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WO2010109477A2 - Procédé de préparation d'un adsorbant de tamis moléculaire pour l'adsorption sélective taille/forme du dioxyde de carbone à partir de son mélange gazeux avec l'azote - Google Patents

Procédé de préparation d'un adsorbant de tamis moléculaire pour l'adsorption sélective taille/forme du dioxyde de carbone à partir de son mélange gazeux avec l'azote Download PDF

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WO2010109477A2
WO2010109477A2 PCT/IN2010/000027 IN2010000027W WO2010109477A2 WO 2010109477 A2 WO2010109477 A2 WO 2010109477A2 IN 2010000027 W IN2010000027 W IN 2010000027W WO 2010109477 A2 WO2010109477 A2 WO 2010109477A2
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carbon dioxide
zeolite
adsorbent
adsorption
nitrogen
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PCT/IN2010/000027
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WO2010109477A3 (fr
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Raksh Vir Jasra
Rajesh Shantilal Somani
Beena Tyagi
Sunil Adavanal Peter
Renjith Sasimohanan Pillai
Ulka Sharma
Prakash Dulhadinomal Hirani
Rabishanker Mukhopadhyay
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Council Of Scientific & Industrial Research
Ntpc Ltd
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Publication of WO2010109477A2 publication Critical patent/WO2010109477A2/fr
Publication of WO2010109477A3 publication Critical patent/WO2010109477A3/fr

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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
    • 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
    • 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
    • B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • 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
    • B01J20/3092—Packing of a container, e.g. packing a cartridge or column
    • 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
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • B01D53/0462—Temperature 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This invention relates to a process for the preparation of molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen, at ambient to elevated temperature. More specifically, the present invention provides a process for the preparation of a molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen especially from the flue gas; such an adsorbent is prepared by the surface modification of a zeolite either by simple ion exchange process or by liquid phase alkoxide deposition at external surface of the zeolite.
  • CO 2 emissions due to human activity come from the fossil fuels used for generating electricity, with each power plant capable of emitting several million tones of CO 2 annually. These fossil fuels provides >80 % energy needs all over the world and will continue to do so for the foreseeable future.
  • Typical CO 2 emission from coal fired power plant is 800 kg CO 2 /MWh of electricity produced (IEA Greenhouse Gas R&D Programme, 2003, "Greenhouse gas emissions from power stations", Available on web at http://www.ieagreen.org.uk/emis4.htm).
  • a variety of other industrial processes also emit large amounts of CO 2 from each plant, for example oil refineries, cement works, and iron and steel production.
  • flue gas from a coal fired thermal power plant contains around 15% CO 2 , 81 % N 2 and the rest contains other gases such as oxygen, SO x , NO X _ etc. on dry basis.
  • the flue gas from a natural gas fired thermal power plant contains around 4% CO 2 , 81% N 2 and around 15% O 2 and some minor quantities of SO x , NO X _ etc. on dry basis.
  • the ultimate objective of the CO 2 capture is the stabilization of greenhouse gas concentrations in the atmosphere at a level that prevents dangerous anthropogenic interference with the climate system.
  • Carbon dioxide present in any gas stream can be removed either by chemically absorbing in a solution of an alkali or amine, or by physically adsorbing on an adsorbent such as activated carbon or zeolite.
  • the methods of physical adsorption of carbon dioxide using a zeolite adsorbent include a pressure swing adsorption (PSA) process, pressure temperature swing (PTSA) process, or vacuum swing adsorption (VSA) process.
  • PSA pressure swing adsorption
  • PTSA pressure temperature swing
  • VSA vacuum swing adsorption
  • adsorption o f carbon dioxide by a zeolite adsorbent is effected at high pressure and low temperature and desorption thereof from the zeolite is effected at lower pressure and/or at a higher temperature than the adsorption conditions.
  • the zeolite may be purged with a gas which is less adsorbed than carbon dioxide.
  • the adsorbent is a combination of sodium form of a low-silica faujasite, having a residual content of potassium ions less than about 8.0 percent (equiv.), a low content of crystalline and amorphous admixtures and crystal sizes generally within the range of 1- 4 ⁇ m, and a binder.
  • the process for the adsorbent preparation comprises of low silica faujasite synthesis, sodium-potassium ion exchange, blending and granulation.
  • the zeolite adsorbent is ion-exchanged with lithium and/or sodium, and is prepared by a process including a step of contacting with a caustic solution a calcined product of a mixture of a low-silica type X zeolite and kaolin clay whereby the kaolin clay is converted to a low- silica type X zeolite.
  • the method of the present invention is claimed to be employed for purification of air when cryogenic separation of air is conducted, or for purification of natural gas.
  • this patent does not disclose adsorption data for adsorptive separation of carbon dioxide from a gaseous mixture wherein carbon dioxide content is higher; about 10 -15%, as in flue gas from power plant.
  • chemical vapor deposition technique was used for controlling the pore opening size of the zeolites by the deposition of silicon alkoxide (Niwa et al, JCS Faraday Trans. I, 1984, 80, 3135-3145; Niwa et al., J. Phys. Chem., 1986, 90, 6233- 6237; Ohayon et al., Applied Catalysis A- General, 2001, 217, 241-251).
  • Chemical vapor deposition is carried out by taking a requisite quantity of zeolite in a glass reactor, which is thermally activated at 723 K in situ under an inert gas like nitrogen flow.
  • the vapors of silicon alkoxide are continuously injected into inert gas stream, which carries the vapors to zeolite surface where alkoxide reacts chemically with silanol groups of the zeolite.
  • the sample is heated to 823 K in air for 4-6 hrs after which it is brought down to ambient temperature and used for adsorption.
  • the disadvantages of the chemical vapor deposition are, (i) non-uniform coating of alkoxide which leads to the non-uniform closure of the pore mouth of zeolite, (ii) the process has to be carried out at higher temperature in order to vaporize the alkoxide, (iii) the deposition of the alkoxide requires to be done at a slow rate for better diffusion and (iv) the method is expensive and a commercial level at higher scale will be difficult.
  • the present invention provides a process for the preparation of a molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its mixture with nitrogen by the modification of. the pore mouth opening of the zeolite- A adsorbent.
  • the novelty of the present invention lies in adjusting the desired surface properties of zeolite based adsorbents ' by using ion exchange or liquid phase alkoxide deposition for making it suitable to selectively remove carbon dioxide from its mixture with nitrogen.
  • the main object of the present invention is to provide a process for the preparation of a molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen.
  • Another object of the present invention is to provide a carbon dioxide size/shape selective adsorbent by the modification of the pore mouth opening of the zeolite -A adsorbent.
  • Another object of the present invention is to provide an adsorbent which selectively excludes larger molecules like nitrogen from its gaseous mixture with carbon dioxide during adsorption process.
  • Yet another object of the present invention is to modify the pore mouth opening of the zeolite A by simple ion exchange process or by liquid phase alkoxide deposition at external surface of the zeolite A for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen.
  • Still further object of the present invention is to use the size/shape selective adsorbent for the adsorption of carbon dioxide in a pressure swing adsorption (PSA) process, vacuum pressure swing adsorption (VPSA) process, or pressure temperature swing adsorption (PTSA) process, for the - removal of carbon dioxide from its gaseous mixture, - especially from flue gases.
  • PSA pressure swing adsorption
  • VPSA vacuum pressure swing adsorption
  • PTSA pressure temperature swing adsorption
  • the present invention provides a process for the preparation of molecular sieve adsorbent for the size/shape selective adsorption- of carbon dioxide from its gaseous mixture with nitrogen, at ambient to elevated temperature wherein the said process comprising providing A-type zeolite as an adsorbent either pore engineered by the treatment of tetra alkyl alkoxide or exchanged with potassium ions up to a desired degree of total exchangeable sodium ions to preferentially adsorb carbon dioxide to obtain a pore engineered adsorbent having unit cell composition Na 12 [(Al 2 O 2 ) 12 (SiO 2 ) 12+ J 27H 2 O wherein the value of 'x' varies from 0.001 to 1.0 and potassium exchanged adsorbent containing 15 to 50% potassium ions exchanged with sodium ions present in A-type zeolite, followed by removing carbon dioxide from the adsorbent by pressure swing or applying vacuum or by heating the adsorbent above the adsorption temperature
  • the tetra alkyl alkoxide used is tetra ethyl ortho silicate.
  • the tetra alkyl ortho silicate deposited on zeolite surface is converted into silica by calcination in air at a temperature between 773 to 923 K for 3 to 6 hrs.
  • the alkoxide deposited zeolite is having very high selectivity for carbon dioxide over nitrogen in the range of 314 - 36 for a partial pressure in the range of 100 - 760 mm Hg at 303 K.
  • the potassium exchanged zeolite adsorbent completely exclude nitrogen from its gaseous mixture with carbon dioxide and shows infinite equilibrium selectivity for carbon dioxide over nitrogen.
  • the adsorption temperatures are in the range of 298 - 353 K.
  • the said size/shape selective adsorbent for the selective adsorption of carbon dioxide from its gaseous mixture with nitrogen especially from the flue gas can be used in a vacuum swing adsorption process; pressure swing adsorption process; pressure vacuum swing adsorption process; or pressure temperature swing adsorption process.
  • the present invention is the size selective exclusion of nitrogen from its gaseous mixture with carbon dioxide during adsorption process.
  • shaped products were also subjected to the dynamic adsorption studies in an adsorption breakthrough setup.
  • FIG. 1 is a diagram of equilibrium adsorption isotherms of carbon dioxide and nitrogen at 303 K, in the adsorbent described in Example - 1.
  • FIG. 2 is a diagram of equilibrium adsorption isotherms of carbon dioxide and nitrogen at 303 K, in the adsorbent described in Example - 9.
  • FIG. 3 is a diagram of breakthrough curve of carbon dioxide in the adsorbent described in Example - 11 at 303 K.
  • FIG. 4 is a diagram of breakthrough curve of carbon dioxide in the adsorbent described in Example - 12 at 303 K.
  • the present invention provides a process for the preparation of a molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen especially from the flue gas at ambient to elevated temperature.
  • 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 ⁇ 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.
  • zeolites can be produced synthetically under relatively moderate hydrothermal conditions.
  • a known amount of zeolite NaA powder is treated with an aqueous solution of potassium salt at 353 K for 2-4 hrs.
  • the amount of the potassium salt was taken in such manner that the concentration of K + ions in the aqueous solution was theoretical equivalent of the particular value for the percentage exchange of sodium ions present in NaA.
  • the amount of K + ions in the potassium salt taken was contained just equivalent for this 20% of sodium ions.
  • the cation exchanged samples were filtered, washed and dried in a hot air oven at 353 K for overnight, and the samples were named as KA-20 and KA-30 for 20% and 30% of the sodium ions theoretically exchanged with potassium ions.
  • Carbon dioxide and nitrogen equilibrium adsorption studies in these samples were carried out at 303 K and 333 K in a static volumetric adsorption system (Micromeritics, 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).
  • zeolite NaA powder was used as the starting material.
  • a known amount of zeolite NaA powder was activated at 673 K under an inert atmosphere in order to remove the adsorbed water and then it was cooled to room temperature.
  • This activated zeolite sample was treated with a solution having known amount of tetra alkyl ortho silicate in a dry solvent at a solid to liquid ratio of 1:10 for 4-8 hrs at room temperature, the sample was filtered, dried and the tetra alkyl ortho " silicate species deposited on the zeolite surface was converted into silica by calcination of zeolite at 823 K.
  • the sample was named as NaA-IO(TEOS) which means that 10 volume/ weight percentage of tetra ethyl ortho silicate is treated with zeolite NaA sample.
  • Carbon dioxide and nitrogen equilibrium adsorption studies in these samples were carried out at 303 K and 333 K in a static volumetric adsorption system (Micromeritics, 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.
  • V A and V 8 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.
  • Another important embodiment of present invention is the dynamic adsorption data of carbon dioxide from its gaseous mixture with nitrogen in the carbon dioxide selective adsorbent.
  • potassium exchanged samples at particular cation exchange levels are prepared by treating the NaA spherical granules with an aqueous solution of potassium salt sufficient for the particular percent exchange of sodium ions ' in NaA granules with potassium ions.
  • Liquid phase ' alkoxide deposited samples were shaped into 3 mm extrudate pellets for the dynamic adsorption studies.
  • NaA-IO(TEOS) adsorbent pellets To make 100 parts by weight of NaA-IO(TEOS) adsorbent pellets, 80 parts by weight of NaA-IO(TEOS) powder and 20 parts by weight of bentonite clay were incorporated and mixed together for 15 minutes and then a required amount of water was added, followed by kneading for 1.5 hours. The kneaded product was extruded by using a hand-operated, extrusion machine to give a shaped product in the form of extrudates having an average diameter of 3 mm. Extrudates were dried at 80° C overnight and broken in to pieces of about 3 mm length manually.
  • the dried extrudates were calcined at 873 K for 3 hours under air a muffle furnace to give a shaped product containing zeolite NaA-IO(TEOS).
  • the adsorbent samples prepared as per the above mentioned procedure were filled in an adsorbent column having a dimension of 35 cm length and 1.9 cm diameter and activated in situ in the adsorbent column at heating rate of 2 K/min to 623 K and the temperature was maintained for 12- 24 hrs under N 2 flow for 8 - 24 hrs and then cooled to the breakthrough measurement temperatures, 303 K and 348 K respectively.
  • the feed gas consist of around 15% CO 2 and 85% N 2 , in which N 2 acts as a carrier gas for the dynamic adsorption measurements, is passed through the adsorbent column at a flow rate of around 120 ml/min.
  • the feed concentration and the product concentration at the other end of adsorbent column are measured in a GC instrument (GC-7610, Chemito Technologies Pvt. Ltd., Nasik, India) equipped with a TCD detector (TCD 866) using a Porapaq packed column with H 2 gas as a carrier gas at a flow rate of 40ml/min.
  • GC-7610 Chemito Technologies Pvt. Ltd., Nasik, India
  • TCD 866 TCD detector
  • Around 1.5 ml of the gas samples were taken in a gas tight syringe and analyzed in the- GC.
  • the concentration profile of carbon dioxide at the outlet of the adsorbent column is plotted against time and it is defined hereafter as the breakthrough curve of carbon dioxide in the particular
  • zeolite NaA 0.5 g was activated at 623 K under vacuum (5xlO ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 348 K.
  • the equilibrium adsorption isotherms of carbon dioxide and nitrogen in NaA powder at 303 K are given in FIG. 1.
  • the heats of adsorption, adsorption capacity and selectivity of CO 2 and N 2 in NaA are given in Table 1.
  • zeolite NaA 10.0 g is treated with 0.1 molar aqueous solution of potassium chloride at 353 K with a solid to liquid ratio of 1:80 for 4 hrs and then filtered, washed with distilled water and dried at 353 K in a hot air oven. The cation exchange was conducted for 4 times in order to replace the sodium ions present in the zeolite completely with potassium ions. A known amount of the sample was activated at 623 K under vacuum (5 ⁇ lO ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • zeolite NaA powder 10.0 g is treated with around 0.82 g of potassium chloride in 400 ml of distilled water, at 353 K for 4 hrs and then filtered, washed with distilled water and dried at 353 K in a hot air oven.
  • the sample is named as KA-20 and a known amount of the sample was activated at 623 K under vacuum (5 ⁇ l0 ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon, dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K. Nitrogen gas did not adsorbed and the adsorbent sample is having almost infinite selectivity carbon dioxide over nitrogen.
  • the heats of adsorption, adsorption capacity and selectivity of CO 2 and N 2 in KA-20 are given in Table 1,
  • zeolite NaA powder 10.0 g is treated with around 1.23 g of potassium chloride in 400 ml of distilled water, at 353 K for 4 hrs and then filtered, washed with distilled water and dried at 353 K in a hot air oven.
  • the sample is named as KA-30 and a known amount of the sample was activated at 623 K under vacuum (5x10 ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K. Nitrogen gas did not adsorbed and the adsorbent sample is having almost infinite selectivity carbon dioxide over nitrogen.
  • the heats of adsorption, adsorption capacity and selectivity of CO 2 and N 2 in KA-30 are given in Table 1.
  • 10.0 g of zeolite NaA powder is treated with around 0.41 g of potassium chloride in 400 ml of distilled water, at 353 K for 4 hrs and then filtered, washed with distilled water and dried at 353 K in a hot air oven.
  • a known amount of the sample was activated at 623 K under vacuum (5 ⁇ l0 ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption 'system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K.
  • the equilibrium adsorption capacities for nitrogen and carbon dioxide were 4.9 cc /gram and 83.6 cc /gram respectively at 303 K and 1 atm.
  • 10.0 g of zeolite NaA powder is treated with around 0.205 g of potassium chloride in 400 ml of distilled water, at 353 K for 4 hrs and then filtered, washed with distilled water and dried at 353 K in a hot air oven.
  • a known amount of the sample was activated at 623 K under vacuum (5 ⁇ l0 ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K.
  • the equilibrium adsorption capacities for nitrogen and carbon dioxide were 6.2 cc /gram and 85.3 cc /gram' respectively at "303 K and 1 atm.
  • zeolite NaA powder 10 g, of zeolite NaA powder was activated at 673 K under nitrogen atmosphere in order to remove the adsorbed water and then it was cooled to room temperature.
  • This activated zeolite sample was treated . with 0.25 ml of tetra ethyl ortho silicate (TEOS) in 100 ml dry toluene for 8 hrs at room temperature, the sample was filtered, dried and the tetra ethyl ortho silicate species deposited on the zeolite surface was converted into silica by calcination of zeolite at 823 K for 5 hours.
  • TEOS tetra ethyl ortho silicate
  • the sample is named as NaA-2.5(TEOS) and a known amount of the sample was activated at 623 K under vacuum (5xlO ⁇ 3 mm Hg) for 12 hrs and then cooled ' to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K.
  • the equilibrium adsorption capacities for nitrogen and carbon dioxide were 6.8 cc /gram and 84.2 cc /gram respectively at 303 K and 1 atm.
  • zeolite NaA powder 10 g was activated at 673 K under nitrogen atmosphere in order to remove the adsorbed water and then it was cooled to room temperature.
  • This activated zeolite sample was treated with 0.5 ml of tetra ethyl ortho silicate (TEOS) in 100 ml dry toluene for 8 hrs at room temperature, the sample was filtered, dried and the tetra ethyl ortho silicate species deposited on the zeolite surface was converted into silica by calcination of zeolite at 823 K for 5 hours.
  • TEOS tetra ethyl ortho silicate
  • the sample is named as NaA ⁇ 5(TEOS) and a known amount of the sample was activated at 623 K under vacuum (5xlO "3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this activated adsorbent were carried out in a static volumetric adsorption system (iMicromeritics, USA, Model ASAP 2010) at 303 K and 333 K.
  • the equilibrium adsorption capacities for nitrogen and carbon dioxide were 4.2 cc /gram and 81.7cc /gram respectively at 303 K and 1 atm.
  • zeolite NaA powder 50 g was activated at 673 K under nitrogen atmosphere in order to remove the adsorbed water and then it was cooled to room temperature.
  • This activated zeolite sample was treated with 5 ml of tetra ethyl ortho silicate (TEOS) in 500 ml dry toluene for 8 hrs at room temperature, the sample was filtered, dried and the tetra ethyl orthc silicate species deposited on the zeolite surface was converted into silica by calcination of zeolite at 823 K for 5 hours.
  • TEOS tetra ethyl ortho silicate
  • the sample is named as NaA-IO(TEOS) and a known amount of the sample was activated at 623 K under vacuum (5 ⁇ lO ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • Equilibrium adsorption measurements of pure carbon dioxide and nitrogen gases in this actiyated adsorbent were carried out in a static volumetric adsorption system (Micromeritics, USA, Model ASAP 2010) at 303 K and 333 K.
  • the equilibrium adsorption isotherms of carbon dioxide and nitrogen in NaA-IO(TEOS) powder at 303 K are given in FIG. 2.
  • the heats of adsorption, adsorption capacity and selectivity of CO 2 and N 2 in NaA-IO(TEOS) are given in Table 1.
  • adsorbent NaA spherical granules were filled in an adsorbent column having a dimension of 35 cm length and 1.9 cm diameter and activated in situ in the adsorbent column at heating rate of 2 K/min to 623 K and the temperature was maintained for 24 hrs under N 2 flow and then cooled to the breakthrough measurement temperatures, 303 K and 348 K respectively.
  • the feed gas consist of around 15% CO 2 and 85% N 2 , in which N 2 acts as a carrier gas for the dynamic adsorption measurements, is passed through the adsorbent column at a flow rate of around 120 ml/mm.
  • Desorption of CO 2 was carried out by passing N 2 at a flow rate of 102 ml/min, counter-currently to the feed flow.
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in NaA granules were found to be 51.9 cc /gram and 32.4 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120ml/min. .
  • the feed gas consist of around 15% CO 2 and 85% N 2 , in which N 2 acts as a carrier gas for the dynamic adsorption measurements, is passed through the adsorbent column at a flow rate of around 120 ml/min.
  • Desorption of CO 2 was carried out by passing N 2 ' at a flow rate of 102 ml/min, counter-currently to the feed flow.
  • the .column pressure was 1 atm (absolute) during adsorption and desorption.
  • the CO 2 breakthrough in KA-20(G) granules at 303 K is shown in FIG. 3.
  • the adsorbent mentioned in Example 9 was shaped into 3 mm extrudate pellets for the dynamic adsorption studies.
  • To make 100 parts by weight of NaA-IO(TEOS) adsorbent pellets 80 parts by weight of NaA-IO(TEOS) powder and 20 parts by weight of bentonite clay were incorporated and mixed together for 15 minutes and then a required amount of water was added, followed by kneading for 1.5 hours.
  • the kneaded product was extruded by using a hand-operated, extrusion machine to give a shaped product in the form of extrudates having an average diameter of 3 mm. Extrudates were dried at 80° C overnight and broken in to pieces of about 3 mm length manually.
  • the dried extrudates were calcined at 873 K for 3 hours under air a muffle furnace to give a shaped product containing zeolite NaA-IO(TEOS).
  • adsorbent sample was filled in an adsorbent column having a dimension of 35 cm length and 1.9 cm diameter and activated in situ in the adsorbent column at heating rate of 2 K/min to 623 K and the temperature was maintained for 24 hrs under N 2 flow for 8 - 24 hrs and then cooled to the breakthrough measurement temperatures, 303 K and 348 K respectively.
  • the feed gas consist of around 15% CO 2 and 85% N 2 , in which N 2 acts as a carrier gas for the dynamic adsorption measurements, is passed through the adsorbent column at a flow rate of around 120 ml/min.
  • Desorption of CO 2 was carried out by passing N 2 at a flow rate of 102 ml/min, counter-currently, to the feed flow.
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the CO 2 breakthrough in NaA-IO(TEOS) pellets at 303 K is shown in FIG. 4.
  • the breakthrough capacity of CO 2 in NaA-IO(TEOS) adsorbent pellets were found to be 44.7 ml/g and 25.0 ml/g at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120ml/min.
  • the size/shape selective adsorbent for the selective adsorption of carbon dioxide from its gaseous mixture with nitrogen, can be prepared simply by the ion exchange of zeolite or by the liquid phase alkoxide deposition on the external surface of the zeolite A.
  • the alkoxide deposition is uniform on the zeolite surface.

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Abstract

Cette invention concerne un procédé d'adsorption sélective taille/forme du dioxyde de carbone à partir de son mélange gazeux avec l'azote, en particulier, comme dans le gaz de combustion à température ambiante ou à température élevée avec un adsorbant comprenant une zéolite de type A fabriquée avec des pores par traitement d'alcoxyde de tétraalkyle ou par échange avec des ions potassium jusqu'à obtention du degré souhaité d'échange du total des ions sodium pour adsorber préférentiellement le dioxyde de carbone. L'adsorbant fabriqué avec des pores renferme une composition cellulaire unitaire de Na12[(A12O2)12(SiO2)12+x] 27 H2O, la valeur de ´x´ variant entre 0,001 et 1,0, et l'adsorbant à échange de potassium devant contenir au moins 15 % à 50 % d'ions potassium échangés avec les ions sodium de la zéolite de type A. Le dioxyde de carbone est ensuite éliminé de l'adsorbant par modulation de pression ou par application de vide, ou alors par chauffage de l'adsorbant au-delà de la température d'adsorption et récupération du dioxyde de carbone comme un courant de produit.
PCT/IN2010/000027 2009-03-27 2010-01-18 Procédé de préparation d'un adsorbant de tamis moléculaire pour l'adsorption sélective taille/forme du dioxyde de carbone à partir de son mélange gazeux avec l'azote WO2010109477A2 (fr)

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WO2014045302A3 (fr) * 2012-09-11 2014-07-03 Reliance Industries Limited Zéolite modifiée en surface pour sécher de fluides frigorigènes
WO2018148022A1 (fr) 2017-02-13 2018-08-16 Praxair Technology, Inc. Adsorbants accordables
WO2020009968A1 (fr) 2018-07-02 2020-01-09 Praxair Technology, Inc. Adsorbants accordables à large cristal
US10792610B2 (en) 2017-04-07 2020-10-06 Praxair Technology, Inc. Process for generating higher VPSA product pressure
CN114408941A (zh) * 2022-01-13 2022-04-29 润和催化剂股份有限公司 一种逆流交换制备锂x分子筛的工业方法、及其制备的锂x分子筛
CN117160429A (zh) * 2023-10-11 2023-12-05 中国科学院过程工程研究所 一种疏水性核壳结构co2吸附剂及其制备方法与应用

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014045302A3 (fr) * 2012-09-11 2014-07-03 Reliance Industries Limited Zéolite modifiée en surface pour sécher de fluides frigorigènes
WO2018148022A1 (fr) 2017-02-13 2018-08-16 Praxair Technology, Inc. Adsorbants accordables
US10717035B2 (en) 2017-02-13 2020-07-21 Praxair Technology, Inc. Tunable adsorbents
US11529582B2 (en) 2017-02-13 2022-12-20 Praxair Technology, Inc. Tunable adsorbents
US10792610B2 (en) 2017-04-07 2020-10-06 Praxair Technology, Inc. Process for generating higher VPSA product pressure
WO2020009968A1 (fr) 2018-07-02 2020-01-09 Praxair Technology, Inc. Adsorbants accordables à large cristal
CN112334225A (zh) * 2018-07-02 2021-02-05 普莱克斯技术有限公司 大晶体可调吸附剂
CN112334225B (zh) * 2018-07-02 2023-09-29 普莱克斯技术有限公司 大晶体可调吸附剂
US12076707B2 (en) 2018-07-02 2024-09-03 Praxair Technology, Inc. Large crystal tunable adsorbents
CN114408941A (zh) * 2022-01-13 2022-04-29 润和催化剂股份有限公司 一种逆流交换制备锂x分子筛的工业方法、及其制备的锂x分子筛
CN117160429A (zh) * 2023-10-11 2023-12-05 中国科学院过程工程研究所 一种疏水性核壳结构co2吸附剂及其制备方法与应用
CN117160429B (zh) * 2023-10-11 2024-05-03 中国科学院过程工程研究所 一种疏水性核壳结构co2吸附剂及其制备方法与应用

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