WO2005039755A1 - Process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air - Google Patents
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- WO2005039755A1 WO2005039755A1 PCT/IN2004/000280 IN2004000280W WO2005039755A1 WO 2005039755 A1 WO2005039755 A1 WO 2005039755A1 IN 2004000280 W IN2004000280 W IN 2004000280W WO 2005039755 A1 WO2005039755 A1 WO 2005039755A1
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- 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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/087—X-type faujasite
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- 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
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- 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
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
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- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
Definitions
- the present invention relates to a process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air.
- the present invention also relates to the use of rare earth exchanged zeolites as selective adsorbents for separation of gases having closely related physical properties. More particularly, the present invention relates to the preparation and use of adsorbent, which is selective towards oxygen, from a gaseous mixture of oxygen with argon.
- Background of the invention The use of adsorption techniques to separate a gaseous component from a gaseous stream was initially developed for the removal of carbon dioxide and water from air. Gas adsorption techniques are now employed in processes for the recovery of hydrogen from its mixture with hydrocarbons, and enrichment of oxygen from air.
- adsorbents include activated carbon, zeolite molecular sieves, silica gel and activated alumina.
- Carbon molecular sieves (CMS) which exhibit very narrow pore size distribution, facilitates separation of air to recover nitrogen has provided a secure and growing market for carbon molecular sieve.
- Adsorption processes for the separation of oxygen and argon from air are being increasingly used for commercial purposes for the last three decades. Oxygen requirements in sewage treatment, fermentation, cutting and welding, fish breeding, electric furnaces, pulp bleaching, glass blowing, medical purposes and in the steel industries particularly where the required oxygen purity is between 90 to 95% are being largely met by adsorption based pressure swing or vacuum swing processes.
- Argon is also used in welding, cutting, and spraying of metals, depending on the welding process, the noble gas is used pure, as a mixture, or in combination with oxygen, hydrogen, or carbon dioxide.
- Argon/argon-hydrogen mixtures (>5% H 2 ) are used as protective gases for plasma welding.
- argon There are many potential applications of argon and it is expected that this work will lead to increased consumption of argon in the future.
- Adsorption capacity of the adsorbent is defined as the amount in terms of volume or weight of the adsorbent.
- the adsorption selectivity of a component over the other is calculated as the ratio of the volumes of gas adsorbed at any given pressure and temperature.
- the adsorption selectivity of a component results from steric effect, i.e., when the adsorption isotherms of components of a gas mixture differ appreciably; kinetic effect, when the components have substantially different adsorption rates.
- Adsorption for oxygen and nitrogen production is being widely used and tremendous research effort is being directed to improve the adsorption processes for higher adsorption capacity and selectivity.
- Adsorbents affect separations by adsorbing one or more components of the mixture strongly than the others components present in the mixture.
- the various interactive forces involved in adsorption process are van der Waals interactions, acid-base interactions, hydrogen bond, electrostatic, chelation, and clathration. Therefore, adsorbents are appropriately modified to enhance the interactions between adsorbent and adsorbate molecules to improve adsorption capacity and selectivity.
- Zeolites which are crystalline inorganic porous materials having pores with molecular dimensions have largely been used for adsorption separation.
- Preparation of carbon molecular sieve is a multi-step process with utmost care at each state to get totally reproducible carbon molecular sieve. Additionally, the process is very high temperature process, which results into higher cost of the products.
- US Patent 5,081,097 (1992) to Sharma et al. discloses copper modified carbon molecular sieves for selective removal of oxygen from air. The sieve is prepared by pyrolysis of a mixture of a copper-containing material and polyfunctional alcohol to form a sorbent precursor. The sorbent precursor is then heated and reduced to produce a copper modified carbon molecular sieve. Pyrolysis is high temperature process making the whole process of preparation of the adsorbent an energy intensive process.
- US Patent 6,087,289 (2000) to Choudary et al. discloses a process for the preparation of a zeolite-based adsorbent containing cerium cations for the selective adsorption of oxygen from the gas mixture.
- Cerium exchange into zeolite is carried out under reflux conditions using aqueous solution of cerium salt at around 80°C for 4-8 hours and repeating the ion exchange process several times and separation of gases was studied by gas chromatography in very low-pressure range.
- the main drawbacks of this adsorbent are oxygen selectivity being obtained only in the low-pressure region. Additionally, adsorption was studied only by gas chromatography in limited pressure range. Thus higher pressure range adsorption data was not obtained.
- Chemcal vapour deposition is carried out by taking a requisite quantity of zeolite in a glass reactor, which is thermally activated at 450°C in situ under inert gas like nitrogen flow.
- the vapours of silicon alkoxide are continuously injected into inert gas stream, which carries the vapours to zeolite surface where alkoxide chemically reacts with silanol groups of the zeolite.
- sample is heated to 550°C in air for 4-6 hours after which it is brought down to ambient temperature and used for adsorption.
- argon is recovered from a gas stream comprising the same in admixture with oxygen and nitrogen, by a vacuum swing adsorption (VSA) process wherein the mixed gas is passed through an adsorbent bed having thermodynamic selectivity for adsorption of nitrogen and unabsorbed portion is then passed through a second adsorbent bed having kinetic selectivity for retaining oxygen. Both adsorbent beds are regenerated by vacuum desorption, applied to the first bed for a longer time period than that of the second bed.
- the mixed gas stream fed to the VSA unit may be that obtained from the crude argon column associated with a cryogenic air separation plant and waste gas from the VSA unit may be recycled to the main column of the cryogenic air separation plant, thus enhancing argon recovery.
- US Patent 4,817,392 (1989) to Agrawal et al. discloses a process for the production and recovery of an O 2 -lean argon stream from a gas mixture containing argon and oxygen.
- the argon-containing gas mixture is initially treated in a cryogenic separation unit to produce a crude argon stream having an argon concentration between 80-98%.
- the crude argon stream is then passed to a membrane based separation unit where it is separated to produce an O 2 -lean argon stream and an O 2 -rich stream.
- the O 2 -rich stream is recycled to the cryogenic separation unit and the Ar-lean oxygen stream is recovered as product or further purified.
- argon gas specially an argon gas stream obtained by cryogenically separating air, wherein the argon gas is heated and compressed, and then permeated through a solid electrolyte membrane selective to the permeation of oxygen over other components of the gas, and removing oxygen from the argon by selective permeation of oxygen through the membrane.
- the purified argon can then be distilled to remove other components such as nitrogen.
- a process is provided for producing a purified argon stream wherein oxygen and nitrogen are removed from crude bulk argon streams, particularly those produced by cryogenic, adsorptive or membrane separation of air.
- the process comprises separating a heated, compressed crude argon stream containing nitrogen and oxygen into an oxygen permeate stream and an oxygen- depleted argon stream by passing the compressed heated argon stream through a solid electrolyte membrane selective to the permeation of oxygen.
- the oxygen-depleted argon stream is then fed to a distillation column to separate nitrogen from the oxygen-depleted argon stream to form the purified argon stream and a nitrogen waste system.
- the main object of the present invention is to provide a process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air, which obviates, the drawbacks as detailed above.
- Still another object of the present invention is to provide an oxygen selective zeolite based adsorbent. Still another object of the present invention is to provide an adsorbent, which can be prepared by the exchanging rare earth cations especially cerium, europium and gadolinium in ziolite X. Yet another object of the present invention is to provide oxygen selective adsorbent by a simple post-systhesis modification of zeolite X. Yet another object of the present invention is to provide an adsorbent, which can be regenerated by desorption of oxygen by controlling equillibrium adsorption pressure.
- Yet another object of the present invention is to provide an adsorbent, which is selective towards oxygen over argon with high selectivity and can be commercially for the separation and purification of argon.
- the present invention provides a process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air, by exchanging powder and pellet form of sodium zeolite X, with an aqueous solution of rare earth cations such as cerium, europium and gadolinium, at elevated temperature.
- the dry zeolite X containing 20 to 95% rare earth cations of the total exchangeable sodium cations, after activation at high temperature and vacuum were subjected to adsorption studies for oxygen, nitrogen and argon using a static volumetric system of an adsorption equipment supplied by Micromeritics Corporation USA (Model ASAP 2010). Adsorption capacities and selectivity for rare earth exchanged zeolite for oxygen, nitrogen and argon was measured at 15°C and in the pressure range of 0.5 to 760 mmHg. From these data adsorption isotherm were plotted and pure component selectivity of gases were calculated.
- This invention provides a process to prepare zeolite adsorbent having selectivity for oxygen over nitrogen and argon.
- the present invention provides a process for preparing a molecular sieve adsorbent for selective adsorption of oxygen from air, the process comprising (i) exchanging zeolite X in powder or pellet form with water-soluble salt of a rare earth metal selected from the group consisting of cerium, europium, gadolinium and any mixture thereof; (ii) filtering the mixture, washing the powder or pellet with hot distilled water till it is free from anions to obtain an exchanged zeolite; (iii) drying the exchanged zeolite; (iv) and activating the exchanged zeolite.
- zeolite X in powder form having 100% crystallinity and spherical pellet forms can be used for the preparation of the surface modified molecular sieve adsorbent.
- Na cations of zeolite were exchanged with salts or rare earth ions 10 to 100 equivalent percentage (Cerium Europium and Gadolinium) are loaded using any water-soluble salts of chloride nitrate and acetate.
- the cation exchange can be carried at a temperature in the range of 30°C to 90°C for a period in the range of 4 to 8 hours.
- the cation exchange can be carried out at a cation concentration in the range of 0.01 to 0.1 M solution.
- the exchanged zeolite may be dried in a temperature range of 20°C to 80°C in air or under vacuum conditions.
- the exchanged zeolite may be activated in the temperature range of 350 to 450°C for a period in the range of 3-6 hours followed by cooling under inert or vacuum condition.
- Figure 2 represents the adsorption isotherms of nitrogen, argon and oxygen at 15°C on the cerium exchanged zeolite X pellets.
- Figure 3 represents the adsorption isotherms of nitrogen, argon and oxygen at 15°C on the europium exchanged zeolite Z pellets.
- Figure 4 represents the adsorption isotherms of nitrogen, argon and oxygen at 15°C on the gadolunium exchanged zeolite X pellets.
- the present invention provides a process for the preparation of an oxygen selective adsorbent, which has oxygen adsorption selectivity over nitrogen and argon.
- this adsorbent displays higher interaction with oxygen compared to nitrogen and argon as observed from heats adsorption values determined I the in Henry region.
- Zeolites which are microporous crystalline aluminosilicates, are finding increased applications as adsorbents for separating mixtures of compounds having closely related molecular properties.
- the attributes which makes the zeolites attractive for separation include, an unusually high thermal and hydrothermal stability, uniform pore structure, easy pore aperture modification and substantial adsorption capacity even at low adsorbate pressures.
- zeohtes can be produced synthetically under relatively moderate hydrothermal conditions.
- the zeolite NaX powder and pellet [Na 8 6(AIO )s6(SiO 2 ) ⁇ o6wH 2 O] was used as the starting material. X-ray diffraction data showed that the starting material was highly crystalline.
- a known amount of the zeolite NaX powder and pellet [Na 86 ( IO 2 )s 6 (SiO 2 ) 1 o6 H2O] was refluxed with 0.01 M rare earth (Ce, Eu and Gd) acetate and chloride solution taken in 2 litre round bottomed flask with zeolite X (powder or pellet) to rare earth solution ratio 1:80 at 80-120°C for 4h.
- Oxygen, nitrogen and argon adsorption at 15°C was measured using a static volumentric system (Micromeritics, USA. ASAP 2010), after activating the sample at 350°C to 450°C under vacuum for 4-8 hours as described in the examples.
- Addition of the adsorbate gas was made at volumes required to achieve a targeted set of pressures ranging from 100 to 760 mmHg. A minimum equilibrium interval of 5 seconds was used to determine equilibrium for each measurement point.
- the pure component selectivity of one gas over other (A and B) was determined by the equation, where N A and NB are the volumes of gas A and B adsorbed at equilibrium pressure P and temperature T.
- the important inventive steps involved in the present invention are that the molecular sieve adsorbent, formation of oxygen selective species inside the zeolite cavities (i) by exchanging with lanthanide aqueous solution and in addition to cation exchange by forming non-stoichiometric oxide of cerium/europium/gadolinium which can selectively; interact with oxygen molecules (ii) the process lies in providing a new technique, in addition to conventional cation exchange, of introducing sorbate specific metal oxide in the micropores of the zeolites for developing new adsorbents.
- the non-stochiometric oxides of these rare earths like cerium and europium can react with oxygen in a reversible manner and reversibly changes the oxidation state thus acting as chemisorption-assisted adsorption. High heats of adsorption values observed also are indicative chemisorption type interactions with oxygen molecule.
- the adsorbtive capacity of the catalyst was verified evaluated by adsorbing nitrogen, oxygen and argon gases on exchanged zeolites having 99.9% purity at 15°C and in the pressure range of 0.5 to 800 mmHg and then calculating the adsorption selectivity of gases at 15 C and 100 and 760-mmHg pressures.
- EXAMPLE-1 1.0 gm of zeolite NaX pellet, [Na 2 O)86(Al2 ⁇ 3 )86.(Si ⁇ 2 ) 10 6.wH 2 O], was activated at 350 C temperature under vacuum at 10 " mmHg and adsorption measurements were carried out for N 2 ,O 2 , Ar having 99.9% purity at 15°C using volumetric system (Micromeritics ASAP 2010C) operating at 760 mmHg pressure with equilibrium interval of 5 seconds.
- Adsorption capacity for N 2 ,O 2 and Ar is 9.74 cc/g, 3.31 cc/g and 3.29 cc/g respectively at 15°C temperature and 760-mmHg pressures.
- Selectivity for nitrogen over oxygen is 2.9; selectivity for nitrogen over argon is 2.96, and selectivity for oxygen over argon is 1.0 at 15°C at 760- mmHg pressures.
- EXAMPLE-2 25. Og of the molecular sieve NaX pellet was exchanged with 0.301M Cerium acetate solutions in the ratio 1:80 and refluxed at 80°C for 4 hours. The hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C).
- the Cerium content in dry zeolite amount is 25% of the total replaceable sodium cations.
- This ziolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.17 gm.
- the adsorption measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 2.4cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 1.0, selectivity for nitrogen over oxygen is 3.3 and nitrogen over argon is 3.3 at the 100-mmHg pressure.
- EXAMPLE-3 25.
- the adsorption capacity for oxygen is 3.7 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 8.0, selectivity for nitrogen over oxygen is 0.4 and nitrogen over argon is 3.5 at the 100-mmHg pressure.
- EXAMPLE-4 25 Og of the molecular sieve NaX pellet was exchanged with 0.01M Cerium chloride solutions in the ratio 1:80 and refluxed at 80°C for 4 hours. The hot solution was filtered, washed with hot distilled water, until the washings are free from chloride ions and then dried in air at room temperature (28°C). The cerium content in dry zeolite amount is 28% of the total replaceable sodium cations.
- This zeolite was activated at 3500C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.58 gm.
- the adsorption measurement was carried out at 15°C temperature 760-mmHg pressures.
- the adsorption measurement was carried out at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 3.0, selectivity for nitrogen over oxygen is 1.3 and nitrogen over argon is 4.0 at the 100-mmHg pressure.
- the hot solution was filtered, washed with hot distilled water, until the washings are free from chloride ions and then dried in air at room temperature (28°C).
- the cerium content in dry zeolite amount is 93% of the total replaceable sodium cations.
- This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.53 gm.
- the adso ⁇ tion measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 3.1 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 3.5, selectivity for nitrogen over oxygen is 1.4 and nitrogen over argon is 5.0 at the 100-mmHg pressure.
- EXMAPLE-6 25 Og of the molecular sieve NaX powder was exchanged with 0.014M Cerium acetate solutions in the ratio 1:80 and refluxed at 80°C for 4 hours. The hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C). The cerium content in dry zeolite amount is 74% of the total replaceable sodium cations.
- This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.13 gm.
- the adso ⁇ tion capacity for oxygen is 4.6 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 4.0, selectivity for nitrogen over oxygen is 1.1 and nitrogen over argon is 4.2 at the 100-mmHg pressure.
- the hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C).
- the cerium content in dry zeolite amount is 20% of the total replaceable sodium cations.
- This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.22 gm.
- the adso ⁇ tion measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adso ⁇ tion capacity for oxygen is 2.2 cc/g at 15°C temperature and 760mn ⁇ Hg and selectivity for oxygen over argon is 1.5, selectivity for nitrogen over oxygen is 2.2 and nitrogen over argon is 3.2 at the 100-mmHg pressure.
- EXMAPLE-8 25 Og of the molecular sieve NaX pellet was exchanged with 0.1M Cerium acetate solutions in the ratio 1 :80 and refluxed at 80°C for 4 hours. The hot solution was filtered washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C). The cerium content in dry zeolite amount is 30% of the total replaceable sodium cations.
- This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.15 gm.
- the adso ⁇ tion measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 3.2 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 2.0, selectivity for nitrogen over oxygen is 2.4 and nitrogen over argon is 3.8 at the 100-mmHg pressure.
- EXAMPLE-9 25.0g of the molecular sieve NaX pellet was exchanged with 0.01M Europium acetate solutions in the ratio 1:80 and refluxed at 80°C for 4 hours.
- the hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C).
- the europium content in dry zeolite amount is 52% of the total replaceable sodium cations.
- This zeolite was activated at 3500C temperature under vacuum (1 "3 mmHg) and the weight of sample after activation was 0.59 gm.
- the adso ⁇ tion measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 2.3 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 1.7, selectivity for nitrogen over oxygen is 1.1 and nitrogen over argon is 2.7 at the 100-mmHg pressure.
- EXMAPLE-10 25 Og of the molecular sieve NaX pellet was exchanged with 0.01M Europium acetate solutions in the ratio 1:80 and refluxed at 80°C for 4 hours. The hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C). The europium content in dry zeolite amount is 67% of the total replaceable sodium cations. This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.52 gm. The adso ⁇ tion measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 2.6 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 2.3, selectivity for nitrogen over oxygen is 1.3 and nitrogen over argon is 3.1 at the 100-mmHg pressure.
- EXMAPLE-11 25 Og of the molecular sieve NaX pellet was exchanged with 0.01M Gadolinium acetate solutions in the ratio 1:80 and refluxed at 80°C for 4 hours. The hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C). The gadolinium content in dry zeolite amount is 82% of the total replaceable sodium cations.
- This zeolite was activated at 35°C temperature under vacuum (10 "3 mmHg) and the weight of sample after activation was 0.59 gm.
- the adsorption measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adso ⁇ tion capacity for oxygen is 3.2 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 4.0, selectivity for nitrogen over oxygen is 1.3 and nitrogen over argon is 5.0 at the 100-mmHg pressure.
- the hot solution was filtered, washed with hot distilled water, until the washings are free from acetate ions and then dried in air at room temperature (28°C).
- the gadolinium content in dry zeolite amount is 88% of the total replaceable sodium cations.
- This zeolite was activated at 350°C temperature under vacuum (10 "3 mmHg) and weight of sample after activation was 0.66 gm.
- the adsorption measurement was carried out at 15°C temperature and 760-mmHg pressures.
- the adsorption capacity for oxygen is 2.8 cc/g at 15°C temperature and 760mmHg and selectivity for oxygen over argon is 2.0, selectivity for nitrogen over oxygen is 3.0 and nitrogen over argon is 6.0 at the 100-mmHg pressure.
- the adsorbent, prepared by the modification of zeolite X shows oxygen selectivity over nitrogen argon.
- a simple exchange with aqueous solution of rare earth cations is used for the preparation of the adsorbent.
- the exchange is carried out at 80°C and atmospheric pressure.
- the adsorbent is very easy to handle.
- the adsorbent shows oxygen/argon selectivity of nearly 8 in the low-pressure range studied.
- the adsorbent is useful in the commercial separation and purification of oxygen and argon from its mixture with nitrogen.
- the adsorbent is useful for the chromatographic separation of oxygen nitrogen and argon.
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WO2010052736A1 (en) * | 2008-11-07 | 2010-05-14 | Council Of Scientific & Industrial Research | A process for the preparation of molecular sieve adsorbent useful for the selective adsorption of oxygen from its gaseous mixture with argon |
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US7592284B2 (en) * | 2006-03-13 | 2009-09-22 | Honeywell International Inc. | Preparation of ion exchanged polymer bound nitrogen adsorbent |
CN101433817B (en) * | 2007-11-15 | 2012-05-09 | 中国石油化工股份有限公司 | Desulphurization sorbent |
CN102838127A (en) * | 2012-09-28 | 2012-12-26 | 珠海市吉林大学无机合成与制备化学重点实验室 | Primary crystallization hydrothermal preparation method of A-type and X-type molecular sieves containing pure Na ions |
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US20050090380A1 (en) | 2005-04-28 |
KR100803771B1 (en) | 2008-02-15 |
CN1874839A (en) | 2006-12-06 |
JP2007512119A (en) | 2007-05-17 |
EP1677907A1 (en) | 2006-07-12 |
US7319082B2 (en) | 2008-01-15 |
KR20060103439A (en) | 2006-09-29 |
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