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  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
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  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
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  • B01J20/18—Synthetic zeolitic molecular sieves
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  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
  • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
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  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
  • F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
  • F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
  • F25J3/04—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream for air
  • F25J3/04151—Purification and (pre-)cooling of the feed air; recuperative heat-exchange with product streams
  • F25J3/04163—Hot end purification of the feed air
  • F25J3/04169—Hot end purification of the feed air by adsorption of the impurities
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/10—Inorganic adsorbents
  • B01D2253/106—Silica or silicates
  • B01D2253/108—Zeolites
  • B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D—SEPARATION
  • B01D2256/00—Main component in the product gas stream after treatment
  • B01D2256/12—Oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/10—Single element gases other than halogens
  • B01D2257/102—Nitrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D2259/416—Further details for adsorption processes and devices involving cryogenic temperature treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
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• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
  • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
  • B01D53/047—Pressure swing adsorption
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
  • C10L2290/143—Injection, e.g. in a reactor or a fuel stream during fuel production of fuel
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  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
  • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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  • F25J2205/00—Processes or apparatus using other separation and/or other processing means
  • F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
  • F25J2205/64—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end by pressure-swing adsorption [PSA] at the hot end
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  • F25J2220/40—Separating high boiling, i.e. less volatile components from air, e.g. CO2, hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

• the invention relates to the use of zeolite adsorbent materials in the form of agglomerates comprising at least one faujasite type zeolite, said adsorbents having 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 (Pressure Swing Adsorption) type or of the VSA (Vacuum Swing Adsorption) type; English language), either of the VPSA type (hybrid process of the two previous ones), or of the RPSA type ("Rapid Pressure Swing Adsorption" in English language), in temperature modulated processes of the TSA type (temperature-modulated adsorption or "Temperature Swing”). Adsorption "in English language) and / or in processes modulated in pressure and temperature type PTSA (Pressure and T modulated adsorption "Temperature and Temperature Swing Adsorption").
• PSA Pressure Swing Adsorption
• VSA Va
• the present invention also relates to a gas separation and purification process using said zeolite adsorbents having a large 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.
• 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).
• the document WO2008 / 152319 describes the preparation, by atomization, of mechanically resistant adsorbents of small sizes, which are for example used in portable medical oxygen concentrators, as shown in the document 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 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.
• WO2008 / 051904 proposes a process for manufacturing by extrusion / spheronization of zeolite adsorbent beads based on LiX zeolite with improved diffusion.
• the document 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 silicic binder introduced in colloidal form.
• 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 threshold of mechanical strength 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 sufficiently wide to allow a flow with limited pressure losses.
• Adsorbent sheets and fabrics, monoliths of the honeycomb type, foams or others may be mentioned.
• the 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.
• 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.
• 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 invention relates to the use for the separation of gas, of at least one zeolitic adsorbent material comprising at least one zeolite of the FAU type, said adsorbent having:
• An external surface measured by nitrogen adsorption and expressed in m 2 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 more preferably between 30 m 2 . g -1 and 250 m 2 . g -1 and so even more preferred between 40 m 2 . g "1 and 200 m 2 g -1 , and especially between 50 m 2 . g "1 and 200 m 2 .g-
• a non-zeolite phase content 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,
• Vmeso mesoporous volume
• 0.08 cm 3 . 1 to 0.25 cm 3 g -1 preferably 0.08 cm 3 . g -1 and 0.22 cm 3 . g -1 , and more preferably between 0.09 cm 3 . g -1 and 0.20 cm 3 . g -1 , more preferably between 0.10 cm 3 . g -1 and 0.20 cm 3 . g -1 , limits included,
• 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.
• 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.
• 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.
• non-zeolite phase denotes any phase present in the adsorbent material, other than the zeolite (s) defined above, referred to as “zeolite phase” or "PZ".
• % PNZ represents the weight percentage of PNZ and% PZ the weight percentage of zeolitic phase, relative to the total weight of the adsorbent.
• 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 with 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 / g. The operation is repeated n times, n being at least 1, preferably at least 2, preferably at least 3, more preferably at least 4.
• the solids from the exchange operations n-1 and n are successively four times washed by immersion in water at 20 mL.g -1 to remove excess salt, and then dried for 12 hours at 80 ° C under air, before being 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 at ⁇ 1%, said adsorbent material zeolitic is considered to be "in its form at least 95% exchanged with 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.
• 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.
• 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.
• Vmicro is meant the microporous volume of the zeolitic adsorbent material whose measurement technique is explained below.
• Vmeso is meant the mesoporous volume of the zeolite adsorbent material whose measurement technique is explained below.
• said at least one zeolitic adsorbent material that can be used in the context of the present invention has a ratio (Vmicro-VmésoyVmicro 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, more 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-method.
• BJH Joyner-Halenda
• 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, of between 0.210 cm 3 . 1 and 0.360 cm 3 .g -1 , preferably between 0.230 cm 3 .g -1 and 0.350 cm 3 .g -1 , preferably between 0.240 cm 3 .g -1 and 0.350 cm 3 . g "1 , more preferably 0.250 cm 3 .g -1 and 0.350 cm 3 . g "1 , measured on the adsorbent material exchanged with at least 95% sodium.
• Vmicro microporous volume
• 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 cm 3 . g "1 and 0.5 cm 3, g " 1 , preferably between 0.20 cm 3 . g "1 and 0.40 cm 3 g -1 and very preferably between 0.20 cm 3 . g "1 and 0.35 cm 3 .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 may 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.
• 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.
• the use according to the invention uses a zeolitic adsorbent material comprising at least one mesoporous FAU type zeolite.
• mesoporous is meant a zeolite which presents, jointly to the microporosity inherent in the structure of the zeolite, 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.
• said zeolite FAU zeolite adsorbent material is a mesoporous FAU zeolite, that is to say a zeolite having an outer surface, defined by the t-plot method described below, between 40 m 2 . g -1 and 400 m 2 . g -1 , preferably between 60 m 2 . g -1 and 200 m 2 . g -1 , limits included.
• 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 .
• 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 / 1 inequation.
• AI ⁇ 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 Resonance Nuclear magnetic (NMR) solid silicon 29 ( 29 Si NMR), according to techniques well known to those skilled in the art.
• NMR Resonance Nuclear magnetic
• the Si / Al ratio of each zeolite present (s) in the adsorbent is also measured by solid NMR.
• the zeolite FAU zeolite adsorbent material is in the form of crystals whose number average diameter, measured by scanning electron microscope (SEM), is less than 20 ⁇ , preferably between 0.1 ⁇ and 20 ⁇ , preferably between 0.1 and 10 ⁇ , preferably between 0.5 ⁇ and 10 ⁇ , more preferably between 0.5 ⁇ and 5 ⁇ , terminals included.
• SEM scanning electron microscope
• said zeolitic adsorbent material comprises at least one cation chosen from the ions of groups IA, II A, NIA, IB, MB, IIIB of the periodic classification, the trivalent ions of the series. lanthanides or rare earths, zinc ion (II), silver ion (I), cupric ion (II), chromium ion (III), ferric ion (III), ion ammonium 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.
• U2O content between 0 and 12% by weight relative to the total weight of the zeolite 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 zeolitic adsorbent material, limits included,
• Na 2 O 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 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 included,
• the zeolitic adsorbent material comprises at least one of the three metals chosen from lithium, sodium and calcium,
• Said zeolitic adsorbent material may also comprise at least one rare earth, chosen from lanthanides and actinides, preferably from lanthanides, in a content generally ranging between 0 and 10%, preferably between 0 and 7%,
• Said zeolitic 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.
• 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, or 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.
• the present invention relates to the use of at least one zeolitic adsorbent material, comprising at least one FAU type zeolite, such as defined above, for gas separation.
• 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.
• the zeolitic adsorbent materials that can be used for gas purification are materials that generate only a small amount of pressure drop or acceptable pressure drop for the aforementioned uses.
• 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 generally has a mean volume diameter, or an average length (greater dimension when 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 mm, 5 mm.
• 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:
• a bed crush strength measured according to the ASTM 7084-04 standard of between 0.5 MPa and 3 MPa, preferably between 0.75 MPa and 2.5 MPa, for a material of volume diameter medium (D50) or length (larger dimension when material is not spherical), less than 1 mm, inclusive
• a grain crush strength measured according to ASTM D 4179 (201 1) and ASTM D 6175 (2013), of between 0.5 daN and 30 daN, preferably of between 1 daN and 20 daN, for a material of medium volume diameter (D50) or a length (larger dimension when the material is not spherical), greater than or equal to 1 mm, inclusive.
• 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 cm. 3 . cm -3 of adsorbent material exchanged at least 95% sodium, said microporous volume volume being greater than 0.10 cm 3 . cm -3 , preferably greater than 0.12 cm 3 . cm -3 , more preferably greater than 0.15 cm 3 . cm -3 , more preferably greater than 0.16 cm 3 . cm 3 , more preferably greater than 0.18 cm 3 cm -1 , most preferably greater than 0.20 cm 3 . cm "3 .
• the use according to the invention preferably implements at least one zeolitic adsorbent material having a loss on ignition, measured at 950 ° C according to standard NF EN 196-2, included between 0 and 5%, preferably between 0 and 3% by weight.
• the present invention relates to the use of at least one zeolite adsorbent material as just defined for the purification of natural gas, in particular for the removal of impurities and preferably for the removal of impurities. 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.
• PSA or TSA or PTSA pressure and / or temperature
• the adsorbent materials comprising a FAU zeolite, preferably mesoporous, of a type chosen from NaX and CaX, and mixtures thereof.
• a zeolitic adsorbent material is preferred, the volume average diameter (or the greatest length) of which is between 0.3 mm and 7.0 mm, preferably between 0.8 mm and 5 mm. , 0 mm, and more preferably between 2.0 mm and 5.0 mm, inclusive.
• 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 (typically between 0.1 seconds and 10 seconds, preferably between 0.1 seconds and 5 seconds), and especially in respiratory assistance oxygen concentrators, as described for example in the application WO2008 / 152319.
• PSA pressure swing adsorption devices
• the zeolitic adsorbent material comprising at least one FAU zeolite is furthermore preferred. preferably mesoporous, of the type selected from NaX, LiX, CaX, LiCaX, NaLSX, LiLSX, CaLSX, LiCaLSX, and mixtures of two or more thereof, said material zeolitic adsorbent comprising at least one alkali metal or alkaline earth metal selected from sodium, calcium, lithium, mixtures of two or three of them in all proportions, whose contents expressed in oxides are as defined above.
• 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 one 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, preferably still at least one LiLSX zeolite, preferably mesoporous LiLSX.
• FAU zeolite preferably mesoporous
• a zeolitic 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.
• 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.
• the invention relates to the use of at least one zeolite adsorbent material as just defined for the purification of synthesis gas.
• 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.
• PSA adsorption methods modulated by pressure
• 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.
• 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").
• 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.
• ASU Air Separation Unit
• zeolitic adsorbent materials comprising a FAU zeolite, preferably mesoporous, of types selected from NaX, are preferred. NaLSX, CaX, CaLSX, and mixtures of two or more of them.
• 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.
• the invention relates to a zeolitic adsorbent material having:
• An Si / Al ratio of said adsorbent such that 1 ⁇ Si / Al ⁇ 2.5, preferably 1 ⁇ Si / Al ⁇ 2, more preferably 1 ⁇ Si / Al ⁇ 1, 8, and more preferably between 1 ⁇ If / AI ⁇ 1, 6,
• Vmicro-Vmeso • 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, more preferably 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 such that 0 ⁇ PNZ ⁇ 30%, preferably 3% ⁇ PNZ ⁇ 25%, more preferably 3% ⁇ PNZ ⁇ 20%, advantageously 5% ⁇ PNZ ⁇ 20%, better still 7% ⁇ PNZ ⁇ 18%, measured by XRD, by weight relative to the total weight of the zeolitic adsorbent material,
• the zeolitic 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 (TEM or "TEM" in English), as described for example in US7785563.
• TEM microscope electronic transmission
• 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, of between 40 m 2 . g “1 and 400 m 2, g " 1 , preferably between 60 m 2 . g “1 and 200 m 2, g " 1 , inclusive terminals.
• 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.
• 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.
• 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. 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.
• organic or mineral binder preferably mineral, more preferably a binder selected from clays, zeolitizable or not, and in particular among kaolins, kaolin
• Agglomeration and shaping can be carried out according to all the 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.
• agglomeration binder for example clays, as indicated above
• zeolite s
• 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 desired PNZ content 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 zeolite adsorbent materials according to the invention is easily adaptable from the preparation processes known to those skilled in the art, as already indicated, the implementation of at least one mesoporous FAU zeolite not modifying These processes are not substantially known, which means that the preparation process is an easy, fast and inexpensive implementation process and 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.
• macro-pores is meant pores whose opening is greater than 50 nm, preferably between 50 nm and 400 nm.
• meso-pores is meant pores whose opening is between 2 nm and 50 nm, terminals not included.
• micro-pores is meant pores whose opening is less than 2 nm.
• 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 cm 3 . g -1 , preferably between 0.230 cm 3 . g -1 and 0.350 cm 3 . g -1 , more preferably between 0.240 cm 3 . g -1 and 0.350 cm 3 . g -1 , advantageously between 0.250 cm 3 . g -1 and 0.350 cm 3 . g -1 , said microporous volume being measured on the zeolite adsorbent material exchanged at least 95% sodium.
• a microporous volume Dubinin-Raduskevitch volume
• the total volume of the macro- and meso-pores of the zeolite adsorbent materials according to the invention, measured by mercury intrusion, is advantageously between 0.15 cm 3 . g -1 and 0.5 cm 3 . g -1 , preferably between 0.20 cm 3 . g -1 and 0.40 cm 3 . g -1 and very preferably between 0.20 cm 3 . g -1 and 0.35 cm 3 . g -1 , the measurements being made on the adsorbent material exchanged at least 95% sodium.
• the volume fraction of the macropores of the zeolite 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 zeolitic adsorbent material, are measured by observation under a scanning electron microscope. (SEM).
• the mean diameter of the FAU type zeolite crystals is between 0.1 ⁇ and 20 ⁇ , preferably between 0.5 ⁇ and 20 ⁇ , and more preferably between 0.5 ⁇ and 10 ⁇ .
• the 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.
• the zeolitic adsorbent material according to the invention has an external surface, measured by nitrogen adsorption and expressed in m 2 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 more preferably between 30 m 2 . g -1 and 250 m 2 . g -1 and more preferably between 40 m 2 . g -1 and 200 m 2 . g -1 , and especially between 50 m 2 . g -1 and 200 m 2 . g -1 measurements being made on the zeolite adsorbent material exchanged at least 95% sodium.
• the zeolitic adsorbent material according to the invention has a high adsorption volume capacity, that is to say a microporous volume volume expressed in cm 3 . cm -3 of zeolitic adsorbent material exchanged at least 95% sodium, said microporous volume volume being greater than 0.10 cm 3 . cm -3 , preferably greater than 0.12 cm 3 . cm “3 , more preferably greater than 0.15 cm 3 cm -1 , more preferably greater than 0.16 cm 3 . cm 3 , more preferably greater than 0.18 cm 3 cm -1 , most preferably greater than 0.20 cm 3 . cm "3 .
• the zeolitic adsorbent material according to the invention comprises at least one mesoporous FAU zeolite as defined above, said at least one zeolite having a Si / Al ratio, such that 1 ⁇ Si / Al ⁇ 1, 5, preferably 1 ⁇ Si / Al ⁇ 1, 4.
• the Si / Al ratio of said at least one mesoporous FAU zeolite is equal to 1.00 +/- 0.05, the measurements being carried out on the zeolite adsorbent material exchanged at least 95% with sodium. .
• said zeolitic adsorbent material comprises at least one cation chosen from the ions of groups IA, II A, NIA, IB, MB, IIIB of the periodic table, the trivalent ions of the series. lanthanides or rare earths, zinc ion (II), silver ion (I), cupric ion (II), chromium ion (III), ferric ion (III), ion ammonium 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, as indicated above.
• the metal contents of the zeolite adsorbent material according to the invention, expressed in oxides, are preferably those indicated above, and more particularly:
• U2O content between 0 and 12% by weight relative to the total weight of the zeolite 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,
• 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 quite exactly preferred 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 included,
• the zeolitic adsorbent material comprises at least one of the three metals chosen from lithium, sodium and calcium,
• Said zeolitic adsorbent material may also comprise at least one rare earth, chosen from lanthanides and actinides, preferably from lanthanides, in a content generally ranging between 0 and 10%, preferably between 0 and 7%,
• Said zeolitic 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.
• zeolite adsorbent materials in which the content of barium oxide is less than 0.5%, preferably less than 0.3%, and more preferably less than 0.1%, are furthermore preferred. by weight relative to the total weight of the material.
• 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” means 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, of 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.
• the invention relates to a zeolitic adsorbent material as defined above and having a total volume of macro- and meso-pores, measured by mercury intrusion, of between 0.15 cm 3. . g -1 and 0.5 cm 3 . g -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 adsorbent material exchanged at least 95% sodium. Characterization techniques
• zeolite adsorbent materials The physical properties of zeolite adsorbent materials are evaluated by methods known to those skilled in the art, the main of which are recalled below.
• the estimation of the average number diameter of zeolite crystals of FAU type contained in the zeolite adsorbent materials, and which are used for the preparation of said zeolitic adsorbent material, is carried out by observation under a scanning electron microscope (SEM).
• 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%.
• the determination of the average volume diameter (or "volume average 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 by imaging according to the ISO 13322 standard. -2: 2006, using a treadmill allowing the sample to pass in front of the camera lens.
• volume mean diameter is then calculated from the particle size distribution by applying the ISO 9276-2: 2001 standard.
• volume mean diameter or "size” is used for zeolite adsorbent materials.
• 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.
• An 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 technique of chemical analysis by X-ray fluorescence as described in standard NF EN ISO 12677: 201 1 on a wavelength dispersive spectrometer (WDXRF), for example Tiger S8 of the Bruker company.
• WDXRF wavelength dispersive spectrometer
• 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 atoms usually by an X-ray beam or by bombardment with electrons, generates specific radiations after returning 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.
• AAS atomic absorption spectrometry
• ICP-AES inductively coupled plasma atomic emission spectrometry
• the X-ray fluorescence spectrum has the advantage of depending very little on the chemical combination of the element, which offers a precise determination, both quantitative and qualitative. After calibration for each oxide S102 and Al2O3, 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.
• the elementary chemical analyzes described above allow both to verify the Si / Al ratio of the zeolite used in the zeolite adsorbent material and the Si / Al ratio of the zeolitic adsorbent material.
• 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 considered 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.
• the exchange rate by sodium ions is estimated by evaluating the ratio between the total number of Na + cation and the total number of exchangeable cations (for example Ca 2+ , K + , Li + , Ba 2+ , Cs + , Na + , etc.), the amount of each of the cations being evaluated by chemical analysis of the corresponding oxides (Na2O, CaO, K2O, BaO, L12O, CS2O, etc.).
• This calculation method also accounts for any oxides present in the residual binder of the zeolitic adsorbent material.
• 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. Macroporous and mesoporous volume
• the macroporous and mesoporous volumes are measured, on a sample exchanged at least 95% sodium, by porosimetry by mercury intrusion.
• a mercury porosimeter Autopore kind Micromeritics ® 9500 is used to analyze the distribution of the pore volume contained in macropores and the mesopores.
• the experimental method described in the operating manual of the apparatus referring to ASTM D4284-83 consists in 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 ⁇ Hg for at least 10 min), to fill the cell with mercury at a given pressure (0.0036 MPa), and then to apply increasing pressure stepwise up to 400 MPa in order to gradually penetrate the mercury into the porous network of the sample.
• macroporous and mesoporous volumes of zeolitic adsorbent materials are thus measured by mercury intrusion and reported to the mass of the sample in anhydrous equivalent, that is to say the mass of said material corrected for loss on ignition.
• 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.
• microporous volume is estimated by conventional methods such as measurements of Dubinin-Raduskevitch volumes (adsorption of liquid nitrogen at 77 K or argon liquid at 87 K).
• 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. Before the adsorption, the zeolite adsorbent material is degassed between 300 ° C and 450 ° C for a duration between 9 and 16 hours under vacuum (P ⁇ 6,7.10 "4 Pa). Measurement of isotherms adsorption is then carried out on an ASAP 2020 Micromeritics-type apparatus, taking at least 35 measuring points at relative pressures of ⁇ / ⁇ 0 ratio of between 0.002 and 1.
• microporous volume is determined according to Dubinin and Rohskevitch from isotherm obtained by applying the ISO 15901 -3 (2007) standard
• the microporous volume evaluated according to the Dubinin and Rohskevitch equation is expressed in cm 3 of liquid adsorbate per gram of zeolitic adsorbent material. is ⁇ 0.003 cm 3 .g -1 , the measurements being made on the zeolite adsorbent material exchanged with at least 95% sodium. Measurement of the microporous volume volume:
• microporous volume volume is calculated from the microporous volume as defined above and by multiplying said microporous volume by the bulk density of said zeolitic adsorbent material. Bulk density is measured as described in DIN 8948 / 7.6.
• 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 the NF EN standard.
• the purity of the zeolites in the zeolite adsorbent materials is evaluated by X-ray diffraction analysis, known to those skilled in the art under the acronym.
• the zeolitic adsorbent materials are crushed then spread and smoothed on a sample holder by simple mechanical compression.
• the interpretation of the diffractogram obtained is performed with the EVA software with zeolites identification using the ICDD database PDF-2, release 201 1.
• the amount 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 (m 2 / g) by the so-called t-plot method:
• 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 line passes through 0 the measurements being carried out on the zeolite adsorbent material exchanged with at least 95% sodium.
• Measuring the mesoporous volume, on a sample exchanged at least 95% 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.
• the zeolitic adsorbent material Prior to adsorption, 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). adsorption is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 35 measuring points at relative pressures of P / PO ratio between 0.002 and 1.
• the mesoporous volume is determined according to Barret-Joyner-Halenda from of the isotherm obtained by applying ISO 15901-2 (2007)
• the mesoporous volume evaluated according to the Barret-Joyner-Halenda equation is expressed in cm 3 of liquid adsorbate per gram of zeolitic adsorbent material.
• Step 1 Synthesis of mesoporous LSX type zeolite crystals with a Si / Al ratio equal to 1.01 and an external surface equal to 95 m 2 .g -1
• a) Preparation of gel growth reactor stirred by Archimedean screw 250 tr.min '1.
• a growth gel is prepared by mixing an aluminate solution containing 300 g of hydroxide hydroxide.
• the stoichiometry of the growth gel is as follows: 4.32 Na 2 O / 1.85 K 2 O / Al 2 O 3 / 2.0 S 10 2/1 14 H 2 O. Homogenization growth gel is carried out with stirring at 250 tr.min "1 for 15 minutes at 25 ° C.
• nucleating gel (0.4% by weight) of composition 12 Na 2 0 / Al2O3 / 10 S1O2 / 180 H 2 0 prepared in the same manner as the growth of frost, and ripened for 1 hour at 40 ° C. After 5 minutes of homogenization at 250 tr.min -1, the stirring speed was decreased to 50 tr.min -1 and continued for 30 minutes.
• the solids are recovered on sintered and then washed with deionized water to neutral pH.
• the drying is carried out in an oven at 90 ° C. for 8 hours.
• the calcination of the dried product necessary to release both the microporosity (water) and the mesoporosity by eliminating the structuring agent is carried out by vacuum degassing with a gradual increase in steps of 50 ° C. to 400 ° C. C for a period of between 9 hours and 16 hours under vacuum (P ⁇ 6.7 ⁇ 10 -4 Pa).
• the microporous volume and the external surface measured according to the t-plot method from the 77K nitrogen adsorption isotherm after degassing under vacuum at 400 ° C. for 10 hours are respectively 0.215 cm 3 . g -1 and 95 m 2 g -1 .
• the average number diameter of the crystals is 6 ⁇ .
• the diameters of the mesopores calculated from the nitrogen adsorption isotherm by the DFT method are between 5 nm and 10 nm.
• the X-ray diffractogram corresponds to a pure Faujasite structure (FAU), no LTA zeolite is detected.
• the Si / Al molar ratio of the mesoporous LSX determined by X-ray fluorescence is equal to 1.01.
• FIG. 1 presents a photograph obtained by Transmission Electron Microscopy (TEM) of the zeolite thus synthesized.
• Step 2 Preparation of mesoporous LSX zeolite agglomerates
• the beads are dried overnight in a ventilated oven at 80 ° C. They are then calcined for 2 h at 550 ° C. under a nitrogen sweep and then 2 h at 550 ° C. under a decarbonated dry air sweep.
• Step 3 Lithium exchange and activation of mesoporous LSX zeolite agglomerates
• the beads are dried overnight in a ventilated oven at 80 ° C. They are then activated for 2 hours at 550 ° C. under a nitrogen sweep.
• the content of lithium oxide L12O, determined by ICP-AES, is 8.9% by weight relative to the total weight of the zeolitic adsorbent material.
• the average volume diameter of the balls is 0.55 mm.
• the mechanical crush strength in bed of mesoporous zeolite LSX beads exchanged with lithium is 2.6 daN.
• the zeolitic adsorbent material is at least 95% sodium exchange as follows: the zeolitic adsorbent material is introduced into a solution of sodium chloride at 1 mole of NaCl per liter, at 90.degree. ° C., for 3 h, with a liquid-to-solid ratio of 10 ml.- 1 . The operation is repeated 4 times between each exchange, the solids are successively washed four times by immersion in water at a rate of 20 mL.g -1 to remove the excess salt, and then dried for 12 h at 80 ° C. in air, before being analyzed by X-ray fluorescence.
• the weight percentage of sodium oxide of the zeolitic adsorbent material is equal to 18, 2% and stable at less than 1% between the exchange operations 3 and 4.
• the beads are dried overnight in a ventilated oven at 80 ° C. They are then activated for 2 hours at 550 ° C. under a nitrogen sweep.
• the external surface is equal to 99 m 2 . g -1 of adsorbent
• the microporous volume is 0.264 cm 3 . g -1 of sodium exchanged adsorbent
• the microporous volume volume is 0.150 cm 3 per cm 3 of sodium exchanged zeolite adsorbent material
• the mesoporous volume is equal to 0.165 cm 3 g -1 of sodium exchanged adsorbent.
• the total volume of the macro- and meso-pores, measured by mercury intrusion, is 0.42 cm 3 g- 1 of sodium exchanged adsorbent.
• the Si / Al atomic ratio of the adsorbent is 1, 25.
• the Si / Al ratio of the zeolite present in the zeolite adsorbent material, which is equal to 1.0, is determined by solid-state NMR of silicon 29.
• the content of non-zeolite phase (PNZ), measured by XRD and expressed by weight relative to the total weight of the adsorbent, is 15.3%.
• CECA Siliporite® Nitroxy® SXSDM Screen is a LiLSX zeolite material bonded to attapulgite.
• the average volume diameter of the balls is equal to 0.55 mm.
• the content of lithium oxide L12O, measured by ICP-AES, is 9.2% by weight relative to the total weight of sieves.
• step 4 of Example 1 sodium is exchanged to obtain a solid exchanged at least 95% sodium. As before, this result is obtained with 4 consecutive exchanges.
• the weight percentage of sodium oxide of the zeolite adsorbent material, obtained by X-ray fluorescence, is equal to 18.4% and stable at less than 1% between the exchange operations 3 and 4.
• the beads are dried overnight. in a ventilated oven at 80 ° C. They are then activated for 2 hours at 550 ° C. under a nitrogen sweep.
• the external surface is equal to 31 m 2 . g -1 of adsorbent
• the microporous volume is 0.265 cm 3 . g- 1 of sodium-exchanged adsorbent
• the microporous volume volume is 0.172 cm 3 per cm 3 of sodium-exchanged zeolite adsorbent material
• the mesoporous volume is equal to 0.07 cm 3 g -1 of adsorbent exchanged at
• the total volume of the macro- and meso-pores, measured by mercury intrusion, is 0.31 cm 3 g- 1 of sodium exchanged adsorbent.
• the Si / Al atomic ratio of the adsorbent is 1, 23.
• Figure 2 describes the assembly carried out.
• the feed time of the column (1) by the flow (3) is called the adsorption time.
• the flow (3) is vented to the atmosphere by the valve (5).
• the zeolitic adsorbent material preferentially adsorbs nitrogen, so that oxygen-enriched air exits the column through the non-return valve (6) to a buffer capacity (7).
• a regulating valve (8) continuously delivers the output gas (9) at a constant flow rate set at 1 NL.min -1 .
• the column (1) When the column (1) is not energized, that is to say when the valve (4) is closed and the valve (5) is open, the column (1) is depressurized by the valve ( 10) to the atmosphere (1 1) for a period called desorption time.
• the adsorption and desorption phases succeed one another. The durations of these phases are fixed from one cycle to another and they are adjustable.
• Table 1 shows the respective state of the valves according to the adsorption and desorption phases.
• Example 1 The tests are carried out successively with the zeolitic adsorbent materials of Example 1 (according to the invention) and Example 2 (comparative).
• the column is charged at constant volume, with respectively 204.5 g and 239.7 g of adsorbent materials.
• the inlet pressure is set at 280 kPa relative.
• the output flow rate is set at 1 NL.min -1, the adsorption time is set at 0.25 S.
• the desorption time is variable between 0.25 s and 1, 25 s.
• the oxygen concentration at the outlet (9) is measured using a Servomex 570A oxygen analyzer.
• FIG. 3 shows the oxygen content of the output stream (9) as a function of the desorption time set for the materials of Example 1 and Example 2.
• the material of Example 1 (according to the invention) is much more efficient (in terms of the oxygen content of the product gas) than the solid of Example 2 (comparative).

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