Zeolite Adsorbent Material Method Of Preparation And Use For Non Cryogenic Separation Of Industrial Gases
Abstract:
The present invention concerns novel zeolite adsorbent materials, in particular specific zeolite adsorbent materials suitable for the non-cryogenic separation of industrial gases, and more particularly for the separation of nitrogen by adsorption in gas flows such as air and the purification of hydrogen by adsorption of carbon monoxide (CO) and/or nitrogen (N2), and the use of same, in particular, for preparing medical oxygen in breathing assistance oxygen concentrators.
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Notices, Deadlines & Correspondence
51 avenue du chateau d'Este, Billiere 64140, france
2. LUTZ, Cécile
L'Armadière
Chemin Bernathaur
64290 GAN
3. SZENDROVICS, Sylvie
40, Route de Caubin
64370 ARTHEZ-DE-BEARN
4. PERSILLON, Quitterie
29, Rue du Luy du Béarn
64160 MORLAAS
Specification
The present invention relates to specific adsorbent materials for the non-cryogenic separation of industrial gases, and more particularly for the separation of nitrogen adsorption in the gas streams such as air and the purification of hydrogen adsorption by carbon monoxide (CO) and / or nitrogen (N2).
[0002] The separation of gas mixtures of nitrogen is at the basis of several non-cryogenic industrial processes, including the production of oxygen from air by PSA method ( "Pressure Swing Adsorption", in English, or "pressure Swing Adsorption") or VPSA ( "vacuum and pressure Swing Adsorption" in English or "pressure Swing Adsorption and vacuum"), the PSA process is one of the most important.
[0003] In this application, air is compressed and sent through a column of adsorbent having a preference for the nitrogen molecule. Is thus produced during the adsorption cycle of oxygen at about 94-95% and argon. After a certain period, the column is depressurized and then maintained at low pressure, during which time nitrogen is desorbed. A recompression is then ensured by means of a portion of the oxygen product and / or by air, and the cycle continues. The advantage of this process compared to cryogenic processes is the greatest simplicity of facilities and greater ease of maintenance.
[0004] The quality of the adsorbent used is the key to an efficient and competitive process. The performance of the adsorbent is related to several factors, among which there may be mentioned nitrogen adsorption capacity and selectivity between nitrogen and oxygen that will be decisive for sizing column sizes and optimize production efficiency (ratio the oxygen produced and entered oxygen), the adsorption kinetics that will optimize cycle times and improve productivity of the plant.
[0005] The use of molecular sieves as selective adsorbents for nitrogen is a technology well known today. Family of zeolites having a pore diameter of at least 0.4 nm (4 Å) is presented for example in US3140931 for the separation of oxygen and nitrogen mixtures. The comparative performance of different ionic forms of zeolites is described in US3140933, especially that of the lithium form presented as the most effective in terms of selectivity.
[0006] FR2766476 discloses a demand improved zeolitic adsorbent for the separation of air gases and its production process. This document describes a material
zeolite LSX adsorbent comprising lithium, optionally potassium, and binder zéolithisé. This adsorbent material has a higher nitrogen adsorption capacity than or equal to 26 cm 3 . g -1 . Said material is made from at least 95% of LSX type zeolite (molar ratio Si / Al = 1) exchanged with lithium. It is however seen that the strength of these agglomerates may be insufficient in some applications.
[0007] The international application WO2008 / 152319 discloses a sinter process for preparing zeolitic which the zeolite content is greater than 70% by weight and the ball diameter (dso) less than 600 μηι and density between 0, 5 g. cm -3 and 0.8 g. cm -3 . Potentially used zeolites are zeolites LSX, X and A and agglomeration clays are zéolithisables or not. This application also describes the possible addition of silica in an amount of 1% to 5% by weight relative to the total mass of solids (calcined equivalent) in preparing the agglomerates.
[0008] The patent US6478854 discloses a sinter process for preparing zeolite-based LiLSX "binderless" (ie "binderless") and their use in gas separation. The agglomeration binder is converted by percolation with a solution of sodium and potassium hydroxides with a Na / ratio (Na + K) between 0.1 and 0.4. An aluminum source can be added to the caustic solution to convert the binder preferably in LSX type zeolite. Converting the binder LSX is measured by a peak intensity ratio of the diffraction pattern, between the peak corresponding to the diffraction plane (Miller index) 220 and the peak corresponding to the diffraction plane 31 1.
[0009] The international application WO2013 / 106017 describes a zeolite preparation process X binderless atomic Si / Al ratio between 1, 0 and 1, 5 usable after agglomeration and exchange with barium, for the separation of xylene isomers. The size of the zeolite X crystals is 2.7 μηι and the crystal size of zeolite binder converted to (between 5% and 30% by weight relative to the total weight of zeolite) is not defined. The binder is partially converted to zeolite A.
[0010] The international WO2014 / 176002 application describes a method of preparing an adsorbent material agglomerate from a choice of two binders having different particle sizes, zeolitization then exchange the lithium. It is also possible to add a source of liquid or solid to zéolithiser silica binder to zeolite X having an atomic ratio Si / Al may differ from that of the initial zeolite.
[0011] The current importance of the non-cryogenic separation processes of industrial gases implementing zeolitic adsorbent materials (also known as "molecular sieves) shows that the discovery and development of increasingly efficient adsorbents is an important goal for both companies producing gas and for companies providing said molecular sieves.
[0012] One objective of the present invention is therefore the provision of zeolitic adsorbent materials with improved adsorption capacity compared with zeolitic adsorbent materials LiLSX type binder existing zéolithisé, for the separation of industrial gases, in particular nitrogen and oxygen.
[0013] It has now been discovered that it is possible to prepare zeolite adsorbent materials highly capacitive, from LSX zeolite crystals, containing lithium, for the non-cryogenic separation of industrial gases (V) PSA, particularly for the separation of nitrogen and oxygen (N2 / O2), especially for the preparation of medical oxygen from air and for the industrial preparation of oxygen (V) PSA.
[0014] Thus, according to a first aspect, the present invention relates to a zeolitic adsorbent material:
- based on zeolite LSX crystals whose particle size distribution is characterized by a peak width (2o) between 6.0 and 20.0, inclusive to a number average diameter (dso) of from 0.5 μηη and 20.0 μηι,
- atomic Si / Al ratio between 1, 00 and 1, 15, inclusive,
- of which the lithium content, expressed by weight of L12O is between 9% and 12% by weight relative to the total weight of the zeolitic adsorbent material, and
- of content of non-zeolitic phase (PNZ), such that 0
Documents
Application Documents
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Name
Date
1
201917021722-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [31-05-2019(online)].pdf
2019-05-31
2
201917021722-STATEMENT OF UNDERTAKING (FORM 3) [31-05-2019(online)].pdf
2019-05-31
3
201917021722-REQUEST FOR EXAMINATION (FORM-18) [31-05-2019(online)].pdf