WO2018100318A1 - Matériau adsorbant zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique des gaz industriels - Google Patents
Matériau adsorbant zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique des gaz industriels Download PDFInfo
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- 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
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- 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
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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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
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- B01D—SEPARATION
- 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
- B01D53/047—Pressure swing adsorption
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- 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
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/28002—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 physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- 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
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- 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
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/308—Pore size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
Definitions
- the present invention relates to specific adsorbent materials for the non-cryogenic separation of industrial gases, and more particularly for the separation of nitrogen by adsorption in gas streams such as air and purification of the hydrogen by adsorption of carbon monoxide (CO) and / or nitrogen (N2).
- gas streams such as air and purification of the hydrogen by adsorption of carbon monoxide (CO) and / or nitrogen (N2).
- the air is compressed and sent to an adsorbent column having a marked preference for the nitrogen molecule.
- oxygen is produced at about 94-95% and argon.
- the column is depressurized and then maintained at low pressure, during which time the nitrogen is desorbed. Recompression is then provided by means of a portion of the product oxygen and / or by air, and the cycle continues.
- the advantage of this process over cryogenic processes lies in the simplicity of the installations and greater ease of maintenance.
- the quality of the adsorbent used remains the key to an effective and competitive process.
- the performance of the adsorbent is related to several factors, among which mention may in particular be made of the nitrogen adsorption capacity and the selectivity between nitrogen and oxygen which will be decisive for sizing the column sizes and optimizing the production yield (ratio between oxygen product and oxygen input), adsorption kinetics that will optimize the cycle time and improve the productivity of the installation.
- the application FR2766476 describes an improved zeolite adsorbent for the separation of gases from the air and its production process.
- This document describes a material LSX zeolite adsorbent comprising lithium, optionally potassium, and zeolite binder.
- This adsorbent material has a nitrogen adsorption capacity greater than or equal to 26 cm 3 . g -1 .
- International application WO2008 / 152319 describes a process for the preparation of zeolite agglomerates whose zeolite content is greater than 70% by weight and the diameter of the balls (dso) is less than 600 ⁇ and has a density of between 0, 5 g. cm -3 and 0.8 g. cm -3 .
- the zeolites potentially used are zeolites of LSX, X and A type and agglomeration clays are zeolitizable or not.
- This application also describes the possible addition of silica in a proportion of 1% to 5% by weight relative to the total mass of the solids (in calcined equivalents) during the preparation of the agglomerates.
- US6478854 discloses a process for the preparation of agglomerates based on LiLSX zeolite "binderless" (i.e. "without binder") and their use in the separation of gases.
- the agglomeration binder is converted by percolation with a solution of sodium hydroxide and potassium hydroxide with an Na / (Na + K) ratio between 0.1 and 0.4.
- An aluminum source may be added to the caustic solution to convert the binder preferably to LSX type zeolite.
- the conversion of the binder to LSX is measured by a ratio of intensity of the peaks on the diffractogram, between the peak corresponding to the diffraction plane (Miller index) 220 and the peak corresponding to the diffraction plane 31 1.
- the international application WO2013 / 106017 describes a process for the preparation of zeolite X binderless atomic ratio Si / Al between 1.0 and 1.5, used after agglomeration and barium exchange, for the separation of isomers of xylene.
- the size of the zeolite X crystals is 2.7 ⁇ and the size of the binder crystals converted into zeolite (between 5% and 30% by weight relative to the total weight of zeolite) is not defined.
- the binder is also partially converted to zeolite A.
- the international application WO2014 / 176002 describes a process for preparing an adsorbent material agglomerated from a choice of two binders having different particle sizes, zeolite then lithium exchange. It is also possible to add a source of liquid or solid silica to zeolitize the binder in zeolite X whose atomic ratio Si / Al may differ from that of the initial zeolite.
- zeolite adsorbent materials also known as "molecular sieves”
- zeolitic adsorbent materials with improved adsorption capacity compared to zeolite adsorbent materials of the LiLSX type with zeolite binder existing, for the separation of industrial gases, in particular nitrogen and oxygen.
- the subject of the present invention is a zeolitic adsorbent material:
- LSX zeolite crystals the particle size distribution of which is characterized by a peak width (2o) of between 6.0 and 20.0, limits included for a number average diameter (dso) of between 0.5 ⁇ ; and 20.0 ⁇ ,
- Non-zeolite phase content such that 0 ⁇ PNZ ⁇ 8%, by weight relative to the total weight of the zeolitic adsorbent material.
- the particle size distribution of the crystals of the zeolite adsorbent material of the present invention is one of the parameters for achieving the high capacity sought for the separation of gases.
- the particle size distribution is typically a Gaussian distribution whose peak width (2o) is most often between 6.0 and 20.0, preferably between 8.0 and 18.0, more specifically between 9 and 20.0. , 0 and 17.0, most preferably between 10.0 and 16.0 inclusive.
- This particle size distribution is further characterized by a number average diameter (dso) of zeolite LSX crystals of between 0.5 ⁇ and 20.0 ⁇ , preferably between 1.0 ⁇ and 15.0 ⁇ , more preferably between 4.0 ⁇ and 12.0 ⁇ .
- the zeolitic adsorbent material has a certain amount of non-zeolitic phase, called PNZ, said quantity being preferably 0 ⁇ PNZ ⁇ 6%, more preferably 0.5% ⁇ PNZ ⁇ 4%, measured by XRD, by weight relative to the total weight of the zeolitic adsorbent material.
- the possible different types of zeolites present in the zeolite adsorbent material are determined by XRD.
- the total amount of zeolite (s) 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 zeolitic adsorbent material according to the invention, other than the zeolite (s) present (s). ) in said zeolitic adsorbent material, referred to as “zeolite phase” or "PZ".
- zeolite 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 to say according to the following equation:
- % PNZ 100 -% PZ
- % PNZ represents the weight percentage of PNZ and% PZ the weight percentage of zeolitic phase, relative to the total weight of the zeolitic adsorbent material.
- the PNZ of the zeolitic adsorbent material according to the present invention is such that 0 ⁇ PNZ ⁇ 8%, preferably 0 ⁇ PNZ ⁇ 6%, more preferably 0.5% ⁇ PNZ ⁇ 4% .
- 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.
- 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 ASTM 7084-04 greater than 1.5 MPa, preferably greater than 2.0 MPa, preferably greater than 2.5 MPa, for a mean diameter (dso) or length (greater dimension when the material is not spherical), less than 1 mm, limits included,
- a grain crush strength measured according to ASTM D 41 79 (201 1) and ASTM D 6175 (201 3), of between 0.5 daN and 30 daN, preferably of between 1 daN and 20 daN. daN, for a medium volume diameter material (dso) or a length (larger dimension when the material is not spherical), greater than or equal to 1 mm, inclusive.
- the zeolitic adsorbent material is in the form of balls whose average volume diameter is between 0.05 mm and 5 mm, inclusive.
- this average volume diameter is between 0.05 mm and 1.0 mm, more preferably between 0.15 mm and 0.65 mm, and most preferably between 0.25 mm and 0.55 mm.
- this average volume diameter can be more specifically and more generally between 1.0 mm and 5.0 mm.
- Another preferred characteristic of the zeolitic adsorbent material of the invention is its apparent density which is generally between 0.58 kg. m -3 and 0.80 kg. m “3 , preferably between 0.60 kg. m “ 3 and 0.75 kg. m “3 , more preferably between 0.62 kg. m “ 3 and 0.70 kg. m “3 .
- the invention also relates to a method for preparing the zeolitic adsorbent material according to the invention which comprises the following steps:
- dso number average diameter
- zeolite crystals may be prepared by any means known to those skilled in the art and may for example be obtained by a method similar to that described in FR2925478, with the difference that the crystallization is carried out with little or slightly shear stirring typically with a shear rate of less than 20 s -1 , preferably less than 15 s -1 , more preferably less than 10 s -1 .
- the weight amount of LSX zeolite crystals is generally between 75% and 90% by weight, relative to the total weight of said product obtained at the end of step a / and the amount of zeolite clay as for it is generally between 5% and 25% by weight, relative to the total weight of said product obtained at the end of step a /.
- the source of silica is added in an amount between 0.1% and 10% by weight, preferably between 0.2% and 6% by weight, relative to the total weight of said product obtained at the end of the process. step a /.
- the source of silica that can be used is of any type known per se, and for example solid silica, colloidal silica, sodium silicate, and other sources well known to those skilled in the art.
- step a / is performed according to the techniques well known to those skilled in the art. Similarly, the drying and calcination are carried out according to the usual descriptions also well known to those skilled in the art. Thus, the drying is typically carried out at a temperature between 50 ° C and 200 ° C.
- the calcination can be carried out according to any calcination method known to those skilled in the art and, for example, and without limitation, the calcination can be carried out under an oxidizing and / or inert gas scavenging, in particular with gases such as oxygen , nitrogen, air, a dry air and / or decarbonated oxygen depleted air, optionally dry and / or decarbonated, at a temperature or temperatures above 200 ° C, typically between 250 ° C and 700 ° C, preferably between 300 ° C and 650 ° C, for a few hours, for example between 2 and 6 hours.
- gases such as oxygen , nitrogen, air, a dry air and / or decarbonated oxygen depleted air, optionally dry and / or decarbonated
- the agglomeration binder used in step a / may be of any type known to those skilled in the art and preferably contains at least 80% by weight of clay (s) zeolitizable (s) (called “ zeolitic part ”) relative to the total weight of the agglomeration binder.
- clay (s) zeolizable (s) is meant a clay or a mixture of clays may (s) to be converted (s) zeolite material by action of an alkaline basic solution, according to techniques now well known to those skilled in the art.
- the zeolitizable clays that can be used in the context of the present invention typically belong to the family of kaolinites, halloysites, nacrites, dickites, kaolins and / or metakaolins, clays which can also be added a source silica, as described above.
- non-zeolitizable clays such as, for example and without limitation, selected clays. among attapulgites, sepiolites, bentonites, montmorillonites, and others. This embodiment is however not preferred.
- step a / of agglomeration it is also possible, during step a / of agglomeration, to incorporate one or more organic additive (s), in particular for the purpose of facilitating the shaping and / or to confer particular properties of the agglomerated material, such as mechanical strength, porous profiles, and others.
- organic additives are well known to those skilled in the art and may be incorporated at levels of between 0 and 5% by weight relative to the total weight of said product obtained at the end of step a /.
- step b / of zeolitization the transformation into zeolite material is obtained, at least 50% and preferably at least 70%, more preferably at least 80% and more preferably at least 85% by weight of the zeolitizable clay (s) contained in the binder; it can be seen that zeolitization makes it possible in particular to enhance the mechanical strength of agglomerated zeolite adsorbents.
- the zeolitization can be performed by immersion of the agglomerate in an alkaline basic solution, generally aqueous, for example an aqueous solution of sodium hydroxide and / or potassium hydroxide, the concentration of which is preferably greater at 0.5 M. Said concentration is generally less than 5 M, preferably less than 4 M, advantageously less than 3 M.
- the zeolitization is preferably carried out hot (temperature above room temperature) typically at the order of 80 ° C to 100 ° C, to improve the kinetics of the process and thus reduce immersion times to less than 8 hours. However, it is not beyond the scope of the invention operating at lower temperatures and longer immersion times. It would also not be departing from the scope of the invention to add, during this zeolitization step, a source of liquid or solid silica in the basic alkaline solution, for example sodium silicate or dissolved silica.
- the cl cation replacement step of exchangeable sites of the product obtained in step b / with lithium cations is carried out according to methods also well known to those skilled in the art and described for example in patent EP0893157.
- the lithium exchange is carried out so that the lithium content (expressed as lithium oxide U2O) in the zeolitic adsorbent material of the invention is between 9% and 12% by weight relative to the total weight of the zeolite adsorbent material .
- step d / the last step of the process for obtaining the zeolitic adsorbent material according to the invention, is intended to fix the water content, as well as the loss on ignition of the adsorbent in optimal limits.
- the procedure is generally carried out by thermal activation which is preferably carried out between 300 ° C. and 600 ° C. for a certain time, typically from 1 to 6 hours, depending on the desired water content and loss on ignition and according to use of the adsorbent that is targeted.
- the zeolitic adsorbent material according to the present invention finds a particularly advantageous use as a nitrogen adsorbent material for the separation of air gases and excellent adsorbents of nitrogen and / or carbon monoxide. for the purification of hydrogen.
- the zeolitic adsorbent material according to the present invention most often has a mass adsorption capacity of nitrogen (N2), measured under 1 bar at 25 ° C, greater than 24 Ncm 3 .g -1 , preferably greater at 25 Ncm 3 .g -1 , more preferably greater than 26 Ncm 3 .g -1 , and typically greater than 26.5 Ncm 3 .g -1 , very particularly preferably greater than 27 Ncm 3 .g -1 .
- N2 mass adsorption capacity of nitrogen
- the adsorption processes employing the zeolitic adsorbent material according to the present invention are most often of the PSA, VSA or VPSA type, and preferably of the PSA or VPSA type for the N 2 / O 2 separation of the industrial gases and for N2 / O2 separation in medical oxygen production equipment.
- the zeolitic adsorbent material according to the present invention thus finds a particularly interesting application as an adsorption element in oxygen concentrators respiratory assistance.
- the zeolitic adsorbent material according to the invention constitutes the active ingredient of a consumable zeolite adsorbent cartridge, insertable into a breathing assistance oxygen concentrator, whether it is transportable, mobile, preferably portable.
- the consumable zeolite adsorbent cartridge can be of any form adapted to be easily inserted and replaced in oxygen concentrators respiratory assistance.
- said cartridge may be prepared from the zeolitic adsorbent material according to the invention in the form of beads made cohesive with them by virtue of at least one resin, preferably a polymer resin chosen from among the homo- and / or thermoplastic copolymers and polycondensates.
- Non-limiting examples of such polymer resins are polyolefins, especially low and / or high and / or ultra-high density polyethylene, polypropylene, ethylene copolymers, ethylene-vinyl acetate copolymers, polyacrylics, acrylonitrile homo- and / or copolymers, polyacrylates, polymethacrylates, acrylate copolymers and / or methacrylate copolymers, polystyrenes and / or styrene copolymers, polyesters, p. ex.
- polyethylene terephthalate polybutylene terephthalate, halogenated polymers and copolymers such as polyvinylidene difluoride (PVDF) polymers, polymers and / or copolymers of polytetrafluoroethylene (PTFE), polyamides, such as polyamide -1 and polyamide-12, as well as other even and odd polyamides, aromatic polyamides, polyvinyl chlorides, polyurethanes, polyethersulfones, polyetherketones, polycarbonates, epoxy resins, phenolic resins, thermosetting resins and elastomeric resins, and the like, as well as mixtures of two or more of them in all proportions.
- PVDF polyvinylidene difluoride
- PTFE polytetrafluoroethylene
- polyamides such as polyamide -1 and polyamide-12, as well as other even and odd polyamides
- aromatic polyamides polyvinyl chlorides, polyurethanes, polyethersulfone
- the consumable cartridge may further comprise or instead of the zeolite adsorbent material, a fixed bed of zeolitic adsorbent material according to the invention.
- the invention relates to a portable, portable, preferably portable respiratory assistance oxygen concentrator comprising at least one zeolitic adsorbent material, or at least one fixed adsorption bed, or at least one composite material, or at least one cartridge, as just described above.
- the zeolitic adsorbent material according to the present invention has a better volume efficiency than the adsorbent materials available today. This gain in volume efficiency offers many advantages among which one of the main is to allow a reduction in the size of equipment, including oxygen concentrators respiratory assistance.
- the zeolitic adsorbent material according to the present invention has a better nitrogen adsorption capacity capacity (N2) than the known non-zeolite binder adsorbent materials available on the market, but also a better capacity of nitrogen adsorption (N2) than zeolite-bonded adsorbent materials known in the prior art, for example in patent EP0893157.
- the zeolitic adsorbent material according to the invention also has the dual advantage of a high mass adsorption capacity combined with a high density of agglomerates due to the particular particle size distribution of the crystals to obtain a high compactness. Furthermore, the zeolitic adsorbent material according to the invention is provided with very good mechanical properties, and in particular a very good resistance to crushing in bed (REL).
- REL resistance to crushing in bed
- the physical properties of the zeolite adsorbent material according to the invention are evaluated by methods known to those skilled in the art, the main of which are recalled below.
- the estimation of the number average diameter of LSX zeolite crystals which are used for the preparation of the zeolitic adsorbent material of the invention 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 size selected for each crystal is that of the largest section of said crystal considered. Particles smaller than 0.5 ⁇ which could possibly be present in the zeolitic adsorbent material are not taken into account in the counting.
- the resulting particle size distribution is equivalent to the average particle size distribution observed on each of the shots.
- the width of the peak and the number average diameter are calculated according to the conventional methods known to those skilled in the art, by applying the statistical rules of Gaussian distribution.
- the determination of the average volume diameter (or "volume average diameter") of the zeolite adsorbent material of the invention is carried out by analysis of the particle size distribution of a sample of adsorbent material by imaging according to the ISO 13322-2 standard. : 2006, using a treadmill allowing the sample to pass in front of the lens of the camera.
- 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.
- the accuracy is of the order of 0.01 mm for the size range of the zeolite adsorbent materials of the present invention.
- An elemental chemical analysis of a zeolitic adsorbent material according to the invention 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 the atoms generally by an X-ray beam or by bombardment with electrons, generates specific radiations after return to the ground state of the atom.
- 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
- 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 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.
- 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 (Na 2 O, CaO, K 2 O, BaO, U 2 O, CS 2 O , 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.
- 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.
- the apparent density of the zeolitic adsorbent material according to the present invention is measured as described in the DIN 8948 / 7.6 standard.
- the loss on ignition of the zeolite adsorbent material according to the invention 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. 196-2 (April 2006). The standard deviation of measurement is less than 0.1%.
- the purity of the zeolites in the zeolite adsorbent materials of the invention is evaluated by X-ray diffraction analysis, known to those skilled in the art under the acronym DRX. This identification is carried out on a DRX device of the brand Bruker.
- 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 as follows:
- the interpretation of the diffractogram obtained is performed with the EVA software with identification of zeolites 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.
- the adsorption mass capacity at 25 ° C., under 1 bar, of the zeolite adsorbent material is determined from the measurement of the gas adsorption isotherm, such as nitrogen or oxygen, at 25 ° C.
- the zeolitic adsorbent material 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 (pressure less than 6.7 ⁇ 10 -4 Pa). adsorption isotherms is then carried out on an ASAP 2020 Micromeritics type apparatus, taking at least 10 measurement points at relative pressures with a ratio ⁇ / ⁇ 0 of between 0.001 and 1.
- the adsorption mass capacity of the zeolite adsorbent material is read on the isotherm at 25 ° C under a pressure of 1 bar, and expressed in Ncm 3 g -1 .
- the adsorption capacity at 25 ° C., under 1 bar, of the zeolitic adsorbent material is calculated from the adsorption mass capacity as defined above and by multiplying said mass capacity of adsorption by the bulk density of said zeolite adsorbent material. Bulk density is measured as described in DIN 8948 / 7.6.
- the dough thus prepared is used on a granulating plate in order to produce balls of agglomerated zeolite adsorbent material.
- Selection by sieving of the beads obtained is carried out so as to collect beads having a diameter of between 0.3 mm and 0.8 mm and a volume average diameter equal to 0.50 mm.
- the beads are dried overnight in a ventilated oven at 80 ° C. They are then calcined for 2 hours at 550 ° C. under a decarbonated dry air sweep.
- the beads are dried overnight in a ventilated oven at 80 ° C. They are then activated for 2 hours at 550 ° C. under a decarbonated dry air sweep.
- the content of lithium oxide L12O, determined by ICP-AES, is 10.6% by weight relative to the total weight of the zeolitic adsorbent material.
- the average volume diameter of the balls is 0.50 mm.
- the mechanical crush strength in bed of zeolite LSX beads exchanged with lithium is 1.4 MPa, the bulk density is 0.58 kg. m -3 , the Si / Al ratio of the zeolite material is equal to 1.02, the PNZ is equal to 3%
- the adsorption capacity at 25 ° C., under 1 bar, is equal to 24.7 Ncm 3 g -1 .
- the zeolitic adsorbent material is then prepared according to the protocol described in Example 1.
- the content of lithium oxide L12O, determined by ICP-AES, is 10.7% by weight relative to the total weight of the zeolitic adsorbent material.
- the average volume diameter of the balls is 0.50 mm.
- the bed crush strength (REL) of lithium exchanged LSX zeolite beads was 2.6 MPa, the bulk density was 0.63 kg. m -3 , the Si / Al ratio of the zeolite material is 1.03, the PNZ is 2.7%.
- the specific adsorption capacity at 25 ° C., under 1 bar, is equal to 27 Ncm 3 g -1 .
- Example 3 N2 / O2 separation tests on a fixed bed of adsorbent with modulation of pressure adsorption (PSA)
- PSA pressure adsorption
- Figure 1 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.
- 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. The tests are carried out successively with the zeolitic adsorbent materials of Example 1 and Example 2.
- the column is charged at constant volume, with respectively 219 g and 228.5 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 1 S.
- the desorption time is variable between 2 s and 4.5 s.
- the oxygen concentration at the outlet (9) is measured using a Servomex 570A oxygen analyzer.
- FIG. 2 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 2 is is much more efficient in terms of the oxygen content of the product gas than the solid of Example 1.
Abstract
Description
Claims
Priority Applications (9)
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JP2019529517A JP7083346B2 (ja) | 2016-12-02 | 2017-12-01 | ゼオライト吸着材料、製造方法、及び工業用ガスの非極低温分離のための使用 |
EP17822362.4A EP3548171A1 (fr) | 2016-12-02 | 2017-12-01 | Matériau adsorbant zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique des gaz industriels |
CN201780085401.3A CN110214050B (zh) | 2016-12-02 | 2017-12-01 | 沸石吸附性材料、制备方法和用于工业气体非低温分离的用途 |
CA3044620A CA3044620C (fr) | 2016-12-02 | 2017-12-01 | Materiau adsorbant zeolithique, procede de preparation et utilisation pour la separation non-cryogenique des gaz industriels |
US16/465,417 US11007505B2 (en) | 2016-12-02 | 2017-12-01 | Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases |
AU2017367216A AU2017367216B2 (en) | 2016-12-02 | 2017-12-01 | Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases |
KR1020197018049A KR102257867B1 (ko) | 2016-12-02 | 2017-12-01 | 산업용 가스들의 비극저온 분리를 위한 제올라이트 흡착제 재료, 제조 방법 및 용도 |
IL266856A IL266856A (en) | 2016-12-02 | 2019-05-23 | Zeolite material on which aggregation can occur, method of preparation and use for non-cryogenic separation of industrial gases |
ZA2019/03945A ZA201903945B (en) | 2016-12-02 | 2019-06-18 | Zeolite adsorbent material, method of preparation and use for non-cryogenic separation of industrial gases |
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Cited By (2)
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WO2020128270A1 (fr) * | 2018-12-21 | 2020-06-25 | Arkema France | Matériau aggloméré zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique de gaz |
FR3103393A1 (fr) | 2019-11-27 | 2021-05-28 | Arkema France | Séparation des gaz de l’air |
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KR102375233B1 (ko) * | 2020-03-20 | 2022-03-17 | 주식회사 씨앤씨랩 | 산성 유해가스 흡착력을 갖는 유-무기 복합 소재용 고분자 바인더 조성물 및 이를 포함하는 유-무기 복합 소재 |
WO2023250300A1 (fr) * | 2022-06-20 | 2023-12-28 | Zeochem Llc | Adsorbant pour la séparation d'un flux gazeux |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020128270A1 (fr) * | 2018-12-21 | 2020-06-25 | Arkema France | Matériau aggloméré zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique de gaz |
FR3090412A1 (fr) * | 2018-12-21 | 2020-06-26 | Arkema France | Matériau aggloméré zéolithique, procédé de préparation et utilisation pour la séparation non-cryogénique de gaz |
KR20210100706A (ko) * | 2018-12-21 | 2021-08-17 | 아르끄마 프랑스 | 제올라이트 응집재, 제조 방법, 및 비극저온 가스 분리를 위한 용도 |
JP2022514390A (ja) * | 2018-12-21 | 2022-02-10 | アルケマ フランス | ゼオライト性アグロメレート化材料、調製方法及び非極低温ガス分離のための使用 |
US20220072505A1 (en) * | 2018-12-21 | 2022-03-10 | Arkema France | Zeolitic agglomerated material, preparation process and use for non-cryogenic gas separation |
AU2019411145B2 (en) * | 2018-12-21 | 2022-03-31 | Arkema France | Zeolite agglomerate material, method of production, and use for the non-cryogenic separation of gas |
KR102601786B1 (ko) * | 2018-12-21 | 2023-11-13 | 아르끄마 프랑스 | 제올라이트 응집재, 제조 방법, 및 비극저온 가스 분리를 위한 용도 |
FR3103393A1 (fr) | 2019-11-27 | 2021-05-28 | Arkema France | Séparation des gaz de l’air |
WO2021105598A1 (fr) | 2019-11-27 | 2021-06-03 | Arkema France | Séparation des gaz de l'air |
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FR3059571A1 (fr) | 2018-06-08 |
CN110214050A (zh) | 2019-09-06 |
KR102257867B1 (ko) | 2021-05-28 |
JP2019536625A (ja) | 2019-12-19 |
US11007505B2 (en) | 2021-05-18 |
FR3059571B1 (fr) | 2018-11-16 |
US20190388871A1 (en) | 2019-12-26 |
CN110214050B (zh) | 2022-10-28 |
KR20190086000A (ko) | 2019-07-19 |
ZA201903945B (en) | 2020-12-23 |
CA3044620A1 (fr) | 2018-06-07 |
TWI667067B (zh) | 2019-08-01 |
AR110276A1 (es) | 2019-03-13 |
JP7083346B2 (ja) | 2022-06-10 |
IL266856A (en) | 2019-07-31 |
AU2017367216A1 (en) | 2019-06-13 |
CA3044620C (fr) | 2021-03-23 |
EP3548171A1 (fr) | 2019-10-09 |
TW201825175A (zh) | 2018-07-16 |
AU2017367216B2 (en) | 2019-09-26 |
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