WO2010052736A1 - Procédé de préparation d’un adsorbant pour tamis moléculaire utile pour l'adsorption sélective de l’oxygène d’un mélange gazeux contenant de l’argon - Google Patents

Procédé de préparation d’un adsorbant pour tamis moléculaire utile pour l'adsorption sélective de l’oxygène d’un mélange gazeux contenant de l’argon Download PDF

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WO2010052736A1
WO2010052736A1 PCT/IN2009/000399 IN2009000399W WO2010052736A1 WO 2010052736 A1 WO2010052736 A1 WO 2010052736A1 IN 2009000399 W IN2009000399 W IN 2009000399W WO 2010052736 A1 WO2010052736 A1 WO 2010052736A1
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oxygen
argon
adsorbent
zeolite
adsorption
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Raksh Vir Jasra
Sunil Peter Adavanal
Arun Sadashio Moharir
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Council of Scientific and Industrial Research CSIR
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • 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
    • 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
    • B01D2256/18—Noble gases
    • 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
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01D53/0476—Vacuum pressure swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y

Definitions

  • the present invention relates to a process for the preparation of a molecular sieve adsorbent for the selective adsorption of oxygen from its gaseous .mixture with argon.
  • the present invention also relates to the use of a cation exchanged zeolite of faujasite type as a selective adsorbent for the separation of gases having closely related physical properties. More particularly, the present invention relates to process for the preparation of an adsorbent, which is more selective towards oxygen from a gaseous mixture of oxygen with argon, and also relates to the processes which utilize this adsorbent as an oxygen selective adsorbent.
  • Adsorption process is established commercially as pressure swing adsorption (PSA) or vacuum swing adsorption (VSA) for the separation of gases. Since the advent of synthetic zeolites in 1959, innovations in adsorbent development and adsorption process cycle have made adsorption a key separation process in the chemical, petrochemical and pharmaceutical industries. The selection of a proper adsorbent for a given separation is the most important step in any adsorption processes. Oxygen production from air using zeolite adsorbent is one of the main commercial PSA processes. However, the maximum attainable oxygen purity by adsorption processes is around 95% and the rest consists of mostly argon present in the feed air.
  • this crude argon is purified by a combination of distillation and "de-oxo" process.
  • de-oxo process the crude argon is heated and the oxygen in the stream is reacted with controlled amount of hydrogen to form water.
  • This hot gas stream is cooled and the resulting water vapour from oxygen-hydrogen reaction is removed, usually in a dual bed adsorber drier system.
  • pure argon is produced by removing the nitrogen and unreacted hydrogen in a "pure argon tower" by cryogenic distillation.
  • this process is very energy intensive due to the heating and cooling of the crude argon stream and also the capital cost is high for additional installation on the cryogenic distillation unit.
  • Adsorption based process can be compete with the energy intensive cryogenic separation of oxygen-argon mixture if a suitable adsorbent, which is selective towards one of the components and is having requisite adsorption capacity, is available.
  • U. S. Pat. No. 4,713,362 (1987) to Maroulis et al. disclosed the preparation and activation of a selective zeolite adsorbent for the chromatographic separation of argon- oxygen from their gaseous mixture.
  • the adsorbent of their choice was mainly divalent cation containing chabazite zeolite, particularly calcium exchanged chabazite and the thoroughly dehydrated adsorbent was activated in an oxidising atmosphere for the argon- oxygen separation.
  • the separation mechanism was mainly based on kinetic selectivity towards oxygen in its mixture with argon.
  • U. S. Pat. No. 5,601,634 (1997) disclosed a cryogenic temperature swing adsorption process for the production of high purity argon from a two-phase vapour-liquid- mixture.
  • the two phase mixture of argon, oxygen and nitrogen is passed through two adsorbent beds; each of them contains a nitrogen selective adsorbent layer and an oxygen adsorbent layer preceding to the nitrogen selective adsorbent layer, at a temperature between the bubble point and the dew point of the two phase mixture.
  • the nitrogen selective adsorbent was zeolite X or mordenite
  • the oxygen selective adsorbent layer was carbon molecular sieve or zeolite 4A. This process has drawbacks in terms of being at cryogenic temperatures and also employing different adsorbents.
  • U. S. Pat. No. 5,159,816 (1992) to Kovak et al. disclosed the production of high purity argon by cryogenic adsorption wherein a crude argon stream flows through a bed of adsorbent that preferentially adsorbs nitrogen, and then through another adsorbent bed that preferentially adsorbs oxygen.
  • U. S. Pat. No. 4,477,265 (1984) to Kumar et al. also discloses the adsorption of oxygen and nitrogen from an argon-rich feed taken from the rectification column of a cryogenic air separation plant.
  • high purity argon is separated and recovered from the crude argon stream containing minor amounts of oxygen and nitrogen, by passing through two separate adsorbent columns in series wherein the first column contains a nitrogen equilibrium selective adsorbent used for nitrogen removal and the second bed contains an oxygen kinetic selective adsorbent used for oxygen removal. Further purification of the recovered argon is carried out by catalytic hydrogenation of residual oxygen therein. The process needs additional catalytic hydrogenation step to obtain high purity argon, which is a drawback of this invention.
  • U. S. Pat. No. 6,527, 831 (2003) to Baksh et al. disclosed a vacuum pressure swing process (VPSA) for the purification of argon in crude argon stream from cryogenic air separation plant.
  • VPSA vacuum pressure swing process
  • the adsorbent used for this VPSA process was oxygen rate selective adsorbent such as carbon molecular sieve (CMS) to separate the argon-oxygen mixture.
  • CMS carbon molecular sieve
  • the process makes use of expensive carbon molecular sieve type adsorbent for the selective adsorption of oxygen.
  • U. S. Pat. No. 5,081,097 (1992) to Sharma et al. disclosed finely divided elemental copper modified carbon molecular sieves for the selective adsorption of oxygen at elevated temperatures.
  • the copper modified carbon molecular sieves were prepared by pyrolysis of a mixture of a copper-containing material and polyfunctional alcohol to form an adsorbent precursor.
  • the adsorbent precursors were then heated and reduced to produce copper modified carbon molecular sieves.
  • the process suffers from a drawback of being as a high temperature process.
  • U. S. Pat. No. 6,878,657 (2005) to Jasra et al. disclosed a process for the manufacturing of a pore mouth controlled zeolite molecular sieve adsorbent for the size/shape selective adsorption of gas molecules from their gaseous mixture. More specifically, their invention related to the preparation and use of a molecular sieve adsorbent, which is selective towards oxygen from its gaseous mixture with nitrogen and argon by pore mouth control of zeolite NaA with liquid phase alkoxide deposition on the external surface at ambient conditions of temperature and pressure. The process has limitation as the adsorbent has a very small adsorption capacity.
  • U. S. Pat. No. 7,319,082 (2008) to Jasra et al. disclosed another process for the preparation of oxygen selective adsorbent for the separation of oxygen from its gaseous mixture with nitrogen and/or argon. More specifically, the invention related to the manufacture and use of molecular sieve adsorbent by cation exchange in zeolite X especially using rare earth cations like cerium to obtain oxygen selective adsorbent for the adsorption of oxygen from its gaseous mixture with nitrogen and oxygen at ambient temperature and pressure.
  • U. S. Pat. No. 5,226,933 (1993) to Knaebel et al. disclosed a pressure swing adsorption (PSA) process for splitting oxygen from a feed gas comprising 95% oxygen and 5% argon to achieve an oxygen purity of at least about 99.7%.
  • a column used in the PSA process includes therein a bed of silver mordenite, as an argon selective adsorbent.
  • LJ. S. Pat. No. 5,470,378 (1995) to Kandybin et al. disclosed a process for removing argon from a feed gas stream comprising oxygen and argon to yield a high purity oxygen stream and the system for carrying out the process.
  • the process included the steps of: (a) providing a feed gas of oxygen and argon at a temperature between -30° C. and 100° C.
  • the main object of the present invention is to provide a process for the preparation of a molecular sieve adsorbent for the selective adsorption of oxygen from its gaseous mixture with argon at ambient temperatures.
  • Another object of the present invention is to provide an oxygen selective zeolite based adsorbent prepared by a simple post-synthesis modification.
  • Yet another object of the present invention is to provide an adsorbent with high adsorption selectivity and capacity for oxygen from its gaseous mixture with argon.
  • Yet another object of the present invention is to provide a process for the preparation of a commercially inexpensive oxygen selective adsorbent which can be used in a pressure swing adsorption (PSA) process, vacuum swing adsorption (VSA) process or vacuum pressure swing adsorption (VPSA) process for the production of pure argon gas product either in conjunction with cryogenic air separation process where crude argon can be purified, or in combination with oxygen PSA process where the product oxygen gas contains around 5% argon and this argon gas can be separated to get pure argon gas product.
  • PSA pressure swing adsorption
  • VSA vacuum swing adsorption
  • VPSA vacuum pressure swing adsorption
  • the present invention provides a process for the preparation of a molecular sieve adsorbent for the selective adsorption of oxygen from its gaseous mixture with argon, the process comprising the steps of:
  • the divalent alkaline earth metal cation used in step (i) is selected from the group consisting of calcium, strontium and barium.
  • zeolite X in powder form or in granular form can be used for the preparation of the oxygen selective molecular sieve adsorbent.
  • zeolite X is exchanged with alkaline earth metal cations at a temperature range of 303 to 363 K for 4- 24 hrs using 0.01 - 1 molar solution of the specific salt.
  • At least 30% of any exchangeable ion capacity of zeolite is exchanged with an alkaline earth metal cation or the mixture of alkaline earth metal cations thereof.
  • the molecular sieve adsorbent is useful for the selective adsorption of oxygen from its mixture with argon, for the production of highly pure argon from a feed gas consists of argon at varying concentration with other gases like oxygen.
  • the molecular sieve adsorbent obtained is useful for the preparation of chromatographic column for the analysis air samples, particularly for argon-oxygen mixtures.
  • the molecular sieve adsorbent obtained is useful for the preparation of chromatographic column, which is selective towards oxygen and argon as in the order of oxygen > argon.
  • the alkaline earth metal exchanged zeolite X in binderless pellet form can be used as the adsorbent for the preparation of the chromatographic column having a dimension of 2 meter length and 3 mm outside diameter for the chromatographic separation of argon-oxygen gaseous mixture.
  • the alkaline earth metal exchanged zeolite X in binderless pellet form especially strontium cation exchanged zeolite X pellets are activated at high temperature in the range of 473K - 773K, specifically 523K - 673K under an inert atmosphere like helium, nitrogen, argon, oxygen or under vacuum.
  • strontium exchanged zeolite X spherical beads were used for the dynamic adsorption studies of argon and oxygen gas mixture in an adsorbent column at different feed concentration of 5 -95% of oxygen in argon.
  • the alkaline earth metal exchanged zeolite X spherical beads were activated under argon gas flow at a heating rate of 2 K/min upto 623 K and kept at this temperature for 8 hrs, prior to the dynamic adsorption studies of argon-oxygen gas mixtures.
  • the saturated cation exchanged zeolite X adsorbent after dynamic adsorption studies of argon-oxygen gas mixture can be reused after activation under argon gas purge or by applying vacuum inside the adsorbent column at ambient temperature.
  • the alkaline earth metal cation exchanged zeolite X adsorbent; especially strontium exchanged zeolite X adsorbent can be used in pressure swing adsorption or vacuum swing adsorption process for the separation of argon from its gaseous mixture with oxygen.
  • the cation exchanged zeolite adsorbent has an oxygen equilibrium adsorption capacity in the range of 5.0 - 8.0 cc/g and an equilibrium selectivity for oxygen over argon in the range of 1.4 - 2.0, at 303 K and 760 mmHg.”
  • FIG. 1 is a diagram of equilibrium adsorption isotherms of oxygen and argon in NaX(Pe) at 303 K.
  • FIG. 2 is a diagram of equilibrium adsorption isotherms of oxygen and argon in SrX(Pe) at 303 K.
  • FIG. 3 is a chromatogram for the separation of argon and oxygen utilizing the adsorbent material produced in Example 2, at 308 K.
  • the concentration of argon was 5.5% and that of oxygen was 94.5% on volume basis.
  • FIG. 4 is a chromatogram for the separation of argon and oxygen utilizing the adsorbent material produced in Example 2, at 308 K.
  • the concentration of argon was 10% and that of oxygen was 90% on volume basis.
  • FIG. 5 is a chromatogram for the separation of argon and oxygen utilizing the adsorbent material produced in Example 2, at 308 K.
  • the concentration of argon was 54% and that of oxygen was 46% on volume basis.
  • FIG. 6 is a diagram of break-through curves of oxygen in SrX(G) adsorbent at 303 K as described in Example 4.
  • FIG. 7 is a diagram of breakthrough curves of oxygen in SrX(G) adsorbent at 303 K as described in Example 5.
  • FIG. 8 is a diagram of breakthrough curves of oxygen in SrX(G) adsorbent at 303 K as described in Example 6.
  • FIG. 9 is a diagram of breakthrough curves of oxygen in SrX(G) adsorbent at 303 K as described in Example 7.
  • the present invention provides mainly a process for the preparation of a molecular sieve adsorbent for the selective adsorption of oxygen from its gaseous mixture -with argon, such an adsorbent is prepared by cation exchange of faujasite type zeolite taken in the form of powder, binderless pellets and granular beads, with an aqueous solution of alkaline earth metal salts at an elevated temperature for 2 - 24 hrs using 0.01 - 1 molar solution of the specific salt followed by activation of the molecular sieve at an increased temperature under an inert atmosphere or vacuum.
  • the dry zeolite X containing 50 to 100% strontium cations of the total exchangeable sodium cations, after activation at high temperature and vacuum was subjected to adsorption studies of oxygen and argon using a static volumetric adsorption system supplied by Micromeritics Corp. USA (Model ASAP 2010).
  • the pure component adsorption isotherms, capacity and selectivity of cation exchanged zeolite X for oxygen and argon were measured at 288 K and 303 K, in the pressure range of 0.5 mm Hg - 850 mm Hg.
  • the present invention provides a process for the preparation of a zeolite molecular sieve adsorbent for the selective adsorption • of oxygen from its gaseous mixture with argon.
  • Zeolites which are microporous crystalline aluminosilicates, are finding increased applications for the separation of mixtures of compounds having closely related molecular properties.
  • SiO 2 and AlO 2 tetrahedra are connected by sharing oxygen atoms.
  • Al 3+ and Si 4+ ions are buried in the tetrahedra of oxygen atoms and are not directly exposed to adsorbate molecules.
  • the zeolite of interest in the present invention was of faujasite type zeolite, specifically zeolite X.
  • Zeolite NaX powder procured from Zeolites and Allied Products, Mumbai, India having a chemical composition Na 88 Al 88 Si 104 O 384 -WH 2 O (w changes from 220 to 280) was used as the starting material and zeolite X spherical beads were procured from Zeochem AG, Switzerland which was used for the dynamic adsorption measurements.
  • the zeolite X with exchangeable cations mainly consists of sodium ions, was first pressed up to 5 tonnes force to make pellets using a hydraulic pelletizer. These pellets are then crushed and sieved to collect adsorbent particles in the range of 30 - 100 mesh size. The adsorbent particles are exchanged repeatedly with alkaline earth metal cations in an aqueous solution of their salts, especially chloride, nitrate and acetate, and more particularly chloride salt, until the complete exchange of sodium cations with alkaline earth metal cations.
  • their salts especially chloride, nitrate and acetate, and more particularly chloride salt
  • the concentration of the aqueous solution of alkaline earth metal salt was in the range of 0.01 M - I M, particularly between 0.05 M - 0.25 M and the adsorbent particles were treated with this solution for two times repeatedly and then filtered, washed with distilled water until the washings are free from chloride ions and dried in a hot air oven for overnight at 353 K.
  • the percentage exchange of alkaline earth metal cations into the zeolite X samples were measured using energy dispersive ⁇ -ray analyzer (Oxford INCA, Energy 200 Suite) attached to the scanning electron microscope (LEO 1430 VP).
  • Oxygen and argon adsorption at 288 K and 303 K were studies in a static volumetric adsorption system (Micormeritics, USA, Model ASAP 2010), after activating the sample at 623 K under vacuum for about 4 - 8 hrs as described in the examples herein.
  • the samples were evacuated completely and requisite amount of the adsorbate gas was injected into the volumetric set up at volumes required to achieve a targeted set of pressures ranging from 0.1 to 850mmHg.
  • a minimum equilibrium interval of 5 seconds with a relative target tolerance of 5.0% of the targeted pressure and an absolute target tolerance of 5.000 mmHg were used to determine equilibrium for each measurement point.
  • Adsorption temperature was maintained (+0.1K) by circulating water from a constant temperature bath (Julabo F25, Germany).
  • VA and VB are the volumes of gas A and B respectively adsorbed at any given pressure P and temperature T.
  • Isosteric heats of adsorption were calculated from the adsorption data collected at 288 K and 303 K using Clausius-Clapeyron equation.
  • R is the universal gas constant
  • ⁇ is the fraction of the adsorbed sites at a pressure P and temperature T.
  • the important inventive step of the process includes . in developing a material with very high oxygen adsorption capacity of 6.86 cc/g and oxygen/argon selectivity of 1.8 at 303 K and 760 mm Hg.
  • Another important inventive step involved in the present invention is the preparation of a chromatographic column which can be used for the chromatographic analysis of air, especially argon-oxygen mixtures, at ambient temperatures or even at higher temperatures.
  • very long fused silica PLOT Molecular Sieve 5A columns (capillary columns) are used for the separation of permanent gases especially for argon- oxygen separation.
  • this column can handle only very low sample volume and also needed cryogenic temperatures for the separation of argon and oxygen.
  • strontium exchanged zeolite X adsorbent was used as the packing material for the chromatographic column for the analysis of argon-oxygen mixture.
  • Strontium exchanged zeolite X particles having a size in the range of 30 - 100 mesh size were activated externally at a temperature in the range of 473 K - 673 K under an inert atmosphere or vacuum for 12 - 48 hrs.
  • the activated adsorbent is cooled to room temperature and then transferred suddenly to the column under moisture free conditions and this column is coiled into spiral form and then connected to the GC instrument (GC-7610, Chemito Technologies Pvt.
  • Another important embodiment of present invention is the dynamic adsorption data of oxygen from its gaseous mixture with argon in the oxygen selective adsorbent.
  • zeolite X spherical beads were exchanged with an aqueous solution of strontium salts as described above for zeolite X binderless pellets.
  • the completely strontium exchanged zeolite X beads were dried in a hot air oven for overnight and the dried oxygen selective adsorbent was filled in an adsorbent column having a dimension of 35 cm length and 1.9 cm diameter.
  • the adsorbent inside the column was activated at heating rate of 2 K/min to 623 K and the temperature was maintained for 12- 24 hrs.
  • the activated adsorbent is then cooled to the adsorption temperature, 303 K and feed containing oxygen and argon at particular concentration and feed flow rate passed through the adsorbent column to get the dynamic adsorption data of oxygen in strontium exchanged zeolite X.
  • the feed concentration and product concentration at the other end of adsorbent column is measured in a GC instrument (GC-7610, Chemito Technologies Pvt. Ltd., Nasik, India) equipped with a TCD detector (TCD 866) using the packed column mentioned above in the present invention.
  • the concentration profile of oxygen at the outlet of the adsorbent column is plotted against time and it is defined hereafter as the breakthrough curve of oxygen in the particular adsorbent.
  • Zeolite NaX powder was first pressed up to 5 tonnes force to make pellets using a hydraulic pelletizer. These pellets are then crushed and sieved to collect adsorbent particles in the range of 30 -100 mesh size and is named as NaX(Pe). Around 0.5 g of this NaX(Pe) particles were activated at 623 K under vacuum (5xlO "3 mm Hg) for 6 - 12 hrs. Equilibrium adsorption measurements of ultra high pure oxygen and argon gases in this adsorbent were carried out in a static volumetric adsorption system (Micormeritics, USA, Model ASAP 2010) at 288 K and 303 K.
  • the equilibrium adsorption isotherms of oxygen and argon in NaX(Pe) particles at 303 K are give in FIG. 1.
  • the equilibrium adsorption capacities of oxygen and argon were 2.96 cc/g and 2.75 cc/g respectively at 303 K and 760 mm Hg.
  • the equilibrium selectivities for oxygen over argon were 1.09, 1.03 and 1.08 respectively at 25 mm Hg, 100 mm Hg, 760 mm Hg pressure and 303 K.
  • the adsorbent sample thus prepared was named as SrX(Pe).
  • SrX(Pe) particles were activated at 623 K under vacuum (5x10 ⁇ 3 mm Hg) for 6 hrs.
  • Equilibrium adsorption measurements of ultra high pure oxygen and argon gases in this adsorbent were carried out in a static
  • FIG. 3 - FIG. 5 shows the chromatograr ⁇ of argon and oxygen at different concentrations in the gaseous mixture. There was a clear peak separation for argon and oxygen at different concentrations of argon-oxygen gaseous mixture with argon and oxygen retention times observed at 1.46 -1.5 and 1.95 - 2.20 minutes respectively.
  • zeolite NaX powder 20 g was treated with 0.1M aqueous solution of barium chloride at a solid to liquid ratio of 1:80 and the solids were filtered, washed with copious amount of distilled water until the filtrate is free from chloride ions, and dried at 353 K in a hot air oven for overnight.
  • the cation exchange was conducted at each time at a temperature of 353 K for 8 hrs until the total exchangeable sodium cations are replaced with barium cations.
  • the adsorbent sample thus prepared was named as BaX. Around 0.5 g of this BaX powder was activated at 623 K under vacuum (5xlO ⁇ 3 mm Hg) for 12 hrs.
  • zeolite NaX powder 20 g was treated with 0.1M aqueous solution of calcium chloride at a solid to liquid ratio of 1:80 and the solids were filtered, washed with copious amount of distilled water until the filtrate is free from chloride ions, and dried at 353 K in a hot air oven for overnight.
  • the cation exchange was conducted at each time at a temperature of 353 K for 8 hrs until the total exchangeable sodium cations are replaced with calcium cations.
  • The- adsorbent sample thus prepared was named as CaX. Around 0.5 g of this CaX powder was activated at 623 K under vacuum (5xlO "3 mm Hg) for 12 hrs.
  • zeolite NaY 0.5 g was activated at 623 K under vacuum (5xlO ⁇ 3 mm Hg) for 6 hrs.
  • Equilibrium adsorption measurements of ultra high pure oxygen and argon gases in this adsorbent were carried out in a static volumetric adsorption system at 288 K and 303 K.
  • the equilibrium adsorption capacities of oxygen and argon were 2.23 cc/g and 2.0 cc/g respectively at 303 K and 760 mm Hg.
  • zeolite NaX spherical beads 100 g were treated with 0.1M aqueous solution of strontium chloride at a solid to liquid ratio of 1:40 and the solids were filtered, washed with copious amount of distilled water until the filtrate is free from chloride ions, and dried at 353 K in a hot air oven for overnight. The cation exchange was conducted at each time at a temperature of 353 K for 4 8 hrs until the total exchangeable sodium cations are replaced with strontium cations.
  • the adsorbent sample thus prepared was named as SrX(G). Around 70 g of this sample is used for the breakthrough measurements of oxygen in SrX(G) adsorbent column. The adsorbent column was 35 cm long with 1.9 cm internal diameter. The adsorbent was activated at 623
  • Breakthrough measurement of oxygen in the adsorbent system described in Example 7 was conducted with a feed concentration of 90% oxygen and 10% argon on volume basis at a flow rate of 60 ml/min and the desorption of was carried out by passing pure argon at a flow rate of 60 ml/min. through the oxygen saturated adsorbent bed, counter- currently to the feed flow.
  • FIG.7 shows the adsorption and desorption curves of oxygen described above in this example.
  • Breakthrough measurement of oxygen in the adsorbent system described in Example 7 was conducted with a feed concentration of 50% oxygen and 50% argon on volume basis at a flow rate of 50 ml/min.
  • the concentration profile of oxygen with respect to time, at the outlet of the adsorbent column is shown in FIG. 8.
  • Breakthrough measurement of oxygen in the adsorbent system described in Example 7 was conducted with a feed concentration of 6.5% oxygen and 93.5% argon on volume basis at a flow rate of 107 ml/min.
  • the column pressure was 4 atm (absolute) during the adsorption measurements.
  • the concentration profile of oxygen with respect to time, at the outlet of the adsorbent column is shown in FIG. 9.
  • the starting temperature of all the oxygen breakthrough measurements was 303 K.
  • the breakthrough measurements of oxygen in SrX(G) adsorbent showed that strontium exchanged zeolite X can be used as a oxygen selective adsorbent for the separation of argon-oxygen for the production of argon, either from the crude argon stream coming from the cryogenic air separation plant, or from the product stream of oxygen PSA where the product contains around 5 % argon on volume basis along with the oxygen gas.

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Abstract

La présente invention concerne un procédé de préparation d’un adsorbant pour tamis moléculaire à base de zéolite destiné à une adsorption sélective de l’oxygène d’un mélange gazeux contenant de l’argon. L'invention concerne plus particulièrement un procédé de préparation d’un adsorbant, qui est plus sélectif pour l’oxygène d’un mélange gazeux contenant de l’oxygène et de l’argon, ainsi que des procédés utilisant cet adsorbant comme adsorbant sélectif de l’oxygène.
PCT/IN2009/000399 2008-11-07 2009-07-13 Procédé de préparation d’un adsorbant pour tamis moléculaire utile pour l'adsorption sélective de l’oxygène d’un mélange gazeux contenant de l’argon Ceased WO2010052736A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114130422A (zh) * 2021-11-29 2022-03-04 江西省杰夫环保科技有限公司 一种深度脱氧银x分子筛净化剂的制备方法
CN114261975A (zh) * 2021-11-12 2022-04-01 江苏中科敬远节能科技有限公司 一种连续逆流离子交换工艺生产高效银分子筛的方法
CN116396486A (zh) * 2023-01-04 2023-07-07 华南理工大学 优先吸附氩气的铝基金属有机骨架材料及其制法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US4744805A (en) * 1986-05-22 1988-05-17 Air Products And Chemicals, Inc. Selective adsorption process using an oxidized ion-exchanged dehydrated chabizite adsorbent
US6087289A (en) * 1997-03-10 2000-07-11 Indian Petrochemical Corporation Limited Process for the preparation of a molecular sieve adsorbent for selectively adsorbing oxygen from a gaseous mixture
WO2005039755A1 (fr) * 2003-10-27 2005-05-06 Council Of Scientific And Industrial Research Procede de preparation d'un adsorbant sous forme de tamis moleculaire pour l'adsorption selective de l'oxygene contenu dans l'air

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2882244A (en) * 1953-12-24 1959-04-14 Union Carbide Corp Molecular sieve adsorbents
US4744805A (en) * 1986-05-22 1988-05-17 Air Products And Chemicals, Inc. Selective adsorption process using an oxidized ion-exchanged dehydrated chabizite adsorbent
US6087289A (en) * 1997-03-10 2000-07-11 Indian Petrochemical Corporation Limited Process for the preparation of a molecular sieve adsorbent for selectively adsorbing oxygen from a gaseous mixture
WO2005039755A1 (fr) * 2003-10-27 2005-05-06 Council Of Scientific And Industrial Research Procede de preparation d'un adsorbant sous forme de tamis moleculaire pour l'adsorption selective de l'oxygene contenu dans l'air

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114261975A (zh) * 2021-11-12 2022-04-01 江苏中科敬远节能科技有限公司 一种连续逆流离子交换工艺生产高效银分子筛的方法
CN114261975B (zh) * 2021-11-12 2023-09-15 江苏中科敬远节能科技有限公司 一种连续逆流离子交换工艺生产高效银分子筛的方法
CN114130422A (zh) * 2021-11-29 2022-03-04 江西省杰夫环保科技有限公司 一种深度脱氧银x分子筛净化剂的制备方法
CN114130422B (zh) * 2021-11-29 2024-04-12 江西省杰夫环保科技有限公司 一种深度脱氧银x分子筛净化剂的制备方法
CN116396486A (zh) * 2023-01-04 2023-07-07 华南理工大学 优先吸附氩气的铝基金属有机骨架材料及其制法与应用
CN116396486B (zh) * 2023-01-04 2023-12-22 华南理工大学 优先吸附氩气的铝基金属有机骨架材料及其制法与应用

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