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WO2025026873A1 - Procédé pour séparer le co2 de l'air et pour fournir du co2 concentré - Google Patents

Procédé pour séparer le co2 de l'air et pour fournir du co2 concentré Download PDF

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Publication number
WO2025026873A1
WO2025026873A1 PCT/EP2024/071145 EP2024071145W WO2025026873A1 WO 2025026873 A1 WO2025026873 A1 WO 2025026873A1 EP 2024071145 W EP2024071145 W EP 2024071145W WO 2025026873 A1 WO2025026873 A1 WO 2025026873A1
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Prior art keywords
sorbent
scrubber
intermediate tank
electrodialysis
enriched
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PCT/EP2024/071145
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German (de)
English (en)
Inventor
Enrica LANGE
Oliver Gröger
Christine SCHÜTZ
Rolf Bank
Klaus Behnke
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Volkswagen AG
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Volkswagen AG
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Publication of WO2025026873A1 publication Critical patent/WO2025026873A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing 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
    • B01D53/14—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 absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20415—Tri- or polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20494—Amino acids, their salts or derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • 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
    • B01D2258/06—Polluted air
    • 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
    • B01D53/32—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 electrical effects other than those provided for in group B01D61/00
    • B01D53/326—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 electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • 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 CO2 from the air and for providing concentrated CO2, as well as to a device for separating CO2 from the air and providing concentrated CO2.
  • Carbon capture and storage (CCS) technologies are efficient and effective methods for reducing the carbon dioxide emitted into the atmosphere.
  • Known methods for capturing carbon dioxide include absorption, adsorption, membrane-based systems, electrochemical separation and cryogenic separation.
  • the absorption of carbon dioxide in an aqueous solvent can be used to purify exhaust gases from power plants and industrial plants.
  • DAC direct air capture
  • Disclosure document (DE 102020 004 542 A1) describes several possibilities for binding and releasing carbon dioxide from a gas mixture on a laboratory scale.
  • Various methods are presented for loading an amine-containing sorbent, such as homogenizing the sorbent with a gas mixture or absorbing the CO2 onto a sorbent by a gas washing column.
  • possibilities for precipitating the bound CO2 as a solid and electrolytically releasing CO2 from an acceptor medium are described.
  • a circulation of the sorbent after loading and subsequent unloading with CO2 in a direct path between a gas washing column for loading and an electrodialysis device for unloading is described.
  • the air has a tendency to become enriched with water up to the respective saturation partial pressure, which, depending on the inlet air humidity, can lead to a high water loss of an aqueous sorbent.
  • Quantitative statements on water loss and the energy balance for a system beyond the laboratory scale depend on several environmental conditions and the specific large-scale design and are not available in general terms.
  • the object of the present invention is to provide a method and a device for the efficient absorption and controlled release of gaseous carbon dioxide from the ambient air, which at least partially overcomes the existing disadvantages of the previous methods.
  • a method according to the invention for obtaining CO2 from a gaseous medium, in particular ambient air, using a CO2 separation device with a CO2 scrubber with a gas supply and a gas discharge, a sorbent supply at an upper end of the CO2 scrubber and a first intermediate tank for receiving a CO2-enriched sorbent from the CO2 scrubber; and an electrodialysis device for separating CO2 into a release medium comprises the following method steps:
  • the process is designed to be carried out continuously, semi-continuously or in batches.
  • a gaseous medium can be ambient air, but industrial gases, exhaust gases, gas mixtures, point sources and the like can also be freed of CO2 and/or other water-soluble gases, such as nitrogen oxides (e.g. NO x ), using the process described herein.
  • the method according to the invention is carried out in a CO2 separation device. This is designed so that gaseous CO2 is first bound to a sorbent and then released from the sorbent in a controlled manner as a gas and can be collected and stored in concentrated form.
  • Such a separation device has a CO2 scrubber.
  • the CO2 scrubber can be a column with packing, also referred to below as an “absorber column”, for example a trickle bed column.
  • the packing can be Raschig rings, or other packing elements.
  • the packing elements have a large surface area and can thus provide a large reaction surface for the absorption process.
  • a gas supply and a gas discharge are provided, with which a gas flow containing CO2, such as ambient air, can be fed into the CO2 scrubber and a gas flow containing little CO2 can be discharged again.
  • the gas supply and gas discharge can be carried out, for example, via a suction fan that is positioned at an upper air inlet and thus sucks, for example, ambient air containing CO2 into the separation device through a lower air inlet. In this way, the gas flow flowing in from below can flow through the CO2 scrubber and form the continuous phase.
  • CO2 is absorbed by a flowable sorbent.
  • the sorbent can be a liquid, a solvent or an aqueous solution of a sorbent.
  • Known liquids for absorbing CO2 are, for example, amine-containing ionic liquids.
  • Known solvents for absorbing CO2 are, for example, monoethanolamine (MEA), ammonia and the like.
  • solutions of amines, diamines and tertiary amines, amino acids and amino acid salts are preferably used as sorbents.
  • the sorbent is fed into the CO2 scrubber through a sorbent feed at its upper end.
  • the sorbent can be dispersed, for example by atomizing or dividing it into fine droplets. This can be done by using a nozzle. This can increase the absorption surface of the sorbent.
  • the sorbent can trickle through the CO2 scrubber and form the disperse phase.
  • a device for carrying out the method according to the invention further comprises a first intermediate tank and an electrodialysis unit, wherein the sorbent enriched with CO2 is collected in the first intermediate tank and the dissolved or absorbed CO2 is transferred into a release medium in the electrodialysis unit.
  • the release medium can be an aqueous solution of a proton donor, such as an organic acid.
  • a method according to the invention comprises enriching the sorbent with CO2 in the CO2 scrubber.
  • the divided sorbent can trickle through the CO2 scrubber.
  • the packing of the CO2 scrubber allows the sorbent to be distributed over a large surface and a large contact area can be created between the CO2-containing gas stream flowing in from below and the sorbent.
  • the enrichment of the sorbent with CO2 can occur when CO2 binds to the sorbent and then dissolves as an anion.
  • the enriched sorption solution i.e. the sorbent loaded with CO2
  • the first intermediate tank is fed into the first intermediate tank.
  • This can be done, for example, through a tank that is attached directly to the lower end of the CO2 scrubber and into which the enriched sorbent can flow.
  • there can also be a pipe connection that leads the loaded sorbent from the CO2 scrubber into the first intermediate tank.
  • a first partial amount of the enriched sorbent is fed into the electrodialysis device. This can take place when the sorbent is sufficiently enriched, for example by determining that saturation with CO2 has been reached.
  • a second partial amount of the enriched sorbent from the first intermediate tank can be fed back into the CO2 scrubber. This can serve to further load the partially CO2-enriched sorbent with CO2 and thus achieve a higher concentration of absorbed CO2 in the sorbent, which has an advantageous effect on the subsequent electrodialysis.
  • the CO2 bound by the process according to the invention can be completely regenerated to gaseous CO2 without any losses due to salting-out effects or flocculation of poorly soluble or insoluble carbonates or bicarbonates.
  • the process according to the invention is designed to be carried out continuously, semi-continuously or batchwise.
  • the absorption and release steps can take place in a continuous cycle.
  • absorption and release i.e. electrodialysis
  • electrodialysis can take place completely separately from one another.
  • electrodialysis can be switched on when absorption has taken place to a sufficient extent.
  • the method also comprises the steps:
  • the sorbent enriched in the CO2 scrubber is depleted in the electrodialysis unit.
  • CO2 that has dissolved (or been absorbed) is removed from the sorbent by electrodialysis and released in gaseous form.
  • Electrodialysis is a process in which a voltage is applied to an aqueous medium, for example.
  • the bound or absorbed CO2 which can be present in the sorbent solution as a carbonate ion or bicarbonate ion, for example, and can desorb from the sorbent as such, can pass through an anion exchange membrane (AAM) and be converted to carbon dioxide in the anolyte chamber and released in a controlled manner as a gas into a release medium.
  • AAM anion exchange membrane
  • a portion of the CO2-depleted (or regenerated) sorbent can be discharged into a second intermediate tank.
  • the second intermediate tank can be connected downstream of the electrodialysis unit, and the CO2-laden sorbent can be regenerated by electrodialysis and then fed into the second intermediate tank.
  • the supply of CO2-enriched sorbent according to the invention can not only be carried out directly from the CO2 scrubber but also from the first intermediate tank, the release of CO2 from the sorbent by electrodialysis can also take place independently of a continuous absorption of CO2 by the sorbent in the CO2 scrubber.
  • the method in this embodiment can also be carried out in such a way that the regenerated sorbent does not have to be fed directly to the CO2 scrubber; accordingly, regenerated sorbent can be kept in the second intermediate tank until the absorption of CO2 by the regenerated sorbent is to take place again.
  • the sorbent from the second intermediate tank can be fed to an upper end of the CO2 scrubber, where it is again finely divided and is available for the absorption of CO2 in the CO2 scrubber.
  • Controlled release means for example, dehumidification and compression and subsequent introduction of carbon dioxide into gas cylinders for storage and/or later use, for example in organic synthesis.
  • the carbon dioxide obtained in this way can, for example, be sufficient for further synthesis in the production of e-fuels.
  • the advantage of returning the regenerated sorbent to either the first or second intermediate tank in the present embodiment allows, in comparison to existing processes, a process in which the sorbent does not have to be pumped through the electrodialysis membranes, which has a positive effect on the service life of the dialysis membranes. Since the column and dialysis unit can have different heights and throughputs, the height of the column would have to be achieved using a pump. If there is a direct return from the dialysis chamber to the column, there is a risk of accelerated wear of the dialysis membrane when using a pump.
  • the absorption and release of carbon dioxide with the embodiment described here can be carried out either continuously, semi-continuously or in batches. This is advantageous because electrodialysis is faster than the absorption of, for example, carbon dioxide by a sorbent. Accordingly, the absorption requires a higher throughput.
  • the electrodialysis can be switched on intermittently (or batchwise), for example when a certain amount of saturated sorbent is available (for example, provided in the first intermediate tank).
  • process can also be operated continuously thanks to the intermediate tanks used and the possibility of recirculation.
  • process control can depend on, for example, site parameters, gas concentrations in the ambient air, plant size and the like.
  • the enrichment and depletion of the sorbent with CO2 is determined by a saturation criterion. This can be done by measuring the electrical conductivity of the sorbent. Since the water-soluble gas molecules such as carbon dioxide dissolve as anions, the electrical conductivity of the sorbent solution increases during the absorption of, for example, carbon dioxide into a sorbent. According to this embodiment, saturation of the sorbent with, for example, carbon dioxide can be determined by the fact that the conductivity of the sorbent no longer increases. The solution is then considered saturated. In an analogous manner, the regeneration of the sorbent can also be monitored, i.e. by a corresponding decrease in the electrical conductivity of the sorbent.
  • the measurement of the electrical conductivity as a saturation parameter of the sorbent enables the saturation level to be determined in direct operation, i.e. no sampling and external measurement of the CO2 loading concentration via gas chromatography, for example, is necessary. Furthermore, the absorption and desorption process can be monitored in-situ by measuring the conductivity and process parameters can be adjusted accordingly to the current absorption and desorption status of the sorbent.
  • the conductivity of the sorption solution during the absorption process can be measured, for example, when it leaves the CO2 scrubber, for example using a conductivity sensor. If the conductivity of the sorbent increases further, for example during the process, the sorbent can be fed back into the CO2 scrubber until a constant conductivity value is measured.
  • the saturated, loaded sorbent can then be stored in the first intermediate tank for a sequential or batchwise operation of the electrodialysis. Alternatively or simultaneously, the sorbent can be fed directly from the first intermediate tank to the electrodialysis in a continuous operation, or partially in a semi-continuous operation.
  • the conductivity during the desorption process is first determined before the loaded sorbent enters the electrodialysis unit and then after it leaves the electrodialysis unit.
  • the regeneration of the sorbent can be determined, e.g. by determining that the electrical conductivity does not decrease further or has reached a predetermined value.
  • the sorbent comprises an aqueous solution of at least one amine.
  • This can be a primary, secondary or tertiary amine.
  • Amines have a free electron pair on the nitrogen atom, which allows them to accept a proton and thus act as bases in aqueous solution, i.e. they produce OH' ions.
  • the sorbent comprises an aqueous solution of at least one agent with a guanidine group.
  • guanidine groups form bases in aqueous solution by adding a proton, which improves the absorption process of CO2 to the sorbent (e.g. to the amine or guanidine group), as explained in more detail below.
  • the sorbent comprises an arginine solution.
  • Arginine is a basic amino acid that has an amine group and a guanidine group and is therefore very suitable for absorbing carbon dioxide in aqueous solution.
  • the chemical processes involved in the absorption of, for example, carbon dioxide by an amino acid are described in more detail below.
  • the concentration of the sorbent can be increased during the circulation of the sorbent without, for example, carbonates and bicarbonates precipitating as solids. Surprisingly, it was found that with the circulation according to the invention, no precipitation of solids or flocculation occurs. Increasing the concentration of the sorbent, such as arginine in aqueous solution, during the circulation of the absorption leads to an even higher binding or absorption rate of gas molecules to the sorbent. It was also found that the solubility of arginine increases after loading with carbon dioxide compared to the solubility of pure arginine in water (solubility of 148 g/l at RT).
  • the concentration can initially be between 0.5 and 2 mol/L and can be increased during the process.
  • the release takes place by means of electrodialysis using an acid.
  • the acid serves to provide protons, which facilitates the dissociation of carbonate or bicarbonate ions into carbon dioxide and water. Accordingly, the bound CO2 is released in gaseous form into the acid as a release medium.
  • the acid can be an organic acid. The requirements for the acid used are, on the one hand, a high electrical conductivity of the acid, with migration in the applied electrical field of the electrodialysis being as low as possible. This can also happen if an acid anion has a molecular size that is too large to pass through the ion exchange membranes of the electrodialysis chambers.
  • the release medium comprises citric acid.
  • the present invention further relates to a device for recovering CO2 from a gaseous medium, comprising a unit for gas supply and gas removal, a unit for sorbent supply, a CO2 scrubber, and a first intermediate tank.
  • the elements are designed and arranged to carry out the method according to the invention.
  • the gas supply and gas removal can be carried out by a suction fan that is attached to an upper opening that serves as an air outlet, while ambient air is introduced as a gas through a lower opening that serves as an air inlet.
  • the ambient air can be analyzed for its composition and properties (e.g. water content, CO2 content, temperature, etc.) at the inlet and outlet.
  • the ambient air at the inlet can be adjusted to the desired process parameters, i.e. conditioned.
  • the ambient air at the inlet can be filtered to remove dust, pollen, soot and the like.
  • the sorbent supply in the device according to the invention can be fed either through a storage tank with sorbent or from regenerated sorbent from the second intermediate tank, or from sorbent that is not yet fully loaded from the first intermediate tank.
  • the sorbent is finely divided when it enters the CO2 scrubber. Accordingly, the sorbent supply can be designed as a pipe with a nozzle at the end.
  • the CO2 scrubber of the device according to the invention can, as already mentioned above, be designed as a column with packing, for example in the form of a trickle bed column, or as A fixed bed reactor is characterized in that a liquid can flow through a solid bed or packing.
  • a trickle bed column in the sense of the device according to the invention is a fixed bed reactor through whose solid bed or packing a liquid flows on the one hand and a gas on the other. The gas flow penetrates the trickle bed reactor from bottom to top as a continuous phase, while the liquid flows from top to bottom through the solid bed or packing of packing elements.
  • the first intermediate tank of the device according to the invention can either be installed under the CO2 scrubber so that the loaded sorbent flows directly from the CO2 scrubber into the tank. However, it can also be supplied via a pipeline.
  • the tank itself can be a stainless steel tank with the appropriate capacity (i.e. tailored to the respective absorption capacity of the system).
  • the individual elements of the device according to the invention are designed and arranged so that they can carry out the method according to the invention.
  • the device according to the invention is further equipped with an electrodialysis unit and a second intermediate tank.
  • Electrodialysis unit is a device for electrodialysis.
  • Electrodialysis is an electrochemical process in which ionic components can be removed from a solution using ion exchange membranes and the driving force of an electric field. Ionic compounds are reduced in one circuit (diluate) and concentrated in another (concentrate).
  • the electrodialysis unit can be constructed from two electrode end plates with membranes stacked between them.
  • the anode can be made of nickel or stainless steel, the cathode of stainless steel.
  • Cell frames are inserted between the membranes as spacers for the supply and removal of the loaded sorbent.
  • the cell frame thickness can be 0.5 mm, for example, and the cell frame thickness defines the membrane spacing accordingly.
  • the cell frame size can be 50 x 50 cm, for example.
  • the membrane package can consist of 16 cell pairs. In an embodiment designed in this way, the effective membrane surface area corresponds to 1750 cm 2 . Further scaling up to large-scale industrial scale is possible.
  • the device further comprises a second intermediate tank which is connected downstream of the electrodialysis unit.
  • the second intermediate tank can be made of stainless steel and connected to the electrodialysis unit by means of a pipeline.
  • the device according to the invention is further equipped with a first bypass, which recirculates the sorbent from the first intermediate tank to the CO2 scrubber for further absorption.
  • a first bypass which recirculates the sorbent from the first intermediate tank to the CO2 scrubber for further absorption.
  • it can be determined, for example, by means of a conductivity sensor that the conductivity of the sorbent continues to rise when it leaves the CO2 scrubber and before it enters the first intermediate tank.
  • This makes it possible, for example, to determine that the sorbent is not yet completely saturated with bicarbonate or carbonate ions (i.e. the sorbent is not yet completely loaded with CO2) and can be led from the first intermediate tank into the first bypass, from where the sorbent can be fed back into the absorber column from above. This can be done by using a pump that is attached to the first bypass.
  • the conductivity sensor can also be located in the first intermediate tank and measure the conductivity of the solution or the liquid in it. If the conductivity value in the first intermediate tank does not increase any further, it can be determined, for example, that the sorbent is saturated and the absorption cycle can be stopped.
  • the device according to the invention comprises a second bypass that returns the sorbent from the second intermediate tank to the CO2 scrubber, whereby the second bypass bypasses the electrodialysis unit.
  • the CO2 scrubber and the electrodialysis unit Due to their design, the CO2 scrubber and the electrodialysis unit have a height difference of several meters. As a result, without the use of a second intermediate tank and second bypass, the regenerated absorber solution would have to be pumped through the electrodialysis unit to compensate for this height difference, which leads to increased membrane wear on the dialysis membranes.
  • the second bypass allows the regenerated absorber solution (or the sorbent) to be collected in the second intermediate tank and from there pumped back to the height of the CO2 scrubber, from where it can be fed to the latter for renewed absorption of CO2.
  • the regenerated absorber solution in order to protect the dialysis membranes, it is possible to feed the regenerated absorber solution to the first intermediate tank directly from the electrodialysis chamber by means of a third bypass. Since the height difference of the CO2 scrubber does not have to be overcome, this can be done without the use of a pump, which protects the electrodialysis membranes. As already described above, the at least partially regenerated absorber solution can be fed back into the absorption circuit in the CO2 scrubber.
  • the device according to the invention can also be equipped with a heat exchanger unit and a heat pump.
  • a heat exchanger unit For example, it can be advantageous to cool the incoming ambient air to an optimal temperature for absorption using a cooling unit (i.e. a first heat exchanger).
  • a further heat exchanger By using a further heat exchanger, the sorbent loaded with CO2 can be heated to an optimal temperature for electrodialysis (e.g. a temperature between 30°C and 50°C).
  • the two heat exchangers can be coupled to a heat pump, for example, which results in optimal and energetically advantageous heat utilization of the device according to the invention.
  • the purpose of cooling or generally preconditioning the incoming ambient air is to increase the hydrophilic interactions between the gas molecules to be dissolved and the aqueous absorber solution (i.e. the sorbent) and thus to ensure a better transition of the gas molecules into the water phase.
  • the device according to the invention is further equipped with sensors which are suitable for measuring the electrical conductivity, temperature, pH value, pressure, flow rate, current and voltage, as well as the humidity of the gas streams and/or liquids used. These parameters can be determined for the sorbent before/after absorption, as well as before/after electrodialysis, for the gaseous medium before/after entry into the absorber column and the CO2 released after exiting the electrodialysis unit.
  • the use of sensors in the device according to the invention also makes it possible to operate the system sensor-based and sensor-monitored, which can be largely autonomous.
  • the use of sensors enables the use of control technology, which, depending on the measured parameters,
  • the device according to the invention is operated either intermittently or continuously, or decides on the connection of one of the bypasses or intermediate tanks described above.
  • Fig. 1 shows schematically an embodiment of the presented method
  • Fig. 2 shows schematically a simplified structure of the absorption and release system
  • Fig.3 shows schematically a detailed structure of the absorption and release system.
  • FIG. 1 An embodiment of a simplified method according to the invention is shown in Fig. 1.
  • the focus will be on the chemical reactions and interactions that take place in the method according to the invention; a detailed description of the process control according to the method is given with reference to Fig. 2.
  • CO2 is absorbed from the air by bringing the air into contact with a liquid absorber solution in a CCh scrubber (10).
  • a liquid absorber solution in a CCh scrubber (10).
  • air is introduced into the CO2 scrubber from below (V1) and the absorber solution, which is divided at the top of the CO2 scrubber, flows in countercurrent from top to bottom through the CCh scrubber (V2).
  • aqueous amino acid solution is used as the sorbent or absorber solution, preferably an arginine solution. It is known that basic amino acids dissolved in water increase the reaction of gases (in this case CO2) with water to form water-soluble compounds. The reason for this lies in the chemical structure of amino acids.
  • the generic formula of an amino acid is HOOC-CHR-NH2.
  • Amino acids have a carboxyl and a primary or secondary amine group as reactive groups, which allows them to undergo an intramolecular acid-base reaction. An internal transfer of a proton from the carboxyl group to the amine group takes place, resulting in a dipolar, zwitterionic form of the amino acid.
  • (1) corresponds to the non-ionic and (2) to the dipolar zwitterionic form of an amino acid:
  • Amino acids are ampholytes, i.e. they can react as acids or bases because the deprotonated carboxyl group can absorb protons and the protonated amine group can release protons. In aqueous solution they usually exist as zwitterions.
  • amino acids react as bases; accordingly, the carboxyl group of an amino acid is protonated in acidic solution, so that the cation form of the amino acid results from the protonated ammonium group (R-NH 3 + ).
  • the pH value of the solution is adjusted so that the amino acid is electrically neutral to the outside, i.e. the charges in the molecule cancel each other out.
  • amphoteric nature of amino acids is important when considering them as solvents for CO2 capture.
  • hydroxyl ions (OH') in equations 2 and 3 are, as mentioned above, generated by the action of amino acids as weak bases in aqueous solution:
  • the degree of hydrolysis is determined by, for example, the concentration of the amine, the pH of the solution and the chemical stability of the carbamate. CO2 absorption is increased when all absorbed CO2 is present as bicarbonate (HCO 3 '). Solutions that have a higher ratio of bicarbonate to carbamate have greater desorption rates in electrodialysis and produce a desirable, leaner desorbed solution. The kinetics of CCh uptake are dominated by the formation of the carbamate anion (Equation 2). The formation of the carbamate anion occurs almost immediately upon contact of the amine-containing sorbent with the gas mixture and represents the rate-determining step.
  • Equation 6 the base-catalyzed bicarbonate formation is significantly slower.
  • Equation 3 The contribution of equation 3 to the kinetics of the absorption process can be important at very low CO2 loadings where the pH of the solution is high. However, this reaction becomes slower with increasing CO2 uptake compared to the reaction with an amine.
  • the CO2 from the supplied air stream is bound to the sorbent in the CO2 scrubber (10), CO2-free or low-CO2 gas leaves the CO2 scrubber (10) at the top (V9) and the absorber solution loaded with CO2 is pumped from the bottom of the column into the electrodialysis unit (20) (V3).
  • the bottom of the column can be designed in the form of a first intermediate tank (11).
  • the bound CO2 which is present in solution in the form of HCOa' as described above, is separated (V8) from the sorbent and the released gaseous CO2 is then concentrated (V4).
  • Electrodialysis is an electrochemical process in which ionic or ionogenic components can be removed from a solution and separated from one another by means of one or more ion exchange membranes using an applied electric field as the driving force.
  • ionic compounds are reduced in one circuit (diluate) and concentrated in another (concentrate).
  • the diluate chamber (2) and concentrate chamber (3) are separated from each other by an anion exchange membrane (AAM) (6).
  • AAM anion exchange membrane
  • An anion exchange membrane here is a membrane that is semi-permeable to anions.
  • the sorbent loaded with CO2 is fed into the diluate chamber (V3).
  • Bicarbonate anions (HCOa') migrate from the diluate chamber (2) through the AAM (6) in the direction of the arrow in Fig. 1 into the adjacent concentrate chamber (3). Further migration towards the anode is prevented by the subsequent bipolar membrane (BPM) (5).
  • BPM bipolar membrane
  • the anode and cathode chambers contain the electrodes through which the external voltage, i.e. the electric field, is applied.
  • the external voltage i.e. the electric field
  • H + and OH' ions are generated at the BPM by electrophoretic water splitting and are released into the adjacent cell chamber.
  • the H + ions react with the HCOa' ions in the concentrate chamber (3) to form water and CO2:
  • the amine-containing sorbent remains in the diluate chamber (2) and is regenerated according to the following equation:
  • the sorbent thus prepared is then fed to the absorber column (10) for further CO2 separation from the air (V5).
  • the concentrate chamber (3) is part of a circuit with an aqueous acid as the absorption and release medium.
  • the aqueous acid neither migrates towards the cathode through the AAM nor towards the anode through the BPM, but remains in the concentrate chamber (3).
  • the migration towards the anode of the acid anions used can be achieved, for example, by using a BPM that has a cut-off in the range of 0.2 -10 kDa, for example by means of a bipolar nanofiltration (NF) membrane.
  • NF bipolar nanofiltration
  • the aqueous acid is citric acid, which is fed to the concentrate chamber (3) (V6). This reduces the pH value in the concentrate chamber (3).
  • the reaction according to equation 7 releases gaseous CO2 and the acid used as a release medium is regenerated (V8) and collected in a storage container (40).
  • Any other aqueous solution of an organic or inorganic acid that has a very high electrical conductivity and is not electrophoretically transported in the direct current electric field, or alternatively has a molecular size larger than the cut-off (i.e. the pore size) of the BPM, can be used as the release medium.
  • the release medium can also be water.
  • Hydrogen (H2) is produced as by-products in the cathode chamber (1) and oxygen (O2) in the anode chamber (4).
  • H2 Hydrogen
  • O2 oxygen
  • NaOH flows from two different storage containers (50; 60) through the two electrode chambers in separate circuits.
  • a bypass allows the CO2 scrubber (10) to be designed smaller, which reduces investment costs.
  • the sorbent can be saturated with CO2.
  • the concentration of the sorbent in the absorber solution such as arginine
  • the concentration of the sorbent in the absorber solution can be gradually increased, resulting in increased CO2 absorption in the sorbent (or in the aqueous solution of the sorbent).
  • a higher CO2 content corresponding to a high proportion of HCOa' ions in the loaded sorbent, promotes the efficient operation of electrodialysis, whereby more CO2 can be produced in concentrated form.
  • arginine solution as a sorbent (or absorber solution) with reference to Fig. 2.
  • ambient air is introduced into the CO2 scrubber (10) from below (V1).
  • fresh arginine solution is introduced into the CO2 scrubber from above (V2) for commissioning.
  • the absorber solution trickles from top to bottom over packing elements (e.g. Raschig rings or other packing elements). The packing elements serve to increase the contact surface between air and liquid.
  • the arginine solution absorbs part of the CO2 from the air stream and CCh-poor air escapes at the head of the CO2 scrubber (V9).
  • a first intermediate tank (11) is attached to the bottom of the CO2 scrubber, which serves to hold loaded absorber solution. If the absorber solution is not yet sufficiently saturated with CO2, in this embodiment it is possible to run the CO2 scrubber in a circle (V10), which means that the absorber solution can trickle through the CO2 scrubber several times until the absorber solution is saturated with CO2. For this purpose, the absorber solution is pumped from the first intermediate tank (11) to the top of the CO2 scrubber (10) using a first bypass (12).
  • the first bypass (12) is also used for the separate commissioning of the CO2 scrubber (10), i.e. without switching on the electrodialysis unit (20).
  • the absorber solution is sufficiently saturated with CO2, it is pumped from the first intermediate tank (11) into the electrodialysis unit (V3). If the CO2 has been separated from the loaded absorber solution in the electrodialysis unit (20), the regenerated absorber solution can be fed back into the CO2 scrubber (10) in two ways:
  • the CCh-poor or CCh-free absorber solution can be led into a second intermediate tank (22) (V12), as shown in Fig. 2, and from there to the top of the CO2 scrubber (10) (V11). Accordingly, a second bypass (13) is provided for this purpose, which can bypass the electrodialysis unit (20).
  • the regenerated sorption solution or the regenerated sorbent can be fed directly from the electrodialysis unit (20) to the first intermediate tank (11) below the CO2 scrubber (10) by means of a third bypass (V13).
  • a direct connection between the outlet of the electrodialysis unit (20) and the head of the CO2 scrubber (10) is not provided according to the invention, since, due to the design, there can be a height difference of several meters between the head of the CO2 scrubber (10) and the outlet of the electrodialysis unit (20).
  • the regenerated absorber solution would have to be pumped up to the head of the CO2 scrubber (10) and pass through the electrodialysis unit (20), which would have a negative effect on the membrane stability of the dialysis membranes and ion exchange membranes.
  • the ambient air to be converted can be preconditioned.
  • the ambient air is introduced into the CO2 scrubber (10) from below (V1).
  • a suction fan is installed at the air outlet of the CO2 scrubber. In this way, ambient air is sucked into the CO2 scrubber from bottom to top.
  • the ambient air first flows through a filter to remove dust, pollen, etc.
  • the air is adjusted to the desired temperature and humidity via a droplet separator and cooler, which can be a heat exchanger (WO).
  • a droplet separator and cooler which can be a heat exchanger (WO).
  • the device according to the invention makes it possible to depict different air parameters for the investigation of different air conditions at different installation locations.
  • the temperature is set via a sensor (S4) and the air flow via a sensor (S5).
  • the CCh content of the introduced air is monitored via the CCh sensor (S1), the humidity and the pressure via the sensors (S2) and (S3).
  • the sorbent in the present embodiment is prepared using arginine and distilled or fully deionized water in concentrations of preferably 1 to 2 mol/L and stored in a first storage tank (30).
  • the fresh absorber solution is pumped from the top of the tank into the CO2 scrubber (10) (V2) using a pump (P1). It is passed through a heat exchanger (W1) to adjust the absorber solution to a defined temperature.
  • the temperature parameters of the absorber solution, which is fed to the CO2 scrubber (10) at the top, are measured via the sensor (S7), the flow via the sensor (S8), the pressure via the sensor (S9) and the conductivity via the sensor (S10) are monitored.
  • the CC>2-poor or CCh-free air leaves the CO2 scrubber (10) at the head (V9), with its parameters humidity being recorded by the sensor (S11), the CCh content by the sensor (S12) and the temperature by the sensor (S13).
  • the operating temperature of the CO2 scrubber (10) can, for example, be determined in the middle using the sensor (S6).
  • further temperature sensors can be attached at various positions on the CO2 scrubber (10) in order to be able to monitor the temperature over the entire length of the CO2 scrubber (10).
  • the conductivity of the absorber solution is continuously measured by a conductivity sensor (S14) in order to be able to draw conclusions about the loading of the sorbent with CO2.
  • the conductivity of the sorbent can be continuously measured in the first intermediate tank (11) (sensor not shown in Fig. 3).
  • a first bypass (12) is therefore provided in order to circulate the sorbent through the CO2 scrubber (10).
  • the absorber solution which is not yet completely loaded with CO2 as determined by the conductivity sensor (S14)
  • P2 the conductivity sensor
  • V10 the absorber solution can trickle through the CO2 scrubber again, where further CCh separation can take place.
  • This process step can be repeated until the value for the conductivity, measured by the sensor (S14), remains constant.
  • the absorber solution is sufficiently saturated with CO2, it is pumped (V3) into the diluate chamber (2) of the electrodialysis unit (20) using the pump (P3).
  • the loaded absorber solution is heated to a favorable temperature between 30°C and 50°C using a heat exchanger (W2).
  • W2 heat exchanger
  • a slightly higher temperature is advantageous for efficient functioning of the electrodialysis, as it promotes hydrophobic interactions and thus the release of the bicarbonate as CO2.
  • the temperature of the CCh-rich absorber solution is controlled by a sensor (S21) before it is fed into the electrodialysis unit (20).
  • the other parameters flow, pH value, conductivity and pressure of the CCh-rich absorber solution are monitored by the sensors (S22), (S23), (S24) and (S25).
  • the conductivity of the sorbent after loading is in the range between 8 and 12 mS, and the electrodialysis unit (20) can be operated with a slight overpressure between 1 and 2 bar (e.g. 1.6 bar).
  • the CO2 is separated from the CCh-rich absorber solution (V8) and concentrated CO2 is released in gaseous form (V4).
  • the parameters current, voltage, temperature and conductivity of the electrodialysis unit are recorded via the sensors (S17), (S18), (S19) and (S20).
  • the at least partially regenerated sorbent can be collected in a second intermediate tank (22) (V12).
  • the fill level of the second intermediate tank can be monitored, for example, via a fill level sensor (S37).
  • the CC>2-poor or regenerated absorber solution can be fed back into the CO2 scrubber (10) in two ways. Firstly, the absorber solution can be fed into the second intermediate tank (22) (V12) and from there pumped by means of a pump (P3) to the top of the CO2 scrubber (10) via the bypass (13) (V11).
  • the conductivity of the CCh-free or regenerated absorber solution is controlled at the outlet of the electrodialysis unit (20) using a sensor (S36). Depending on the degree of loading of the sorbent, it can be determined whether the absorber solution should be fed into the second intermediate tank (22) or the first intermediate tank (11) (see below).
  • the absorber solution Before re-entering (V11) the CO2 scrubber (10), the absorber solution can pass through the heat exchanger (W1), whereby the absorber solution can be adjusted to a desired temperature.
  • the temperature, pressure, flow and conductivity of the CCh-free or regenerated absorber solution is monitored before it enters the CO2 scrubber (10) using sensors (S7), (S8), (S9) and (S10).
  • the CC>2-free or regenerated absorber solution trickles through the CO2 scrubber (10) along the packing and can again absorb CO2 from the incoming air.
  • the second option for feeding the CCh-free or regenerated absorber solution into the CO2 scrubber (10) is the direct feed line (V13) to the first intermediate tank (11), as already mentioned above.
  • a direct connection between the outlet of the electrodialysis unit (20) and the head of the CO2 scrubber (20) is not provided, since due to the design there can be a height difference of several meters between the head of the CO2 scrubber (10) and the outlet of the electrodialysis unit (20).
  • the regenerated absorber solution would have to be pumped up to the head of the CO2 scrubber (10), which has a negative effect on the membrane stability of the dialysis membranes and the ion exchange membranes.
  • the acid is pumped from the storage container (40) into the concentrate chamber (3) of the electrodialysis unit (20) using a pump (P6).
  • the pH value, the flow rate and the conductivity of the acid are recorded using sensors (S31), (S32) and (S33).
  • the acid causes a reduction in the pH value within the concentrate chamber (3).
  • the pH value is preferably in the range between 3 and 4.
  • CO2 is released in gaseous form and the citric acid is regenerated as a release medium (V8) and returned to the storage vessel (40).
  • the still moist CO2 is dehumidified using a cold trap (K1).
  • the temperature is controlled using the sensor (S38).
  • the flow rate and the CCh content of the released CO2 are measured using the sensors (S34) and (S35).
  • the CO2 obtained is compressed and concentrated (V4), e.g. stored in gas cylinders.
  • the volume flow of CO2 is, for example, between 20 and 270 l/h.
  • the quality of the concentrated CO2 can be determined using a gas chromatograph, for example. Any by-products can be recorded qualitatively and quantitatively and separated if necessary.
  • the electrodialysis unit (20) has two separate base circuits. Aqueous NaOH solution is pumped into the cathode compartment (1) as a catholyte from a third storage tank (50) by means of a pump (P4) in order to remove the hydrogen produced as a by-product. The flow and conductivity of the catholyte are monitored by sensors (S26) and (S27).
  • the conductivity of the catholyte is advantageously between 30 and 40 mS/cm.
  • nitrogen is fed into the storage tank (50) of the catholyte in order to prevent an accumulation of hydrogen therein.
  • the flow of nitrogen is monitored by means of a sensor (S28).
  • Aqueous NaOH solution is pumped from another storage container (60) for the anolyte into the anode chamber (4) by means of a pump (P5) in order to remove the oxygen produced as a by-product.
  • the flow and the conductivity of the anolyte are monitored by the sensors (S29) and (S30).
  • the conductivity of the anolyte is advantageously between 30 and 40 mS/cm.
  • AAM anion exchange membrane

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  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treating Waste Gases (AREA)

Abstract

La présente invention concerne un procédé ainsi qu'un dispositif permettant d'obtenir du CO2 à partir d'un milieu gazeux, en particulier de l'air ambiant, par utilisation d'un dispositif de séparation de CO2 comportant un épurateur de CO2 comprenant une amenée de gaz et une évacuation de gaz, une alimentation en sorbant à une extrémité supérieure de l'épurateur de CO2 et un premier réservoir intermédiaire destiné à recevoir un sorbant enrichi en CO2 provenant de l'épurateur de CO2, et un dispositif d'électrodialyse destiné à séparer le CO2 dans un agent de libération. Selon l'invention, le procédé comprend l'enrichissement du sorbant en CO2 dans l'épurateur de CO2, l'acheminement du sorbant enrichi en CO2 jusque dans le premier réservoir intermédiaire, l'évacuation d'une première quantité partielle du sorbant enrichi, du premier réservoir intermédiaire jusque dans le dispositif d'électrodialyse, et le renvoi d'une seconde quantité partielle du sorbant enrichi, du premier réservoir intermédiaire jusque dans l'épurateur de CO2. Selon l'invention, le procédé est conçu de sorte à être mis en œuvre de manière continue, semi-continue ou discontinue.
PCT/EP2024/071145 2023-07-28 2024-07-25 Procédé pour séparer le co2 de l'air et pour fournir du co2 concentré Pending WO2025026873A1 (fr)

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DE102023120194.8A DE102023120194A1 (de) 2023-07-28 2023-07-28 Verfahren zur abtrennung von co2 aus luft und bereitstellung von aufkonzentriertem co2
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013036859A1 (fr) * 2011-09-07 2013-03-14 Carbon Engineering Limited Partnership Capture de gaz cible
DE102020004542A1 (de) 2020-07-27 2022-01-27 Ulrich Dietz Verfahren zur Bindung, Transport, Reaktionsaktivierung, Umsatz, Speicherung und Freisetzung von wasserlöslichen Gasen

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JP7330042B2 (ja) * 2019-09-27 2023-08-21 三菱重工業株式会社 二酸化炭素還元システム及び二酸化炭素還元方法
CA3187519A1 (fr) * 2020-07-28 2022-02-03 Johannes Szivacz Procede et systeme de capture de dioxyde de carbone a partir de l'air

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013036859A1 (fr) * 2011-09-07 2013-03-14 Carbon Engineering Limited Partnership Capture de gaz cible
DE102020004542A1 (de) 2020-07-27 2022-01-27 Ulrich Dietz Verfahren zur Bindung, Transport, Reaktionsaktivierung, Umsatz, Speicherung und Freisetzung von wasserlöslichen Gasen

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