WO2010113169A1 - Procede de preparation et d'utilisation de zeolite du type pentasil pour l'adsorption selective du dioxyde de carbone a partir de gaz de fumee - Google Patents

Procede de preparation et d'utilisation de zeolite du type pentasil pour l'adsorption selective du dioxyde de carbone a partir de gaz de fumee Download PDF

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WO2010113169A1
WO2010113169A1 PCT/IN2009/000753 IN2009000753W WO2010113169A1 WO 2010113169 A1 WO2010113169 A1 WO 2010113169A1 IN 2009000753 W IN2009000753 W IN 2009000753W WO 2010113169 A1 WO2010113169 A1 WO 2010113169A1
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carbon dioxide
adsorbent
adsorption
zsm
range
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PCT/IN2009/000753
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Raksh Vir Jasra
Rajesh Shantilal Somani
Beena Tyagi
Sunil Adavanal Peter
Renjith Sasimohanan Pillai
Ulka Sharma
Prakash Dulhadinomal Hirani
Rabishankar Mukhopadhyay
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Council Of Scientific & Industrial Research
Ntpc Limited
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3014—Kneading
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/34—Regenerating or reactivating
    • B01J20/3491—Regenerating or reactivating by pressure treatment
    • 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
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • 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

  • the present invention relates to a process for the preparation and use of Pentasil type zeolite for the selective adsorption of carbon dioxide from flue gas by selective adsorption of carbon dioxide from a gaseous mixture containing carbon dioxide in the range of 3 to 20 % by volume as in the case of power plant flue gas.
  • the present invention relates to the use of pentasil type zeolites, especially ZSM-5 having SiO 2 / Al 2 O 3 ratio in the range of 25- 900, as a carbon dioxide selective adsorbent for the separation of carbon dioxide from the flue gas of thermal power plants.
  • 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 of 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 use of a treatment cycle involve the steps of a) passing the contaminated gas flow into ari adsorption region comprising the adsorbent bed, the adsorbent bed providing for the separation of the contaminant or contaminants by adsorption, b) desorbing the adsorbed CO 2 by establishing a pressure gradient and gradually reducing the pressure in the adsorption region to recover the CO 2 via the inlet into the adsorption region, c) increasing the pressure in the adsorption region by introducing a pure gas stream via the outlet of the adsorption region.
  • the adsorption is carried out at pressures of between 1 and 10 bar and desorption is carried out at pressures of between 0.1 and 2 bar. It does not disclose the adsorption selectivity between carbon dioxide and nitrogen and also does not provide the breakthrough data of carbon dioxide and nitrogen ad/desorption.
  • 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 specific parameters 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. It 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.
  • 5,917,136 (Gaffeney et al., 1999) wherein they claim a pressure swing process for absorbing CO 2 from a gaseous mixture containing CO 2 by introducing the gaseous mixture at a first pressure into a reactor containing a modified alumina adsorbent maintained at a temperature ranging from 100 0 C and 500 0 C to adsorb CO 2 to provide a CO 2 laden alumina adsorbent and a CO 2 depleted gaseous mixture and the CO 2 laden alumina adsorbent is regenerated by purging with a weakly adsorbing gas at lower pressure.
  • this process needs very high temperature for the CO 2 adsorption.
  • the novelty of the present invention lies in finding out a suitable pentasil type zeolite for selective adsorption of CO 2 from flue gas and the adsorbent have (l) high selectivity and adsorption capacity for carbon dioxide at high temperature; (2) adequate adsorption/desorption kinetics for carbon dioxide at operating conditions; (3) stable adsorption capacity of carbon dioxide after repeated adsorption/desorption cycles; (4) adequate mechanical strength of adsorbent particles after cyclic exposure to high pressure streams.
  • the main object of the present invention is to provide a molecular sieve adsorbent for the selective adsorption and recovery of carbon dioxide from gas streams at ambient to elevated temperatures, especially from the flue gases which contains 3 - 15 % of carbon dioxide on dry volume basis.
  • Another object of the present invention is to provide a molecular sieve adsorbent of pentasil type zeolite, especially ZSM-5 zeolite with different SiO 2 /Al 2 O 3 ratio in the range of 25-900 and forming the adsorbent in shaped product for the selective adsorption of carbon dioxide from its gaseous mixture and the recovery of carbon dioxide thereof.
  • Yet another object of the present invention is the use of a carbon dioxide selective adsorbent in 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 relates to a process for the preparation and use of Pentasil type zeolite molecular sieves for the selective adsorption of carbon dioxide from flue gas generated from thermal power plant, at ambient to elevated temperatures; wherein the said process comprising the steps of- a. preparing a mixture of Pentasil type zeolite powder ZSM-5 with a silica/alumina ratio ranging between 25-900 and clay at a ratio of 4:1 with water, followed by kneading of the mixture for 1-3 hrs; b. shaping the kneaded product as obtained in step (a) by using a hand operated extruder in the form of extrudates having a diameter in the range of 1.5-4.5mm; c.
  • step (b) drying said extrudates as obtained in step (b) at a temperature between 333 - 373 K for 6 to 12 hrs to obtain the adsorbent bodies; d. breaking the dried extrudates in to pieces of about 3-6 mm length, e. subjecting the adsorbent bodies as obtained in step (d) to calcination at a temperature in the range of 723 - 873 K for a period in the range of 2 to 5 hrs;
  • step (e) activating the adsorbent bodies as obtained in step (e) in the adsorbent column at a temperature between 523 - 623 K for 5-10hrs followed by adsorption by passing the feed gas mixture Cl 5% by volume CO 2 + ⁇ 85% by volume N 2 ) through the activated adsorbent column at a flow rate in the range of 100-120ml/min and pressure in the range of 1-1.1 atmosphere.
  • the said molecular sieve adsorbent is of pentasil type zeolite comprising mordenite, ZSM-5 and zeolite beta.
  • the said clay used is bentonite clay.
  • the said clay is present in an amount of 5 to 20% by weight.
  • the adsorbent bodies are activated at a temperature in the range of 823 to 873K for a time period in the range of 6-7hrs .
  • the said zeolite having higher linearity for carbon dioxide adsorption isotherms is ZSM-5 with a silica/ alumina ratio above 100.
  • the column pressure during adsorption and desorption is 1 atm.
  • the said zeolite having favorable carbon dioxide desorption kinetics is ZSM-5 with a silica/alumina ratio above 100.
  • the adsorption temperatures are in the range of 293-423 K.
  • the adsorbent is having linearity for the carbon dioxide adsorption isotherms and favorable carbon dioxide desorption kinetics for easy desorption of adsorbed carbon dioxide from the adsorbent.
  • the processes for the commercial utilization of the said carbon dioxide selective molecular sieve adsorbent are vacuum swing adsorption process; pressure swing adsorption process; vacuum pressure swing adsorption process; or pressure temperature swing adsorption process.
  • FIG. 1 is a diagram of equilibrium adsorption isotherms of CO 2 and N 2 in ZSM ⁇ 5(25) at 303 K.
  • FIG. 2 is a diagram of equilibrium adsorption isotherms of CO 2 and N 2 in ZSM-5(40) at 303 K.
  • FIG. 3 is a diagram of equilibrium adsorption isotherms of CO 2 and N 2 in ZSM ⁇ 5(l00) at 303 K.
  • FIG. 4 is a diagram of equilibrium adsorption isotherms of CO 2 and N 2 in ZSM-5(400) at 303 K.
  • FIG. 5 is a diagram of equilibrium adsorption isotherms of CO 2 and N 2 in ZSM ⁇ 5(900) at 303 K.
  • FIG. 6 is a diagram of breakthrough curve of CO 2 in ZSM ⁇ 5(25) adsorbent pellets at 303 K as described in Example- 9.
  • FIG. 7 is a diagram of breakthrough curve of CO 2 in ZSM ⁇ 5(40) adsorbent pellets at 303 K as described in Example- 10.
  • FIG. 8 is a diagram of breakthrough curve of CO 2 in ZSM ⁇ 5(100) adsorbent pellets at 303 K as described in Example- 11.
  • FIG. 9 is a diagram of breakthrough curve of CO 2 in ZSM ⁇ 5(400) adsorbent pellets at 303 K as described in Example 12.
  • FIG. 10 is a diagram of breakthrough curve of CO 2 in ZSM-5(900) adsorbent pellets at 303 K as described in Example- 13.
  • the present invention provides a process for the preparation of a molecular sieve adsorbent for the selective adsorption of carbon dioxide from its gaseous mixture with nitrogen.
  • 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 main interactions of the adsorbate molecules in a zeolite structure are through lattice oxygen atoms and extra framework cations.
  • the molecular sieve adsorbent of interest in the present invention was of pentasil type zeolite, especially ZSM-5 with a silica/alumina ratio in the range of 25 - 900.
  • the exchangeable extra-framework cations in the ZSM-5 zeolite were sodium ions.
  • Zeolite ZSM-5 in powder form with different silica/ alumina ratios of 25, 40, 100, 400, and 900, hereafter named as ZSM-5(25), ZSM-5(40), ZSM-5(100), ZSM-5(400) and ZSM- 5(900) respectively, were procured from Zeochem AG, Switzerland and used as such for the equilibrium adsorption measurements of carbon dioxide and nitrogen.
  • the ZSM-5 zeolite was shaped into 3 mm extrudate pellets.
  • To make 100 parts by weight of ZSM-5 adsorbent pellets 80 parts by weight of ZSM-5 powder and 20 parts by weight of bentonite clay were incorporated and mixed together for 15 minutes and then 15 - 25 % by weight 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 353 K 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 ZSM-5.
  • Carbon dioxide and nitrogen adsorption at 303 K and 333 K were studied 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 850 mmHg.
  • 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 ( ⁇ O.IK) by circulating water from a constant temperature bath (Julabo F25, Germany).
  • the pure component selectivity of two gases A and B was calculated by using the equation,
  • V A and V B 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.
  • the ZSM-5 pellets 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 ral/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 FVt. 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 40 ml/min.
  • GC-7610 Chemito Technologies FVt. 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 ZSM ⁇ 5(40) 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 333 K.
  • the equilibrium adsorption isotherms of carbon dioxide and nitrogen in ZSM ⁇ 5(40) powder at 303 K and 333 K are given in FIG. 2.
  • the heat of adsorption, adsorption capacity and selectivity Of CO 2 and N 2 in ZSM-5(40) are given in Table 1.
  • zeolite ZSM ⁇ 5(100) 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 333 K.
  • the equilibrium adsorption isotherms of carbon dioxide and nitrogen in ZSM-5(100) powder at 303 K and 333 K are given in FIG. 3.
  • the heat of adsorption, adsorption capacity and selectivity of CO 2 and N 2 in ZSM ⁇ 5(100) are given in Table 1.
  • zeolite ZSM-5(400) 0.5 g 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 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 isotherms of carbon dioxide and nitrogen in ZSM ⁇ 5(400) powder at 303 K and 333 K are given in FIG. 4.
  • the heat of adsorption, adsorption •capacity and selectivity of CO 2 and N 2 in ZSM-5(400) are given in Table 1.
  • zeolite ZSM-5(900) 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 333
  • zeolite mordenite ZM-060 (procured from Zeocat, France) was activated at 623 K under vacuum (5 ⁇ lCT 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 capacity for CO 2 and N 2 in ZM-060 were 70 cc /gram and 16 cc /gram respectively at 303 K.
  • zeolite mordenite ZM-510 (procured from Zeocat, France), was activated at 623 K under vacuum (5xl0 ⁇ 3 mm Hg) for 12 hrs and then cooled to room temperature.
  • zeolite beta, Na j3 ⁇ 25 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 capacity for CO 2 and N 2 in Na )3 -25 were 49.6 cc /gram and 4.7 cc /gram respectively at 303 K.
  • Example 1 80 g of the adsorbent mentioned in Example 1 was mixed thoroughly with 20 g of bentonite clay 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, extruder to give a shaped product in the form of extrudates having an average diameter of 3 mm.
  • Extrudates were dried at 353 K for 16 hours 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 ZSM ⁇ 5(25).
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in ZSM ⁇ 5(25) adsorbent pellets were found to be 25.6 cc /gram and 17.2 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120 ml/min.
  • Example 2 80 g of the adsorbent mentioned in Example 2 was mixed thoroughly with 20 g of bentonite clay 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, extruder to give a shaped product in the form of extrudates having an average diameter of 3 mm.
  • Extrudates were dried at 353 K for 16 hours 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 ZSM ⁇ 5(40).
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in ZSM-5(40) adsorbent pellets were found to be 23.5 cc /gram and 14.8 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120 ml/min.
  • Example 3 80 g of the adsorbent mentioned in Example 3 was mixed thoroughly with 20 g of bentonite clay 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, extruder to give a shaped product in the form of extrudates having an average diameter of 3 mm.
  • Extrudates were dried at 353 K for 16 hours 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 ZSM ⁇ 5(100).
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in ZSM-5(100) adsorbent pellets were found to be 12.1 cc /gram and 6.3 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120 ml/min.
  • Example 4 80 g of the adsorbent mentioned in Example 4 was mixed thoroughly with 20 g of bentonite clay 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, extruder to give a shaped product in the form of extrudates having an average diameter of 3 mm.
  • Extrudates were dried at 353 K for 16 hours 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 ZSM ⁇ 5(400).
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in ZSM-5(400) adsorbent pellets were found to be 8.1 cc /gram and 4 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120 ml/min.
  • Example 5 80 g of the adsorbent mentioned in Example 5 was mixed thoroughly with 20 g of bentonite clay 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, extruder to give a shaped product in the form of extrudates having an average diameter of 3 mm. Extrudates were dried at 353 K for 16 hours 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 ZSM ⁇ 5(900).
  • the column pressure was 1 atm (absolute) during adsorption and desorption.
  • the breakthrough capacity of CO 2 in ZSM ⁇ 5(900) adsorbent pellets were found to be 7.6 cc /gram and 4 cc /gram at temperatures 303 K and 348K respectively and at a total feed gas flow of around 120 ml/min.
  • the adsorbent which is having good adsorption capacity as well as desorption kinetics for CO 2 , is good for the removal of CO 2 from the power plant flue gas.

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Abstract

L'invention concerne un procédé de préparation et d'utilisation de cribles moléculaires de zéolite du type pentasil pour l'adsorption du dioxyde carbone à partir de mélange gazeux contenant du dioxyde de carbone dans la plage de 3 à 20% par volume comme dans le cas de gaz de fumée d'une centrale électrique. Plus précisément, l'invention concerne l'utilisation de zéolites du type pentasil comprenant de la mordenite, la zéolite bêta et ZSM-5, le rapport SiO2ZAl2O3 étant de 25-900 à la température dans la plage de 293à 423K et des pressions ambiantes. La capacité d'adsorption d'équilibre le plus élevé pour CO2 est de 51,5 cc/g et la capacité de percée la plus élevée pour CO2 de 25,6 cc/g à 303K à un écoulement gazeux d'alimentation de boulettes adsorbantes d'environ 120 ml/min dans ZSM-5(25).
PCT/IN2009/000753 2009-03-31 2009-12-30 Procede de preparation et d'utilisation de zeolite du type pentasil pour l'adsorption selective du dioxyde de carbone a partir de gaz de fumee WO2010113169A1 (fr)

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Cited By (3)

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CN113385141A (zh) * 2021-06-23 2021-09-14 浙江大学 一种通过施用zsm-5分子筛提高植物栽培设施co2浓度和农作物生长的方法
CN114455585A (zh) * 2022-02-16 2022-05-10 青海师范大学 一种吸附空气中二氧化碳的方法
CN114849653A (zh) * 2022-05-12 2022-08-05 上海交通大学 高效捕集二氧化碳的胺改性多孔分子筛及制备方法和应用

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113385141A (zh) * 2021-06-23 2021-09-14 浙江大学 一种通过施用zsm-5分子筛提高植物栽培设施co2浓度和农作物生长的方法
CN113385141B (zh) * 2021-06-23 2022-05-31 浙江大学 一种通过施用zsm-5分子筛提高植物栽培设施co2浓度和农作物生长的方法
CN114455585A (zh) * 2022-02-16 2022-05-10 青海师范大学 一种吸附空气中二氧化碳的方法
CN114455585B (zh) * 2022-02-16 2024-01-16 青海师范大学 一种吸附空气中二氧化碳的方法
CN114849653A (zh) * 2022-05-12 2022-08-05 上海交通大学 高效捕集二氧化碳的胺改性多孔分子筛及制备方法和应用

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