 29 (295i NMR), according to techniques well known to those skilled in the art. The Si / Al ratio of each of the zeolites present in the adsorbent is also measured by solid NMR. According to a preferred embodiment, the zeolite FAU of the zeolitic adsorbent material is in the form of crystals whose number-average diameter, measured by scanning electron microscope (SEM), is less than 20 μm, of preferably between 0.1 pm and 20 pm, preferably between 0.1 and 10 pm, preferably between 0.5 pm and 10 pm, more preferably between 0.5 pm and 5 pm inclusive . According to yet another preferred embodiment, said zeolitic adsorbent material comprises at least one cation chosen from the ions of Groups IA, IIA, IIIA, IB, IB, III B of the periodic table, the trivalent ions of the lanthanide or rare-earth series, zinc (II) ion, silver ion (I), cupric ion (II), chromium ion (III), ferric ion (III), ammonium ion and / or hydronium ion, the preferred ions being calcium, lithium, sodium, potassium, barium, cesium, strontium, zinc and rare earth ions, and more preferably the sodium, calcium and lithium ions. According to one embodiment, the zeolitic adsorbent material that can be used in the context of the present invention comprises at least one alkali metal or alkaline earth metal chosen from sodium, calcium, lithium or mixtures of two or three of them. all proportions, the contents, expressed in oxides, are preferably such that: - CaO content between 0 and 20.5% by weight relative to the total weight of the zeolite adsorbent material, preferably between 3 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 7.5 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 9 and 20.5% by weight relative to to the total weight of the zeolitic adsorbent material, limits included, - content of Li 2 O between 0 and 12% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 3 and 12% by weight relative to the weight to tal of the zeolitic adsorbent material, preferably between 5 and 12% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 6.5 and 12% by weight relative to the total weight of the zeolitic adsorbent material, limits included; Na.sub.2 content of between 0 and 22% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 19% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 15% by weight. weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 10% by weight relative to the total weight of the zeolitic adsorbent material, and very preferably between 0 and 7% by weight relative to the total weight zeolitic adsorbent material, advantageously between 0 and 2% by weight relative to the total weight of the zeolite adsorbent material inclusive, - it being understood that the material has Zeolitic absorbent comprises at least one of the three metals selected from lithium, sodium and calcium, said zeolite adsorbent material may also comprise at least one rare earth, chosen from lanthanides and actinides, preferably from lanthanides, in a content generally comprised between 0 and 10%, preferably between 0 and 7%, - said zeolite adsorbent material may also comprise, in small amounts (% expressed as oxide, less than 5%, preferably less than 2%) of one or more other cations other than lithium, sodium and calcium, for example and preferably selected from potassium, barium, strontium, cesium, transition metals such as silver, and others. According to the present invention, the zeolitic adsorbent materials described above are particularly useful adapted and effective in the processes for separation in the gas phase, in particular in processes modulated in pressure and / or temperature, that is to say PSA type, either of the VSA type, or of the VPSA type, or of the RPSA type, or of the TSA type type, and / or in PTSA type processes. More specifically, the present invention relates to the use of at least one zeolitic adsorbent material, comprising at least one type of zeolite FAU, as defined above, for the gas separation. By gas separation is meant purifications, pre-purifications, eliminations, and other separations of one or more gaseous compounds present in a mixture of one or more gaseous compounds. According to a preferred aspect of the present invention, the zeolitic adsorbent materials that can be used for the purification of gases are materials that generate only a small amount of pressure drop or acceptable pressure drop for the aforementioned uses. Thus, agglomerated and shaped zeolite adsorbent materials made according to all techniques known to those skilled in the art are preferred, such as extrusion, compacting, agglomeration on a granulator plate, granulator drum, atomization and the like. The proportions of agglomeration binder and zeolites used are typically those of the prior art, that is to say between 5 parts and 30 parts by weight of binder for 95 parts to 70 parts by weight of zeolite . The zeolitic adsorbent material that can be used in the context of the present invention, whether in the form of beads, extrudates or the like, generally has a mean volume diameter, or an average length (greater dimension when - 10 - is not spherical), less than or equal to 7 mm, preferably between 0.05 mm and 7 mm, more preferably between 0.2 mm and 5 mm and more preferably between 0.2 mm and 2.5 mm. The zeolitic adsorbent materials useful in the context of the present invention also have mechanical properties that are particularly suitable for the applications for which they are intended, that is to say: either a crush resistance in a bed (REL) measured according to standard ASTM 7084-04 between 0.5 MPa and 3 MPa, preferably between 0.75 MPa and 2.5 MPa, for a material of average volume diameter (D50) or a length (greater dimension io when the material is not spherical), less than 1 mm, inclusive, - a crush resistance in grain, measured according to ASTM D 4179 (2011) and ASTM D 6175 (2013) ), between 0.5 daN and 30 daN, preferably between 1 daN and 20 daN, for a material of average volume diameter (D50) or a length (larger dimension when the material is not spherical), greater than or equal to 1 mm, limits included. According to another preferred embodiment, the use according to the invention uses at least one zeolitic adsorbent material having a high adsorption capacity, that is to say a microporous volume volume expressed in cm3. .cm-3 of adsorbent material exchanged at least 95% sodium, said microporous volume volume being greater than 0.10 cm3.cm-3, preferably greater than 0.12 cm3.cm-3, more preferably greater than at 0.15 cm3.cm-3, more preferably greater than 0.16 cm3.cm-3, more preferably greater than 0.18 cm3.cm-3, very preferably greater than 0.20 cm3.cm-3. According to yet another embodiment, the use according to the invention preferably employs at least one zeolitic adsorbent material having a loss on ignition, measured at 950 ° C. according to the NF EN 196-2 standard. between 0 and 5%, preferably between 0 and 3% by weight. In particular, the present invention relates to the use of at least one zeolite adsorbent material as defined above for the purification of natural gas, in particular for the removal of impurities and preferably for the removal of impurities. the elimination of carbon dioxide and / or mercaptans, present in natural gas, and especially according to adsorption processes modulated in pressure and / or temperature (PSA or TSA or PTSA), preferably TSA or PTSA . It is particularly preferred to use for these types of applications, the adsorbent materials comprising a FAU zeolite, preferably mesoporous, of a type selected from NaX and CaX, and mixtures thereof. For these types of applications, a zeolitic adsorbent material having a volume average diameter (or the greatest length) of between 0.3 mm and 7.0 mm, preferably between 0, is preferred. 8 mm and 5.0 mm, and more preferably between 2.0 mm and 5.0 mm, inclusive. According to another embodiment, the present invention relates to the use of at least one zeolite adsorbent material as just defined for the non-cryogenic separation of industrial gases and gases from the air, and in particular for nitrogen adsorption in air gas separation, in particular for the enrichment of oxygen in the air. This use is particularly suitable in pressure swing adsorption devices (PSA) according to very short cycles, and in particular in breathing oxygen concentrators, as described for example in WO2008 / 152319. In the case of the use according to the invention for the non-cryogenic separation of industrial gases and gases from air, these processes are well known from the prior art, and in particular from document EP0893157 which describes In general, gas separation / purification processes using zeolitic adsorbents. For applications of non-cryogenic separation of industrial gases and air gases and preferably of nitrogen separation for oxygen enrichment, the zeolitic adsorbent material comprising at least one FAU zeolite 20 is furthermore preferred. , preferably mesoporous, of a type chosen from NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX, LiCaLSX, and mixtures of two or more of them, said zeolitic adsorbent material comprising at least one alkali metal or alkaline metal. earthy selected from sodium, calcium, lithium, mixtures of two or three of them in all proportions, the contents expressed in oxides are as defined above. More particularly, the use described above is particularly suitable for the separation of nitrogen for oxygen enrichment, and especially for use in oxygen concentrators respiratory assistance. It is preferred in these cases to use at least one zeolitic adsorbent material comprising sodium, calcium and / or lithium, alone or as a mixture, and it is particularly preferred for these types of applications to use a zeolitic adsorbent material comprising at least a FAU zeolite, preferably mesoporous, of a type chosen from NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX, LiCaLSX, and mixtures of two or more of them, preferably from CaLSX, LiLSX, LiCaLSX, more preferably at least one LiLSX zeolite, preferably mesoporous LiLSX. For applications in the separation of industrial gases and air gases in general, a zeolite adsorbent material in the form of beads having a volume average diameter of between 0.05 mm and 5 mm is preferred. preferably between 0.05 mm and 3.0 mm, more preferably between 0.05 mm and 2.0 mm. For specific air oxygen enrichment applications, for example respiratory assistance oxygen concentrators, a zeolitic adsorbent material in the form of beads having a mean volume diameter of between 0.05 mm is preferred. and 1 mm, preferably between 0.1 mm and 0.7 mm, more preferably between 0.3 mm and 0.6 mm. According to another embodiment, the invention relates to the use of at least one zeolite adsorbent material as just defined for the purification of synthesis gas. An example of a synthesis gas purification process is described in patent EP1312406. The synthesis gases referred to herein are in particular synthesis gases based on hydrogen and carbon monoxide and / or hydrogen and nitrogen, and more particularly mixtures of hydrogen and carbon monoxide and / or hydrogen and nitrogen, these synthesis gases may further contain, or be polluted by, carbon dioxide and one or more other possible impurities, such as for example and without limitation one or more impurities selected from nitrogen , carbon monoxide, oxygen, ammonia, hydrocarbons and oxygenated derivatives, in particular alkanes, in particular methane, alcohols, in particular methanol, and others. The use according to the present invention is thus particularly suitable for the removal of nitrogen, carbon monoxide, carbon dioxide, methane, and other impurities, preferably by adsorption methods modulated by pressure (PSA), for the production of hydrogen. For these types of applications, the adsorbent materials comprising a FAU zeolite, preferably mesoporous, of the type chosen from NaX, LiX, LiLSX, CaX, CaLSX, LiCaX and LiCaLSX, preferably chosen from among NaX, NaLSX and LiCaLSX, are preferred. mixtures of two or more of them. For these types of applications, a zeolitic adsorbent material having a volume average diameter (or the greatest length) of between 0.3 mm and 7 mm, preferably between 0.8 mm and 5, is preferred. 0 mm, and more preferably between 1.0 mm and 3.0 mm, inclusive. According to yet another embodiment, the invention also relates to the use of at least one zeolite adsorbent material as just defined for air purification cryogenic units ("Air Separation Units"). In the English language or "ASU"), in particular for the removal of hydrocarbons, carbon dioxide and nitrogen oxides, upstream of the cryogenic distillation units. For these types of applications, preferably carried out in PSA, TSA or PTSA processes, and preferably TSA or PTSA, zeolitic adsorbent materials comprising a FAU zeolite, preferably mesoporous, of selected types are preferred. among NaX, NaLSX, CaX, CaLSX, and mixtures of two or more thereof. For these types of applications, a zeolitic adsorbent material having a volume average diameter (or the greatest length) of between 0.3 mm and 7.0 mm, and more preferably between 0.5 mm, is preferred. and 5.0 mm, terminals included. In another aspect, the invention relates to a zeolitic adsorbent material having: an Si / Al ratio of said adsorbent, such as 1 Si / Al <2.5, preferably 1 Si / Al 2, more preferably 1 Si / Al 1.8, and more preferably between 1 Si / Al 1.6, - a mesoporous volume of between 0.08 cm 3. g-1 at 0.25 cm3g-1, preferably between 0.08 cm3g-1 and 0.22 cm3g-1, and more preferably between 0.09 cm3g-1 and 0, 20 cm3g-1, more preferably between 0.10 cm3g-1 and 0.20 cm3g-1, inclusive terminals of (Vmicro-Vmeso) / Vmicro ratio between -0.5 and 1, 0, terminals not included, preferably -0.1 and 0.9, terminals not included, preferably 0 and 0.9, terminals not included, more preferably between 0.2 and 0.8, terminals not included, of more preferably between 0.4 and 0.8, terminals not included, preferably between 0.6 and 0.8, terminals not included, where the Vmicro is measured by the Dubinin-Raduskevitch method and Vmeso is measured by the BJH method, and - a non-zeolite phase (PNZ) content, such as 0 <PNZ 30%, preferably 3% PNZ 25%, more preferably 3% PNZ 20%, advantageously 5% PNZ 20%, more preferably 7% PNZ 18%, measured by XRD, by weight relative to the total weight of the material zeolitic adsorbent, all measurements being performed on the zeolite adsorbent material exchanged at least 95% sodium. The zeolite adsorbent material of the invention as it has just been defined is a new material in that it results from the agglomeration, with a binder as written below, of at least one zeolite FAU mesoporous, where the term "mesoporous", already defined previously, designates a zeolite which, together with the microporosity inherent in the structure of the zeolite, presents internal cavities of nanometric size (mesoporosity), easily identifiable by observation by means of a microscope electronic transmission (MET or "TEM" in English), as described for example in U57785563. More specifically, the zeolitic adsorbent material comprises at least one mesoporous FAU zeolite, that is to say a zeolite having an external surface, defined by the t-plot method described below, between 40.degree. m2.g-1 and 400 m2.g-1, preferably between 60 m2.g-1 and 200 m2.g-1, limits included. In addition, the zeolitic adsorbent material according to the invention comprises at least one metal chosen from lithium, sodium, calcium and mixtures of two or more of these metals, preferably two metals chosen from lithium and sodium. , calcium, preferably sodium and lithium or sodium and calcium or sodium, lithium and calcium. Zeolite adsorbent materials in which the barium oxide content is less than 0.5%, preferably less than 0.3%, more preferably less than 0.1%, by weight relative to the total weight, are furthermore preferred. of the material. These characteristics make the zeolitic adsorbent material according to the invention particularly suitable for treating gas, as described above in the present description. The zeolitic adsorbent material according to the invention may be in any form known to those skilled in the art, and preferably in simple geometric shapes, that is to say in granular forms, for example of the bead type. or sticks, that is to say in spherical or cylindrical forms, respectively. Such simple shapes are particularly well suited because they are easy to implement especially because of their shapes and sizes compatible with existing technologies. In addition, these simple forms make the processes used energy-efficient, the zeolitic adsorbent material generating low pressure losses, and having improved transfer properties. The zeolitic adsorbent material according to the invention may be prepared according to any method known to those skilled in the art, and in particular, and preferably from the method of preparation of mesoporous FAU as described for example by W.
    [0002] Schwieger (Angew Chem Int.Ed., (2012), 51, 1962-1965) and by agglomerating the crystals obtained with at least one organic or mineral binder, preferably mineral, more preferably a binder selected from clays, zeolitizable or not, and in particular among kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, as well as mixtures of two or more of these clays, in all proportions. Agglomeration and shaping can be carried out according to all techniques known to those skilled in the art, such as extrusion, compaction, agglomeration on granulator plate, granulator drum, atomization and others. These different techniques have the advantage of allowing the preparation of adsorbent materials according to the invention having the sizes and shapes previously described and particularly well suited to the treatment of gases. [0071] The proportions of agglomeration binder (for example clays, as indicated above) and of zeolite (s) used for the preparation are typically those of the prior art, and vary according to the content of PNZ desired and the degree of zeolitization of the binder. These proportions are easily calculable by those skilled in the art of zeolite agglomerate synthesis. The agglomerates of the zeolite adsorbent materials, whether in the form of beads, extrudates or the like, generally have a mean volume diameter, or an average length (larger dimension when they are not spherical), less than or equal to 7 mm, preferably between 0.05 mm and 7 mm, more preferably between 0.2 mm and 5 mm and more preferably between 0.2 mm and 2.5 mm. The process for preparing the zeolitic adsorbent materials according to the invention is easily adaptable from the preparation methods known to those skilled in the art, as already indicated, the use of at least one mesoporous FAU zeolite which does not modify These processes are not substantially known, which means that the preparation process is an easy, fast and economical method of implementation which is therefore easy to industrialize with a minimum of steps. The zeolitic adsorbent material of the invention preferably comprises at the same time macro-pores, mesopores and micropores. By "macro-pores" is meant pores whose opening is greater than 50 nm, preferably between 50 nm and 400 nm. By "meso-pores" is meant pores whose opening is between 2 nm and 50 nm, limits not included. By "micro-pores" is meant pores whose opening is less than 2 nm. According to a preferred embodiment, the zeolitic adsorbent material according to the present invention has a microporous volume (Dubinin-Raduskevitch volume), expressed in cm 3 per gram of zeolitic adsorbent material, of between 0.210 cm 3 .g -1 and 0.360 cm3.g-1, preferably between 0.230 cm3g-1 and 0.350 cm3g-1, more preferably between 0.240 cm3g-1 and 0.350 cm3g-1, advantageously between 0.250 cm3g-1 and 0.350 cm3g-1, said microporous volume being measured on the zeolite adsorbent material exchanged at least 95% sodium. The total volume of the macro- and meso-pores of the zeolitic adsorbent materials according to the invention, measured by mercury intrusion, is advantageously between 0.15 cm3g-1 and 0.5 cm3g-1, preferably between 0.20 cm3g-1 and 0.40 cm3g-1 and very preferably between 0.20 cm3g and 0.35 cm3g-1, the measurements being carried out on the adsorbent material exchanged at least 95% sodium. The volume fraction of the macropores of the zeolitic adsorbent material is preferably between 0.2 and 1.0 of the total volume of the macro- and meso-pores, very preferably between 0.4 and 0. , 8, and even more preferably between 0.45 and 0.65 inclusive, the measurements being made on the zeolite adsorbent material exchanged at least 95% sodium. The size of the FAU-type zeolite crystals used to prepare the zeolite adsorbent material of the invention, as well as the size of the FAU-type zeolite elements in the zeolite adsorbent material, are measured by observation under a scanning electron microscope. (SEM). Preferably, the mean diameter of the FAU type zeolite crystals is between 0.1 μm and 20 μm, preferably between 0.5 μm and 20 μm, and more preferably between 0.5 μm and 10 μm. Observation SEM also makes it possible to confirm the presence of non-zeolitic phase comprising, for example, residual binder (not converted during the possible zeolitization step) or any other amorphous phase in the agglomerates. According to a preferred embodiment, the zeolitic adsorbent material according to the invention has an external surface, measured by nitrogen adsorption and expressed in 15 m 2 per gram of adsorbent, greater than 20 m 2 · g -1, and preferably between 20 m2.g-1 and 300 m2.g-1, and more preferably between 30 m2.g-1 and 250 m2.g-1 and more preferably between 40 m2.g-1 and 200 m2.g-1, and especially between 50 m2.g-1 and 200 m2.g-1 the measurements being made on the zeolite adsorbent material exchanged at least 95% sodium. According to a preferred embodiment, the zeolitic adsorbent material according to the invention has a high adsorption volume capacity, that is to say a microporous volume volume expressed in cm3.cm-3 of zeolitic adsorbent material. exchanged at least 95% with sodium, said microporous volume volume being greater than 0.10 cm3.cm-3, preferably greater than 0.12 cm3.cm-3, more preferably greater than 0.15 cm3.cm -3, more preferably greater than 0.16 cm3.cm-3, more preferably greater than 0.18 cm3.cm-3, most preferably greater than 0.20 cm3.cm-3. According to a preferred embodiment, the zeolitic adsorbent material according to the invention comprises at least one mesoporous FAU zeolite as defined above, said at least one zeolite having an Si / Al ratio, such as 1 Si / Al 1.5, preferably 1 Si / Al 1.4. According to a very particularly preferred aspect, the Si / Al ratio of said at least one mesoporous FAU zeolite is equal to 1.00 ± 0.05, the measurements being performed on the zeolite adsorbent material exchanged at least 95% with sodium. . According to yet another preferred embodiment, said zeolitic adsorbent material comprises at least one cation selected from Groups IA, IIA, IIIA, IB, IB, III B of the Periodic Table, trivalent ions of the lanthanide or rare-earth series, the zinc (II) ion, the silver ion (I), the cupric ion (II), the chromium ion (III), the ferric ion (III) ), the ammonium ion and / or the hydronium ion, the preferred ions being the calcium, lithium, sodium, potassium, barium, cesium, strontium, zinc and rare-earth ions, and more preferably the sodium, calcium and lithium ions; , as indicated previously. The metal contents of the zeolitic adsorbent material according to the invention, expressed as oxides, are preferably those indicated above, and more particularly: CaO content of between 0 and 20.5% by weight relative to the total weight. zeolite adsorbent material, preferably between 3 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 7.5 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 9 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, inclusive, Li20 content between 0 and 12% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 3 and 12% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 5 and 12% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 6.5 and 12% by weight relative to the total weight of the adsorbent, limits included, 20 - Na 2 O content between 0 and 22% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 19% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 15% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 10% by weight relative to the total weight of the zeolitic adsorbent material, and most preferably between 0 and 7% by weight relative to the total weight of the zeolitic adsorbent material, advantageously between 0 and 2% by weight relative to the total weight of the zeolite adsorbent material inclusive; it being understood that the zeolitic adsorbent material comprises at least one of the three metals chosen from lithium, sodium and calcium, said zeolitic adsorbent material possibly also comprising at least a rare earth, selected from lanthanides and actinides, preferably from lanthanides, in a content generally between 0 and 10%, preferably between 0 and 7%, - said zeolitic adsorbent material may also comprise, in weak quantities (% expressed as oxide, less than 5%, preferably less than 2%) of one or more other cations other than lithium, sodium and calcium, for example and preferably selected from potassium, barium, strontium , cesium, transition metals such as silver, and others. As indicated above, the zeolite adsorbent materials in which the barium oxide content is less than 0.5%, preferably less than 0.3%, more preferably less than 0.1%, are furthermore preferred. by weight relative to the total weight of the material. According to another preferred aspect, the zeolitic adsorbent material according to the invention does not have a zeolite structure other than the FAU structure (faujasite). The expression "does not have a zeolite structure other than the FAU structure", it is meant that a X-ray diffraction analysis of the adsorbent material according to the invention does not make it possible to detect more than 5% by weight, preferably not more than 2% by weight, inclusive limits, of zeolite structure other than a faujasite structure, relative to the total weight of the adsorbent material. According to yet another preferred embodiment, the invention relates to a zeolitic adsorbent material as defined above and having a total volume of the macro- and meso-pores, measured by mercury intrusion, of between 0.15 and 0.15. cm3.g-1 and 0.5 cm3g-1, and a volume fraction of the macropores between 0.2 and 1 times said total volume of the macro- and meso-pores, preferably between 0.4 and 0 , 8, limits included, the measurements being made on the adsorbent material exchanged at least 95% sodium. Characterization Techniques The physical properties of the zeolite adsorbent materials are evaluated by methods known to those skilled in the art, the main of which are summarized below. Granulometry of zeolite crystals: The estimation of the number average diameter of zeolite crystals of FAU type contained in zeolitic adsorbent materials, and which are used for the preparation of said zeolitic adsorbent material, is carried out by microscopic observation. scanning electron microscope (SEM). 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%. Granulometry of Zeolite Adsorbents The determination of the average volume diameter (or "volume mean diameter") of the zeolite adsorbent material of the process according to the invention is carried out by analysis of the particle size distribution of a sample of adsorbent material. Imaging according to ISO 13322-2: 2006, using a treadmill allowing the sample to pass in front of the camera lens. The volume mean diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard. In this document, the term "volume mean diameter" or "size" is used for zeolite adsorbent materials. The accuracy is of the order of 0.01 mm for the size range of the adsorbent materials useful in the context of the present invention. Chemical analysis of zeolitic adsorbent materials - Si / Al ratio and exchange rate: [0092] Elemental chemical analysis of a zeolite adsorbent material 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 X-ray fluorescence chemical analysis technique as described in standard NF EN ISO 12677: 2011 on a wavelength dispersive spectrometer (VVDXRF), for example Tiger S8 of the 20 Bruker company. X-ray fluorescence is a non-destructive spectral technique exploiting the photoluminescence of atoms in the X-ray domain, to establish the elemental composition of a sample. The excitation of the atoms generally by an X-ray beam or by electron bombardment, generates specific radiations after return to the ground state of the atom. A measurement uncertainty of less than 0.4% by weight is obtained conventionally after calibration for each oxide. Other methods of analysis are for example illustrated by the methods of atomic absorption spectrometry (AAS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES) described in NF EN standards. ISO 21587-3 or NF EN ISO 21079-3 on a device such as Perkin Elmer 4300DV. 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. After calibration for each oxide SiO 2 and Al 2 O 3 as well as the various oxides (such as those obtained from exchangeable cations, for example sodium), a measurement uncertainty of less than 0.4% by weight is obtained in conventional manner. The ICP-AES method is particularly suitable for measuring the lithium content used to calculate the lithium oxide content. Thus, the elementary chemical analyzes described above make it possible both to verify the Si / Al ratio of the zeolite used in the zeolitic adsorbent material and the Si / Al ratio of the zeolitic adsorbent material. In the description of the present invention, the measurement uncertainty of the Si / Al ratio is ± 5%. Measurement of the Si / Al ratio of the zeolite present in the adsorbent material can also be measured by solid nuclear magnetic resonance spectroscopy (NMR) of silicon. The quality of the ion exchange is related to the number of moles of the cation in question in the zeolite adsorbent material after exchange. More precisely, the exchange rate by a given cation is estimated by evaluating the ratio between the number of moles of said cation and the number of moles of all the exchangeable cations. The respective amounts of each of the cations are evaluated by chemical analysis of the corresponding cations. For example, the sodium ion exchange rate is estimated by evaluating the ratio of the total Na + cation number to the total number of exchangeable cations (eg Ca2 +, K +, Li, Ba2 +, Cs, Na, etc.). the amount of each of the cations being evaluated by chemical analysis of the corresponding oxides (Na 2 O, CaO, K 2 O, BaO, Li 2 O, 0520, etc.). This calculation method also accounts for any oxides present in the residual binder of the zeolitic adsorbent material. However, the amount of such oxides is considered to be minor relative to the oxides originating from the cations of the exchangeable sites of the zeolite or zeolites of the zeolitic adsorbent material according to the invention.
    [0003] Macroporous and mesoporous volume The macroporous and mesoporous volumes are measured, on a sample exchanged at least 95% sodium, by mercury intrusion porosimetry. A mercury porosimeter type Autopore® 9500 from Micromeritics is used to analyze the distribution of the pore volume contained in macropores and in mesopores. The experimental method, described in the operating manual of the apparatus referring to ASTM D4284-83, consists of placing a sample of zeolite adsorbent material to be measured (known fire loss) previously weighed, in a cell. of the porosimeter, then, after a prior degassing (discharge pressure of 30 pm Hg for at least 10 min), to fill the cell with mercury at a given pressure (0.0036 MPa), and then to apply increasing pressure by - 2 1 - bearing up to 400 MPa in order to gradually penetrate the mercury in the porous network of the sample. In this document, the macroporous and mesoporous volumes of the zeolite adsorbent materials, expressed in cm3.g-1, are thus measured by mercury intrusion and reported to the mass of the sample in anhydrous equivalents, that is, that is, the mass of said material corrected for loss on ignition. Mechanical Resistance of Zeolite Adsorbent Materials: The crush resistance in bed of zeolite adsorbent materials as described in the present invention is characterized according to ASTM 7084-04. The mechanical resistance to crushing grains are determined with a device "Grain Crushing Strength" marketed by Vinci Technologies, according to ASTM D 4179 and D 6175.
    [0004] Microporous Volume Measurement: The microporous volume measurement is estimated by conventional methods such as measurements of Dubinin-Raduskevitch volumes (adsorption of 77 K liquid nitrogen or 87 K liquid argon). The Dubinin-Raduskevitch volume is determined from the measurement of the gas adsorption isotherm, such as nitrogen or argon, at its liquefaction temperature, as a function of the pore opening. zeolite: Nitrogen will be chosen for the UF. Prior to the adsorption, the zeolitic adsorbent material 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 adsorption isotherms is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 35 measuring points at relative pressures of P / PO ratio of between 0.002 and 1. The microporous volume is determined according to Dubinin. and Raduskevich from the obtained isotherm, applying the ISO 15901-3 (2007) standard. The microporous volume evaluated according to the Dubinin and Raduskevitch equation is expressed in cm 3 of liquid adsorbate per gram of zeolitic adsorbent material. The measurement uncertainty is ± 0.003 cm3g-1, the measurements being made on the zeolite adsorbent material exchanged at least 95% sodium. Measurement of the microporous volume volume: The microporous volume volume is calculated from the microporous volume as defined above and by multiplying said microporous volume by the apparent density of said zeolitic adsorbent material. Bulk density is measured as described in DIN 8948 / 7.6. Loss on ignition of zeolite adsorbent materials: The loss on ignition is determined in an oxidizing atmosphere by calcining the sample in air at a temperature of 950 ° C. ± 25 ° C., as described in the NF EN standard. 196-2 (April 2006). The standard deviation of measurement is less than 0.1%. Qualitative and Quantitative X-ray Diffraction Analysis The purity of the zeolites in the zeolite adsorbent materials is evaluated by X-ray diffraction analysis, known to those skilled in the art by the acronym XRD. This identification is carried out on a DRX device of the brand Bruker. This analysis makes it possible to identify the various zeolites present in the adsorbent material because each of the zeolites has a single diffractogram defined by the positioning of the diffraction peaks and by their relative intensities. The zeolitic adsorbent materials are crushed then spread and smoothed on a sample holder by simple mechanical compression. The diffractogram acquisition conditions performed on the Brucker D5000 device are the following: zo-Cu tube used at 40 kV-30 mA; - size of the slots (diverging, diffusion and analysis) = 0.6 mm; - filter: Ni; - rotating sample device: 15 rpm; - measuring range: 3 ° <2e <50 °; 25 - no: 0.02 °; - counting time in steps: 2 seconds. The interpretation of the diffractogram obtained is carried out with the EVA software with identification of zeolites using the ICDD base PDF-2, release 2011. The quantity of zeolite fractions FAU, by weight, is measured. by XRD analysis, this method is also used to measure the amount of zeolite fractions other than FAU. This analysis is carried out on a device of Bruker brand, then the amount by weight of zeolite fractions is evaluated using the software TOPAS Bruker company. Measurement of the External Surface (m2 / g) by the so-called t-plot Method: The so-called t-plot calculation method exploits the adsorption isotherm data Q ads = f (P / PO) and allows to calculate the microporous surface. The outer surface can be deduced by differentiating it with the BET surface which calculates the total porous surface in m2 / g (S BET = Microporous surface + External surface). To calculate the microporous surface by the t-plot method, the curve Q ads (cm3.g-1) is plotted as a function of t = thickness of the layer depending on the partial pressure P / PO which would be formed on a non-porous reference material (t log function (P / PO): Harkins equation and applied Jura: [13,991 (0,034-log (P / PO)) "0,5] .In the interval t between 0, At 35 nm and 0.5 nm, a line can be drawn which defines an adsorbed Y intercept which allows the microporous surface to be calculated.If the material is not microporous the straight line passes through 0, the measurements being made on the zeolitic adsorbent material exchanged at least 95% sodium.
    [0005] Mesoporous Volume Measurement: The measurement of the mesoporous volume, on a sample exchanged at least 95% with sodium, is estimated by conventional methods such as measurements of Barret-Joyner-Halenda volumes (adsorption of liquid nitrogen at 77 K). The mesoporous volume is determined from the measurement of the gas adsorption isotherm, such as nitrogen, at its liquefaction temperature, as a function of the pore opening of the zeolite: nitrogen for FAU. Prior to the adsorption, the zeolitic adsorbent material 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 adsorption isotherms is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 35 measuring points at relative pressures of P / PO ratio of between 0.002 and 1. The mesoporous volume is determined according to Barret -Joyner-Halenda from the isotherm obtained, applying the ISO 15901-2 (2007) standard. The mesoporous volume evaluated according to the Barret-JoynerHalenda equation is expressed in cm3 of liquid adsorbate per gram of zeolitic adsorbent material.
    权利要求:
    Claims (25)
    [0001]
    REVENDICATIONS1. Use, for the gas separation, of at least one zeolitic adsorbent material comprising at least one FAU type zeolite, said adsorbent having: an external surface, measured by nitrogen adsorption and expressed in m 2 per gram of adsorbent, greater than 20 m2.g-1, and preferably between 20 m2.g-1 and 300 m2.g-1, and more preferably between 30 m2.g-1 and 250 m2.g-1 and even more preferred between 40 m2. g-1 and 200 m2.g-1, and especially between 50 m2.g-1 and 200 m2.g-1, a non-zeolite phase content (PNZ), such that 0 <PNZ 30%, preferably 3% PNZ 25%, more preferably 3% PNZ 20%, advantageously 5% PNZ 20%, more preferably 7% PNZ 18%, measured by XRD (X-Ray Diffraction), by weight relative to the total weight of the adsorbent, and Si / Al atomic ratio of the adsorbent between 1 and 2.5, preferably between 1 and 2.0, more preferably between 1 and 1.8, and most preferably between 1 and 1.6, all measurements being performed on the adsorbent material exchanged at least 95% sodium.
    [0002]
    2. Use according to claim 1, wherein said at least one zeolitic adsorbent material has a mesoporous volume of between 0.08 cm3g-1 to 0.25 cm3g-1, preferably between 0.08 cm3g. -1 and 0.22 cm3g-1, and more preferably between 0.09 cm3g-1 and 0.20 cm3g-1, more preferably between 0.10 cm3g-1 and 0 , 20 cm3g-1, limits included, measured on the zeolitic adsorbent material exchanged at least 95% sodium.
    [0003]
    3. Use according to claim 1 or 2, wherein said at least one zeolitic adsorbent material has a (Vmicro-Vmeso) Nmicro ratio between -0.5 and 1.0, limits not included, preferably between -0, 1 and 0.9, terminals not included, preferably between 0 and 0.9, terminals not included, more preferably between 0.2 and 0.8, terminals not included, more preferably between 0.4 and 0.8 , terminals not included, preferably between 0.6 and 0.8, terminals not included, where Vmicro is the microporous volume measured by the Dubinin-Raduskevitch method and Vmeso is the mesoporous volume measured by the Barrett-Joyner-method. Halenda (BJH), all measurements being made on the zeolite adsorbent material exchanged at least 95% sodium.
    [0004]
    4. Use according to any one of claims 1 to 3, wherein said at least one zeolite adsorbent material has a microporous volume (Dubinin-Raduskevitch volume), expressed in cm3 per gram of zeolitic adsorbent material, between 0.210 cm3. g-1 and 0.360 cm3g-1, preferably between 0.230 cm3g-1 and 0.350 cm3g-1, preferably between 0.240 cm3g-1 and 0.350 cm3g-1, more preferably 0.250 cm3. 1 g and 0.350 cm 3 .g -1, measured on the zeolite adsorbent material exchanged at least 95% sodium.
    [0005]
    5. Use according to any one of claims 1 to 4, wherein said at least one FAU type zeolite has an Si / Al ratio corresponding to the inequation 1 Si / Al <1.5, preferably 1 Si / Al 1.4, and more preferably an Si / Al atomic ratio of 1.00 +/- 0.05, said Si / Al ratio being measured by solid-state NMR of silicon 29.
    [0006]
    6. Use according to any one of claims 1 to 5, said zeolitic adsorbent material comprises at least one cation selected from the ions of Groups IA, IIA, IIIA, IB, IIB, IIIB of the periodic table, the trivalent ions of the lanthanide or rare-earth series, the zinc (II) ion, the silver ion (I), the cupric ion (II), the chromium ion (III), the ferric ion (III), the ammonium ion and / or hydronium ion, the preferred ions being calcium, lithium, sodium, potassium, barium, cesium, strontium, zinc and rare earth ions, and more preferably sodium, calcium and lithium ions. 25
    [0007]
    7. Use of at least one zeolite adsorbent material according to any one of claims 1 to 6, wherein said at least one material comprises at least one alkali metal or alkaline earth metal selected from sodium, calcium, lithium, mixtures of two or three of them in all proportions, the contents expressed in oxides are such that: - CaO content between 0 and 20.5% by weight relative to the total weight of the zeolite adsorbent material, preferably between 3 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 7.5 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 9 and 20, 5% by weight relative to the total weight of the zeolitic adsorbent material, limits included, - content of Li 2 O between 0 and 12% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 3 and 12% by weight weight relative to the total weight of the zeolitic adsorbent material, preferably between 5 and 12% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 6.5 and 12% by weight relative to the total weight of the adsorbent material zeolite, limits included, - Na.sub.2 content of between 0 and 22% by weight relative to the total weight of the zeolite adsorbent material, preferably between 0 and 19% by weight relative to the total weight of the zeolite adsorbent material, preferably between 0 and 15% by weight with respect to the total weight of the zeolitic adsorbent material, preferably between 0 and 10% by weight relative to the total weight of the zeolitic adsorbent material, and very preferably between 0 and 7% by weight relative to the total weight of the zeolitic adsorbent material, advantageously between 0 and 2% by weight relative to the total weight of the zeolite adsorbent material inclusive terminals, 15 - being the zeolitic adsorbent material comprises at least one of the three metals selected from lithium, sodium and calcium, said zeolite adsorbent material may also comprise at least one rare earth, selected from lanthanides and actinides, preferably from lanthanides, a content generally between 0 and 10%, preferably between 20 and 7%, said zeolite adsorbent material may also comprise, in small amounts (% expressed as oxide, less than 5%, preferably less than 2%); one or more other cations other than lithium, sodium and calcium, for example and preferably selected from potassium, barium, strontium, cesium, transition metals such as silver, and others.
    [0008]
    8. Use according to any one of claims 1 to 7 for the purification of natural gas, in particular for the removal of impurities and preferably for the removal of carbon dioxide and / or mercaptans, present (s) in natural gas. 30
    [0009]
    9. Use according to claim 8, wherein the zeolitic adsorbent material comprises at least FAU zeolite, preferably mesoporous, of a type selected from NaX and CaX, and mixtures thereof. 35
    [0010]
    10. Use according to any one of claims 1 to 7 for the non-cryogenic separation of industrial gases and gases from the air.
    [0011]
    11. Use according to claim 10, for the adsorption of nitrogen in the separation of gas from air, in particular for the enrichment of oxygen in the air.
    [0012]
    The use according to claim 10 or claim 11, wherein the zeolitic adsorbent material comprises at least one FAU zeolite, preferably mesoporous, of the type selected from NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX, LiCaLSX, and mixtures of two or more of them. / o
    [0013]
    13. Use according to any one of claims 10 to 12, in adsorption devices modulated in pressure in very short cycles, and in particular in oxygen concentrators respiratory assistance.
    [0014]
    14. Use according to claim 13, wherein the zeolitic adsorbent material comprises at least one FAU zeolite, preferably mesoporous, of the type selected from CaLSX, LiLSX, LiCaLSX, more preferably at least one LiLSX zeolite, preferably mesoporous LiLSX.
    [0015]
    15. Use according to any one of claims 1 to 7, for the purification of synthesis gas, possibly polluted by carbon dioxide and one or more other possible impurities.
    [0016]
    16. Use according to claim 15, wherein the zeolitic adsorbent material comprises at least one FAU zeolite, preferably mesoporous, of the type selected from NaX, LiX, LiLSX, CaX, CaLSX, LiCaX, LiCaLSX, preferably selected from NaX, NaLSX, LiCaLSX, and mixtures of two or more of them.
    [0017]
    17. Use according to any one of claims 1 to 7 for the purification of air from cryogenic units, in particular for the removal of hydrocarbons, carbon dioxide and nitrogen oxides, upstream of cryogenic distillation units.
    [0018]
    18. Use according to claim 17, wherein the zeolitic adsorbent material comprising at least one FAU zeolite, preferably mesoporous, of types selected from NaX, NaLSX, CaX, CaLSX, and mixtures of two or more thereof. -28-
    [0019]
    19. Zeolitic adsorbent material having: an Si / Al ratio of said adsorbent, such as 1 Si / Al <2.5, preferably 1 Si / Al 2, more preferably 1 Si / Al 1.8, and more preferably between 1 Si / Al 1.6, - a mesoporous volume of between 0.08 cm3g-1 to 0.25 cm3g-1, preferably between 0.08 cm3g-1 and 0.22 cm3. g-1, and more preferably between 0.09 cm3g-1 and 0.20 cm3g-1, more preferably between 0.10 cm3g-1 and 0.20 cm3g-1, terminals inclusive - of ratio (Vmicro - Vmeso) / Vmicro between -0.5 and 1.0, terminals not included, preferably -0.1 and 0.9, terminals not included, preferably 0 and 0.9, terminals not included, more preferably between 0.2 and 0.8, terminals not included, preferably y) still between 0.4 and 0.8, terminals not included, preferably between 0.6 and 0.8, terminals not included, where Vmicro is measured by the Dubinin-Raduskevitch method and Vmeso is measured by the BJH method, and - a non-zeolite phase content (PNZ), such that 0 <PNZ 30%, preferably 3% PNZ 25%, more preferably 3% PNZ 20%, advantageously 15 5% PNZ 20%, more preferably 7% PNZ 18%, measured by XRD, in weight relative to the total weight of the zeolitic adsorbent material, all the measurements being made on the zeolite adsorbent material exchanged at least 95% sodium. 20
    [0020]
    20. Zeolitic adsorbent material according to claim 19, having a microporous volume, expressed in cm 3 per gram of zeolitic adsorbent material, of between 0.210 cm 3 .g -1 and 0.360 cm 3 g -1, preferably between 0.230 cm 3 g -1. and 0.350 cm3g-1, more preferably between 0.240 cm3g-1 and 0.350 cm3g-1, advantageously between 0.250 cm3g-1 and 0.350 cm3g-1, said microporous volume being measured on the material Zeolite adsorbent exchanged at least 95% sodium.
    [0021]
    21. Zeolitic adsorbent material according to any one of claims 19 or 20, the total volume of macro- and meso-pores, measured by mercury intrusion, is between 0.15 cm3g-1 and 0.5 cm3. g-1, preferably between 0.20 cm3g-1 and 0.40 cm3g-1 and very preferably between 0.20 cm3g-1 and 0.35 cm3g-1, measured on the zeolite adsorbent material exchanged at least 95% sodium.
    [0022]
    22. A zeolitic adsorbent material according to any one of claims 19 to 21, having an external surface, measured by nitrogen adsorption and expressed in m2 per gram of adsorbent, greater than 20 m2.g-1, and preferably between 20 m2.g-1 and 300 m2.g-1, and more preferably between 30 m2.g-1 and 250 m2.g-1 and more preferably between 40 m2.g-1. and 200 m2.g-1, and especially between 50 m2.g-1 and 200 m2.g-1, measured on the zeolite adsorbent material exchanged at least 95% sodium.
    [0023]
    23. Zeolitic adsorbent material according to any one of claims 19 to 22, having a microporous volume volume expressed in cm3.cm-3 of zeolite adsorbent material exchanged at least 95% sodium, greater than 0.10 cm3.cm- 3, preferably greater than 0.12 cm3.cm-3, more preferably greater than 0.15 cm3.cm-3, more preferably greater than 0.16 cm3.cm-3, more preferably greater than 0, , 18 cm3.cm-3, quite preferably greater than 0.20 cm3.cm-3.
    [0024]
    24. Zeolitic adsorbent material according to any one of claims 19 to 23, the metal contents, expressed as oxides, are as follows: CaO content of between 0 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 3 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 7.5 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, and preferred way between 9 and 20.5% by weight relative to the total weight of the zeolitic adsorbent material, limits included, - content of Li20 between 0 and 12% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 3 and 12% by weight relative to the total weight of the zeolite adsorbent material, preferably between 5 and 12% by weight relative to the total weight of the zeolitic adsorbent material, and preferably between 6.5 and 12% by weight, relative to the total weight of the adsorbent, limits included, - Na.sub.2 content of between 0 and 22% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 19% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 15% by weight relative to the total weight of the zeolitic adsorbent material, preferably between 0 and 10% by weight relative to the total weight of the zeolitic adsorbent material, and very preferably between 0 and 7% by weight relative to the total weight of the zeolitic adsorbent material, advantageously between 0 and 2% by weight relative to the total weight of the zeolite adsorbent material inclusive, it being understood that the zeolitic adsorbent material comprises at least one of three metals chosen from lithium, sodium and calcium, said zeolite adsorbent material may also comprise at least one rare earth chosen from lanthanid and actinides, preferably from lanthanides, in a content generally between 0 and 10%, preferably between 0 and 7%, - said zeolitic adsorbent material may also comprise, in small amounts (% expressed in oxide, less than 5%, preferably less than 2%) of one or more other cations other than lithium, sodium and calcium, for example and preferably selected from potassium, barium, strontium, cesium, transition metals such as money, and others.
    [0025]
    25. Material according to any one of claims 19 to 24, having a total volume of macro- and meso-pores, measured by mercury intrusion, of between 0.15 cm3g-1 and 0.5 cm3. 1, and a volume fraction of the macropores between 0.2 and 1 times said total volume of the macro- and meso-pores, preferably between 0.4 and 0.8 inclusive, the measurements being made on the material adsorbent exchanged at least 95% sodium.
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    同族专利:
    公开号 | 公开日
    CA2974765C|2019-11-19|
    WO2016124842A1|2016-08-11|
    EP3253483A1|2017-12-13|
    MX2017009826A|2017-11-02|
    EA037828B1|2021-05-25|
    KR102008079B1|2019-08-06|
    AU2016214208A1|2017-08-17|
    US10888837B2|2021-01-12|
    JP6876609B2|2021-05-26|
    JP2020001038A|2020-01-09|
    FR3032130B1|2019-12-27|
    BR112017015583A2|2018-03-13|
    KR20170110672A|2017-10-11|
    SA517382024B1|2021-02-14|
    AU2016214208B2|2018-03-01|
    JP2018505050A|2018-02-22|
    CN107810041A|2018-03-16|
    CA2974765A1|2016-08-11|
    US20180008955A1|2018-01-11|
    EA201791752A1|2017-12-29|
    ZA201705338B|2019-05-29|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1550781|2015-02-02|
    FR1550781A|FR3032130B1|2015-02-02|2015-02-02|ZEOLITHIC ADSORBENTS WITH A HIGH EXTERNAL SURFACE, THEIR PREPARATION METHOD AND THEIR USES|FR1550781A| FR3032130B1|2015-02-02|2015-02-02|ZEOLITHIC ADSORBENTS WITH A HIGH EXTERNAL SURFACE, THEIR PREPARATION METHOD AND THEIR USES|
    CA2974765A| CA2974765C|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    EP16705247.1A| EP3253483A1|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    EA201791752A| EA037828B1|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    CN201680019844.8A| CN107810041A|2015-02-02|2016-01-29|Zeolite adsorbents with high external surface area and application thereof|
    PCT/FR2016/050197| WO2016124842A1|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    US15/546,847| US10888837B2|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    AU2016214208A| AU2016214208B2|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    JP2017540722A| JP6876609B2|2015-02-02|2016-01-29|Use of zeolite adsorbents with a large external surface area and the zeolite adsorbents|
    BR112017015583-4A| BR112017015583A2|2015-02-02|2016-01-29|high outer surface zeolitic adsorbents and their uses|
    MX2017009826A| MX2017009826A|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof.|
    KR1020177024578A| KR102008079B1|2015-02-02|2016-01-29|Zeolite adsorbents having a high external surface area and uses thereof|
    SA517382024A| SA517382024B1|2015-02-02|2017-07-31|Zeolite adsorbents having a high external surface area and uses thereof|
    ZA2017/05338A| ZA201705338B|2015-02-02|2017-08-07|Zeolite adsorbents having a high external surface area and uses thereof|
    JP2019142237A| JP2020001038A|2015-02-02|2019-08-01|Zeolite adsorbent having large outer surface area and use of zeolite adsorbent|
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