WO2014191213A1 - Procédé de séparation de dioxyde de carbone à partir d'un courant de gaz, en particulier, d'un courant de gaz de combustion et procédé de préparation de sulfate de potassium non purifié - Google Patents

Procédé de séparation de dioxyde de carbone à partir d'un courant de gaz, en particulier, d'un courant de gaz de combustion et procédé de préparation de sulfate de potassium non purifié Download PDF

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Publication number
WO2014191213A1
WO2014191213A1 PCT/EP2014/059943 EP2014059943W WO2014191213A1 WO 2014191213 A1 WO2014191213 A1 WO 2014191213A1 EP 2014059943 W EP2014059943 W EP 2014059943W WO 2014191213 A1 WO2014191213 A1 WO 2014191213A1
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WO
WIPO (PCT)
Prior art keywords
potassium sulfate
separation unit
carbon dioxide
washing
detergent
Prior art date
Application number
PCT/EP2014/059943
Other languages
German (de)
English (en)
Inventor
Ansgar Kursawe
Markus Kinzl
Rüdiger Schneider
Ralph Joh
Original Assignee
Siemens Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2014191213A1 publication Critical patent/WO2014191213A1/fr

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Classifications

    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/608—Sulfates
    • 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
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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 invention relates to a method for separating carbon dioxide from a gas stream, in particular from a flue gas stream. Furthermore, the invention relates to a method for the treatment of contaminated potassium sulfate.
  • the flue gas after combustion is brought into contact with a suitable washing medium, with gaseous carbon dioxide contained in the flue gas being dissolved in the washing medium or being absorbed in a chemical sense.
  • the exhaust gas freed of carbon dioxide is finally released into the atmosphere.
  • the loaded with carbon dioxide wash medium can be regenerated by desorption of the absorbed carbon dioxide and again for the absorption of Carbon dioxide can be used from the flue gas.
  • Common washing media are based on primary, secondary or tertiary amines and show good selectivity and high capacity for carbon dioxide.
  • the washing medium In addition to carbon dioxide, which can be effectively removed from the flue gas by means of the amine-containing wash media, pollutants such as solid particles, sulfur oxides (S0 X ) and nitrogen oxides (N0 X ) are also introduced into the C0 2 separation process by the flue gas. Accordingly, the washing medium must be prepared after the separation of the carbon dioxide. For this purpose, the washing medium is cleaned, for example in the context of a so-called SO x recycling process of interfering sulfur oxides. In the SO x recycling process, sulfur oxides are usually precipitated in the washing medium by lowering the temperature and changing the concentration in the washing medium as potassium sulfate (K 2 S0 4 ). The potassium balance is compensated by adding potassium hydroxide (KOH). The potassium sulphate obtained through the SO x recycling process can be used as a fertilizer component, for the production of building materials such as plasterboard, as well as in specialty chemicals. However, the requirements for the purity of the potassium sulfate are correspondingly high.
  • potassium sulfate in the fertilizer sector, but also in chemistry and in the building materials industry require at least partial drying and purification of the crude product obtained in the course of the reprocessing process.
  • the permitted residual moisture in potassium sulfate ie the proportion of water and impurities, depends both on the respective re-use and on the recycler. Particularly stringent requirements are made for use as a special chemical or in high-quality fertilizers.
  • the values for the permitted residual moisture are sometimes in the range below 0.5% by weight. In order to ensure a wide applicability of the potassium sulfate, this must be further treated beyond the actual SO x recycling process.
  • the residual moisture of potassium sulfate in the solid-liquid separation is reduced as far as possible with the aid of a centrifuge.
  • the contaminated crude product may have a residual moisture of up to 10 wt .-% even after this treatment.
  • This residual moisture contains not only water but also parts of the
  • Washing medium which is obtained in the crystallization of potassium sulfate as the mother liquor. This is lost to the deposition process, so that the capacity of the washing medium due to the loss of the active component, so the amino acid salt decreases.
  • a second object of the invention is to provide a process which permits the recovery of potassium sulfate with regeneration. Winning of adhering mother liquor with a comparison with common methods improved product quality allows.
  • the first object of the invention is achieved by a method for separating carbon dioxide from a gas stream, in particular from a flue gas stream, in which the gas stream is brought into contact with a washing medium in an absorber of a separation device under deposition of carbon dioxide contained in the gas stream, which with Carbon dioxide laden scrubbing medium is fed to a desorber of the separator for releasing the carbon dioxide, the scrubbing medium freed from carbon dioxide is fed to a treatment stage, in which sulfur oxides contained in the scrubbing medium are precipitated as potassium sulfate, and the precipitated potassium sulfate to obtain purified potassium sulfate a separation unit is supplied, in which the potassium sulfate is separated from the washing medium.
  • the precipitated potassium sulfate in the separation unit is also subjected to a washing process.
  • the invention takes account of the fact that potassium sulphate, previously obtained in the context of a carbon dioxide deposition process, can not sufficiently meet the sometimes stringent requirements for further use due to impurities contained therein.
  • One of the most important criteria in the evaluation of the quality of the potassium sulfate in this case represent impurities by the washing medium or adhering to the precipitate mother liquor, as well as impurities caused by nitrosamines formed in the washing medium.
  • the concentration of the impurities contained in the potassium sulfate can be reduced following the precipitation of the solid by a solid-liquid separation.
  • the remaining in the potassium sulfate content of impurities and mother liquor - especially in the interstices and pores of the solid - but after such a work-up step is not sufficiently low to the recovered Potassium sulfate for a wide range of applications to make accessible.
  • the invention recognizes that the desired removal of adhering mother liquor and thus a reduction of impurities contained in the potassium sulfate can be achieved if the potassium sulfate precipitated in a separation unit is subjected to an additional work-up step.
  • the potassium sulfate precipitated from the washing medium is separated from the washing medium by means of a separating unit and at the same time subjected to a washing process in the separating unit.
  • the known work-up step of the solid-liquid separation for the removal of adhering mother liquor and the impurities contained is supplemented by an additional treatment step, namely the washing of the potassium sulfate.
  • the separation of the precipitated potassium sulfate as well as the washing process take place at the same time in a common separation unit.
  • the separation unit thus offers the possibility to implement the desired purification and treatment of the potassium sulfate in only one system component.
  • an additional processing step for the potassium sulfate - the washing process - in an already used plant component - the separation unit - are integrated.
  • the purification of the potassium sulfate by the integration of the washing process in the SO x recycling process can be implemented cost-saving without the use of additional equipment necessary.
  • the potassium sulfate obtained by means of the process can be used as valuable material and, thanks to the combined work-up steps, is also suitable for use fertilizer, to which it was previously inaccessible due to the purity requirements.
  • the solid-liquid separation particularly removes the mother liquor adhering to the surface of the potassium sulfate.
  • the solid-liquid separation preferably subsequent washing process of potassium sulfate in the separation unit at the same time contained in the pores and interstices of the solid mother liquor, the corresponding impurities as well as a possible residual portion of the washing medium.
  • the concentrations of interfering minor components, such as amino acid salts, nitrosamines and heavy metals can be reduced by a factor of 5-10 by the washing process.
  • no or only a negligible portion of undesired impurities are contained.
  • the precipitated potassium sulfate is centrifuged in the separation unit in a separation zone.
  • a centrifuge By means of a centrifuge, an effective separation of a large part of the mother liquor adhering to the solid can be achieved by centrifuging.
  • a continuously operating centrifuge is used. In such a centrifuge, the sample, so the contaminated potassium sulfate, the centrifuge is continuously fed while a rotor rotates at a predetermined speed. As the sample passes through the rotor, the separation of potassium sulfate from the mother liquor takes place
  • Centrifugation takes place.
  • the potassium sulfate and the separated mother liquor can be removed separately from the centrifuge.
  • a so-called batch centrifuge can be used in which the separation of the washing medium from the potassium sulfate takes place batchwise.
  • a sample vessel filled with suspension is placed in a sample vessel in a rotor and after centrifuging the potassium sulfate taken separately in the sample vessel and the separated mother liquor.
  • the washing process preferably takes place as displacement washing in a washing zone within the separating unit.
  • an inserted detergent is pressed into a filter cake or on the surface of the filter cake.
  • the detergent penetrates into the filter cake, whereby the existing in the interstices and the pores residual moisture, as in the present case the mother liquor with the impurities contained, is largely displaced.
  • a large part of the adhering mother liquor is graft-like replaced by the detergent.
  • the potassium sulfate flows from the separation zone of the separation unit into its washing zone.
  • the washing zone is thus arranged in the flow direction behind the separation zone.
  • the mother liquor adhering to the particle surface can first be thrown off and finally the mother liquor remaining in the wash zone or the impurities contained can be removed from the interstices and the pores.
  • a continuous centrifuge thus enters in the separation unit by centrifuging pre-purified potassium sulfate in the washing zone, in which before the outlet of potassium sulfate further purification takes place.
  • the detergent used for the washing process is metered into the washing zone via a spray connection.
  • the spray connection can in this case, for example, as a
  • Spray lance be formed and is suitably such arranged on the separation unit that allows accurate metering of the amount of detergent used in the washing zone of the separation unit.
  • a condensate stream discharged at the desorber serves as a source of the added detergent.
  • the detergent can be added fresh.
  • a detergent added to the corresponding amount of detergent at the desorber discharged again can be avoided.
  • water is used as the detergent.
  • the secondary components present in the mother liquor can be effectively dissolved by water, while the solubility of potassium sulfate in water is negligible for the process.
  • the detergent is used in a mass ratio of potassium sulfate between 0.5: 1 and 1: 1.
  • the water solubility of the potassium sulfate at the process temperature prevailing in the separation unit of preferably 10-15 ° C is less than 10 wt .-%.
  • precipitated potassium sulfate particles are separated in the crystallization step prior to entering the separation unit in a crystallizer of their particle size.
  • the crystallizer is part of the treatment stage.
  • the necessary conditions for the separation by means of a separation unit and in particular by means of a centrifuge are created.
  • a suspension containing the number of coarse particles required for separation by means of a centrifuge can be made available in the crystallizer.
  • the suspension is removed from the crystallizer and fed to the separation unit for removal of the mother liquor adhering to the potassium sulfate together with impurities.
  • the separation unit is operated at temperatures in a range between 10 ° C and 15 ° C.
  • temperatures in a temperature range between 10 ° C and 15 ° C usually also prevail in a crystallizer upstream of the separation unit, which can be used as part of the treatment stage. Temperature control of the potassium sulphate suspension to be treated before it enters the separation unit can thus ideally be dispensed with.
  • the detergent flows after passing through the washing zone in the separator for carbon dioxide.
  • the amount of detergent that flows to the separating device from the washing zone in this case is low based on the amount of detergent contained in the overall process.
  • the dilution of the washing medium by the amount of detergent supplied to the process is thus negligible.
  • the inflow of the detergent to the deposition process is preferably carried out with the mother liquor separated from the potassium sulfate.
  • the mother liquor containing about 30 wt .-% amino acid salt By recycling the mother liquor containing about 30 wt .-% amino acid salt, the loss of active component of the washing medium compared to a simple centrifuging can be significantly reduced.
  • the detergent, based on the potassium sulfate is preferably used in a mass ratio of between 0.5: 1 and 1: 1, the amount of detergent added, based on the amount of detergent present in the overall process, is negligibly small.
  • the residual moisture remaining in the purified potassium sulfate is removed by drying following the washing process.
  • the residual moisture, which after the displacement washing consists in particular of water, can be removed.
  • the potassium sulfate obtained can finally be recycled.
  • the second object of the invention is achieved by a process for the treatment of contaminated potassium sulfate, in which the contaminated potassium sulfate separated to obtain purified potassium sulfate by means of a separation unit of a washing medium and is subjected to a washing process in the separation unit at the same time.
  • This process treats contaminated potassium sulfate to meet stringent requirements, especially in the fertilizer sector and / or when used in structural and specialty chemicals.
  • the precipitated potassium sulfate is preferably centrifuged in a separation zone of the separation unit.
  • washing process takes place as displacement washing in a washing zone within the separation unit, since mother liquor can also be removed from the potassium sulfate by means of displacement washing in pores and interspaces.
  • a detergent is used for the washing process, which is metered via a spray connection in the separation unit.
  • Water is particularly suitable as washing agent, since water dissolves the impurities and secondary components contained in the washing medium and / or the mother liquor.
  • the washed potassium sulphate on the other hand, only dissolves in water to a limited extent, depending on the process temperature.
  • the detergent is used in a mass ratio of potassium sulfate between 0.5: 1 and 1: 1, since in this area the proportion of the dissolving potassium sulfate is particularly low.
  • the separation unit is operated at temperatures in a range between 10 ° C and 15 ° C, since at these temperatures, the solubility of the potassium sulfate in the detergent is particularly low.
  • potassium sulfate particles contained in the washing medium are in a separator before entering the separation unit
  • Crystallizer here is preferably part of a treatment stage used for the preparation of the potassium sulfate. From the crystallizer, a suspension is withdrawn which contains the number of coarse particles required for separation by means of a centrifuge. If the process for the treatment of contaminated potassium sulfate is part of a process for separating carbon dioxide from a gas stream, it is particularly advantageous if the detergent after passing through the washing zone in a separator for carbon dioxide, ie in the deposition process for carbon dioxide flows , The amount of detergent flowing to the separation device is minimal with respect to the overall process, so that no undesirable dilution of the washing medium is to be feared. For the final removal of remaining residual moisture in the purified potassium sulfate, this is expediently removed by a subsequent washing process drying. Further advantageous embodiments of the method for
  • Treatment of contaminated potassium sulfate results from the claims directed to the process for separating carbon dioxide from a gas stream.
  • the advantages mentioned for the deposition process can be correspondingly transferred to the treatment process.
  • FIG. 1 shows a schematic representation of a device for
  • the process is part of a separation process for carbon dioxide from a flue gas stream.
  • a flue gas stream to be treated is introduced via a feed line 3 into an absorber 5 of a separation device 7.
  • the carbon dioxide contained in the flue gas is brought into contact with a washing medium and absorbed therein.
  • the released from C0 2 gas stream is released into the atmosphere.
  • the scrubbing medium laden with carbon dioxide is then supplied to a desorber 9 which is connected to the absorber 5 in terms of flow.
  • the carbon dioxide contained in the washing medium is released by increasing the temperature.
  • the C0 2 - rich gas stream is recycled.
  • the scrubbing medium freed from carbon dioxide must be further processed after it leaves the desorber for its regeneration.
  • the washing medium is fed via a feed line 11 to a treatment stage 13 before it can be returned to the absorber for re-absorption of carbon dioxide.
  • the treatment stage 13 which is designed as SO x recyclers, sulfur oxides contained in the washing medium by lowering the temperature and concentration changes in
  • Wash medium as potassium sulfate (K 2 S0 4 ) precipitated.
  • the separated in the treatment stage 13 washing medium is starting from the treatment stage 13 via a return line 15th returned to the deposition process or in the deposition device 7.
  • the potassium sulfate recovered by the SO x recycling process in the treatment stage 13 is contaminated with adhering mother liquor, it must be cleaned before further use or recycling. This requires a separation of adhering mother liquor and impurities contained.
  • the precipitated potassium sulfate is treated in a crystallizer 19, which is part of the treatment stage 13.
  • the operating temperature of the crystallizer 19 is between 10 ° C and 15 ° C.
  • a suspension with potassium sulfate particles with coarse particles necessary for the separation is produced. This suspension is then fed via a further supply line 21 to a separation unit 23.
  • the separation unit 23 is designed as a continuously operating centrifuge into which the suspension flows continuously via the supply line 21.
  • a first separation zone 25 of the centrifuge 23 a large part of the washing medium is separated from the potassium sulfate by centrifuging.
  • the pre-cleaned sample in the separation zone 25, ie the prepurified potassium sulfate, is then subjected to a washing process in a washing zone 27 adjoining the first separation zone 25.
  • a displacement wash is used in which the detergent in the filter cake is pressed from potassium sulfate. The detergent penetrates into the filter cake, whereby the present in the interstices and the pores mother liquor and impurities are largely displaced.
  • water is used as the detergent, which is metered into the washing zone 27 via a flushing connection 29.
  • the amount of dosed water is in this case only half as large as the amount of potassium sulfate to be cleaned, so that less than one twentieth of the potassium sulfate in the water during washing.
  • the separation unit 23 is operated in a temperature range between 10 ° C and 15 ° C, since the water solubility of potassium sulfate in this range is sufficiently low to ensure a high Reclaimer efficiency.
  • the purified potassium sulfate is fed via a feed line 31 to a utilization device 33.
  • a drying unit can be interposed, which enables a final drying of the potassium sulfate to remove residual moisture still contained.
  • the water is fed after the washing of the potassium sulfate from the separation unit 23 via a feed line 35 into the C0 2 - deposition device 7.
  • the feed takes place here together with the separated from the potassium sulfate in the washing process mother liquor, which is returned due to their high amino acid salt content back into the deposition process. A loss of active component can thus be reduced.
  • the feed line 35 in the present case opens into the return line 15, which returns the washing medium from the treatment stage 13 into the separation device 7.
  • the feed of the water and the return of the separated mother liquor take place together due to the fluidic connection of the two lines 15, 35 in the deposition process.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé de séparation de dioxyde de carbone à partir d'un courant de gaz, en particulier, d'un courant de gaz de combustion, dans lequel le courant de gaz est mis en contact dans un absorbeur (5) d'un dispositif de séparation (7) en séparant le dioxyde de carbone contenu dans le courant de gaz avec un milieu de lavage, le milieu de lavage chargé en dioxyde de carbone est acheminé à générateur (9) du dispositif de séparation (7) pour libérer le dioxyde de carbone, le milieu de lavage libéré du dioxyde de carbone est acheminé à une étape de préparation (13), dans laquelle l'oxyde de soufre contenu dans le milieu de lavage est précipité sous forme de sulfate de potassium et le sulfate de potassium précipité est acheminé, pour obtenir du sulfate de potassium purifié, à une unité de séparation (23) dans laquelle le sulfate de potassium est séparé du milieu de lavage. Ainsi, le sulfate de potassium précipité est soumis dans l'unité de séparation (23) en même temps à un processus de lavage. En outre, l'invention concerne un procédé de préparation de sulfate de potassium non purifié, dans lequel le sulfate de potassium non purifié est séparé du milieu de lavage pour obtenir du sulfate de potassium purifié au moyen d'une unité de séparation (23) et est soumis dans l'unité de séparation (23) en même temps à un processus de lavage.
PCT/EP2014/059943 2013-05-28 2014-05-15 Procédé de séparation de dioxyde de carbone à partir d'un courant de gaz, en particulier, d'un courant de gaz de combustion et procédé de préparation de sulfate de potassium non purifié WO2014191213A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013209884.7 2013-05-28
DE102013209884 2013-05-28

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WO2014191213A1 true WO2014191213A1 (fr) 2014-12-04

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1201789A (en) * 1966-11-15 1970-08-12 Wellman Lord Inc Process for the recovery of sulfur dioxide
US4425313A (en) * 1976-08-16 1984-01-10 Cooper Hal B H Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them
WO2012012027A1 (fr) * 2010-07-20 2012-01-26 Powerspan Corp. Milieux d'absorption servant à retirer le co2 d'un courant gazeux et procédé l'utilisant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1201789A (en) * 1966-11-15 1970-08-12 Wellman Lord Inc Process for the recovery of sulfur dioxide
US4425313A (en) * 1976-08-16 1984-01-10 Cooper Hal B H Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them
WO2012012027A1 (fr) * 2010-07-20 2012-01-26 Powerspan Corp. Milieux d'absorption servant à retirer le co2 d'un courant gazeux et procédé l'utilisant

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