WO2022023387A1 - Verfahren zur bindung, transport, reaktionsaktivierung, umsatz, speicherung und freisetzung von wasserlöslichen gasen - Google Patents
Verfahren zur bindung, transport, reaktionsaktivierung, umsatz, speicherung und freisetzung von wasserlöslichen gasen Download PDFInfo
- Publication number
- WO2022023387A1 WO2022023387A1 PCT/EP2021/071081 EP2021071081W WO2022023387A1 WO 2022023387 A1 WO2022023387 A1 WO 2022023387A1 EP 2021071081 W EP2021071081 W EP 2021071081W WO 2022023387 A1 WO2022023387 A1 WO 2022023387A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon dioxide
- acceptor
- gas
- medium
- solution
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 422
- 238000003860 storage Methods 0.000 title claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 title claims description 157
- 239000007789 gas Substances 0.000 title description 454
- 230000004913 activation Effects 0.000 title description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 1440
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 665
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 664
- 150000001875 compounds Chemical class 0.000 claims abstract description 389
- 239000012528 membrane Substances 0.000 claims abstract description 200
- 238000000926 separation method Methods 0.000 claims abstract description 130
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 claims abstract description 114
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims abstract description 108
- 239000012736 aqueous medium Substances 0.000 claims abstract description 79
- 238000000909 electrodialysis Methods 0.000 claims abstract description 50
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- -1 bicarbonate anions Chemical class 0.000 claims description 136
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 129
- 230000008569 process Effects 0.000 claims description 123
- 238000010521 absorption reaction Methods 0.000 claims description 62
- 239000002253 acid Substances 0.000 claims description 47
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- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 20
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- RIVXQHNOKLXDBP-UHFFFAOYSA-K aluminum;hydrogen carbonate Chemical compound [Al+3].OC([O-])=O.OC([O-])=O.OC([O-])=O RIVXQHNOKLXDBP-UHFFFAOYSA-K 0.000 claims description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
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- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 61
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- 238000002848 electrochemical method Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- NMKSBNZBSLHAKW-UHFFFAOYSA-N Cl.ClO Chemical compound Cl.ClO NMKSBNZBSLHAKW-UHFFFAOYSA-N 0.000 description 1
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- 239000006046 creatine Substances 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- TUHVEAJXIMEOSA-UHFFFAOYSA-N gamma-guanidinobutyric acid Natural products NC(=[NH2+])NCCCC([O-])=O TUHVEAJXIMEOSA-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical class [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 238000005192 partition Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—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
- 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
- B01D53/34—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
- B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/60—Preparation of carbonates or bicarbonates in general
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/38—Applying an electric field or inclusion of electrodes in the apparatus
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention relates to methods for the selective binding, selective membrane transport and storage of carbon dioxide (CO 2 ) in aqueous media.
- the method of the present invention comprises providing an aqueous acceptor solution containing at least one acceptor compound having a free guanidino and/or amidino group which is contacted with a gas containing carbon dioxide to remove the carbon dioxide in the acceptor solution tie.
- the resulting acceptor solutions containing bound carbon dioxide are useful for storing carbon dioxide in aqueous media, for releasing carbon dioxide again, and for use in electrochemical processes such as electrodialysis to selectively transport bound carbon dioxide through separation membranes into aqueous media.
- the present invention also relates to the production of carbonates and bicarbonates starting from acceptor solutions which contain bound carbon dioxide.
- Gaseous elements or element molecules or gaseous molecular compounds are often sought-after starting materials for chemical synthesis. Attempts are therefore made to obtain these elements or element molecules or compounds in pure form, which often requires a great deal of technical effort or energy input.
- Methods for obtaining industrial gases by separation using separation membranes are known in the prior art. In the case of air mixtures, the concentrations of the gaseous elements or element molecules or gaseous molecular compounds to be separated are usually very low. The separation efficiency is usually not in the desired range, especially when it comes to elements or element molecules or gaseous molecular compounds that differ only slightly from one another in terms of their physico-chemical properties.
- gaseous elements or element molecules or gaseous molecular compounds that can be absorbed in a liquid
- gaseous elements or element molecules or gaseous molecular compounds that are not or only to a small extent absorbed/dissolved in the liquid can be separated .
- the gaseous element or element molecule or the gaseous molecular compound leads to a dissociation of water molecules in an aqueous medium and a water-soluble compound, e.g. an acid form, of the gaseous element or element molecule or the gaseous compound forms .
- gaseous compounds of carbon and oxygen or sulfur and oxygen such as carbon dioxide (CO 2 ) or sulfur dioxide (SO 2 ), where, for example, carbonic acid or sulfuric acid is formed in low concentrations in an aqueous medium.
- gaseous molecular compounds such as carbon dioxide (CO 2 ) or sulfur dioxide (SO 2 ), which lead to dissociation of water molecules in an aqueous medium and form a water-soluble acid form, are also referred to in the prior art as acid gases.
- Ionic or ionizable compounds, eg salts can be separated with or from the liquid. Methods such as electrodialysis using suitable membranes are known from the prior art for separation from an aqueous medium.
- Electrodialysis is a process for separating ions in salt solutions. Desalination, separation and concentration of salts, acids and bases are possible applications of the electrodialysis process. The necessary separation of the ions takes place by means of an electrical field applied via an anode and a cathode and via ion exchange membranes or semipermeable, ion-selective membranes. Electrodialysis is therefore an electrochemically driven membrane process in which Ion exchange membranes can be used in combination with an electrical potential difference to separate ionic compounds from, for example, uncharged solvents or impurities.
- electrodialysis devices consist of an alternating arrangement of anion and cation exchange membranes, which are arranged between two electrodes, and where the externally attached electrodes are separated from the processes taking place on the membranes and in are immersed in a separate chamber by an electrically conductive, aqueous electrode solution, which is electrolytically decomposed. Hydrogen gas is produced at the cathode and oxygen gas is produced at the anode.
- the problem here is that if the concentration of the compounds dissolved in the liquid, water-soluble gases or gaseous compounds that chemically react with water on contact with water, such as carbonic acid or sulfur dioxide, is only low, the electrophoretic separation performance in the electrochemical process of electrodialysis is limited and there is an energetic loss due to the electrolysis of the water molecules taking place at the same time as the electrodialysis. Furthermore, there is usually the problem that the recording medium, i.e. the medium in which the compound to be separated or its reaction product with water is concentrated, must also be water-based in order to produce electrical conductivity and the separated compound or its Reaction product with water, must first be brought back into a gaseous state before it can be used.
- the recording medium i.e. the medium in which the compound to be separated or its reaction product with water is concentrated
- pressurized water scrubbing A well-known process for cleaning biogas from sulfur and carbon dioxide is the so-called pressurized water scrubbing.
- pressurized water scrubbing water and the raw biogas are cleaned under pressure in an absorber using the countercurrent principle, whereby the gases to be separated and a small part of the methane contained dissolve in the scrubbing solution .
- a subsequent material use of z. B. CO 2 is not possible with the pressurized water wash.
- amine scrubbing Another well-known process for separating carbon dioxide, hydrogen sulfide and other acidic gases from gas mixtures in natural gas processing is what is known as amine scrubbing.
- slightly alkaline aqueous solutions of amines such as diethanolamine and monoethanolamine, but also methyldiethanolamine, diisopropylamine, diisopropanolamine and Diglycolamine used, which can reversibly chemically absorb acidic gas components (chemisorption).
- the gas to be cleaned is usually introduced into the aqueous amine solution at a pressure of approx. 8 bar and at temperatures of approx. 40°C.
- CO 2 When CO 2 is absorbed in the amine/water mixture, the CO 2 first dissolves in the water and forms carbonic acid.
- the resulting carbonic acid first decomposes to form H + and HCO 3 'ions. These can then react with the amine so that the absorbed CO 2 is chemically reversibly bound, with carbamates being formed which can be redissolved in a desorber. In the desorber, the chemical equilibrium is reversed at high temperature and low pressure and the bound acidic gas is thus removed from the amine solution and released.
- amine scrubbing has the particular disadvantage that the amines used are harmful to health and are considered the third most common cause of workplace-related cancer.
- a gaseous element or element molecule or gaseous compound in particular carbon dioxide
- a gaseous element or element molecule or gaseous compound in particular carbon dioxide
- a separation membrane by means of a diffusive or electrophoretic process step and transferred into another aqueous medium (a receiving medium)
- a gas and/or a reactive compound of the separated compound is present in the aqueous medium, which can react with another element or Element molecule or compound is reacted or separated as a gas from the aqueous medium.
- the solubility and ionizability of the gaseous element or element molecule or the gaseous compound should preferably be increased in such a way that energy-efficient transport of the compound to be separated is made possible.
- the object of the present invention is to provide a new method for binding or absorption and subsequent storage of a gaseous element or element molecule or gaseous compound, especially acidic gases and especially carbon dioxide (CO 2 ), in aqueous media as well in the extraction of pure gaseous elements or element molecules or gaseous compounds, in particular carbon dioxide (CO 2 ).
- the object of the present invention therefore relates to the provision of methods for dissolution/binding/transport/reaction activation/chemical conversion and selective release of a water-soluble gaseous compound, in particular carbon dioxide.
- aqueous acceptor media which contain organic acceptor compounds which contain at least one amidino and/or guanidino group and at the same time have hydrophilic properties. It has been found that this enables a (e) solution/binding/transport/reaction activation/chemical conversion and selective release of a water-soluble gaseous compound.
- water-soluble means that the gaseous substance/gaseous compound reacts chemically with water when it comes into contact with it, e.g. B. to form an acid anhydride or an acid. It is then present in water as an organic or inorganic acid or, after dissociation in water, as the corresponding anion.
- Water-soluble reaction products can form when gaseous compounds are brought into contact with water.
- a reaction with water leads to the formation of hydrogen carbonate (HCO 3 ') and carbonate (CO 3 2- ), which are also referred to as carbon dioxide derivatives in the following.
- lyes of alkali and alkaline earth metals e.g. aqueous solutions of sodium hydroxide or potassium hydroxide
- aqueous solutions of sodium hydroxide or potassium hydroxide are used for the production of alkaline solutions.
- the use of these compounds to dissolve and absorb gaseous compounds in an aqueous medium in the presence of carbon dioxide leads to the formation of carbonates or hydrogen carbonates (the salts of carbonic acid) and these precipitate as a solid, such as calcium carbonate, which is practically insoluble in water. This is undesirable if the gaseous compound which has passed into the aqueous solution is to be recovered again in a pure and gaseous state.
- basic amino acids are defined as amino acids that have an amino group or N atoms with lone pairs of electrons in the amino acid residue (side chain). If these N atoms accept a proton, a positively charged side chain is formed.
- the amino acids histidine, lysine and arginine belong to the basic amino acids. According to the invention, preference is given here to basic amino acids which carry at least one guanidino and/or amidino group, such as arginine, for example.
- water-soluble compounds that carry one or more free guanidino and/or amidino group(s) can achieve a very good solution or absorption of carbon dioxide in an aqueous medium and at the same time a very stable binding of carbonate/bicarbonate -Anions on free guanidino/amidino groups are guaranteed. It could be shown that these properties of the acceptor media according to the invention can also be used to dissolve and bind other organic and inorganic gases/gaseous compounds, such as hydrogen sulfide or chlorine gas. As a result, the absorption capacity of gases/gas mixtures that are soluble in water and react with it to form water-soluble compounds can be increased considerably.
- the absorption capacity for carbon dioxide in water can be significantly increased by the presence of water-soluble compounds which carry one or more free guanidino and/or amidino group(s).
- the absorption in the aqueous medium, the reaction with water and the binding of carbon dioxide and its derivatives in water are increased or accelerated.
- acceptor compounds Compounds that have a free guanidino and/or amidino group are therefore called acceptor compounds below, and a medium in which at least one compound that has at least one free guanidino and/or amidino group is present is called acceptor medium below.
- An acceptor solution can therefore be provided with an aqueous solution in which at least one compound which has at least one free guanidino and/or amidino group and which is present in dissolved form.
- a method is preferred in which the solubility of a gaseous compound in an aqueous acceptor medium, i.e. in an acceptor solution, is increased.
- the gaseous compound is carbon dioxide.
- the aqueous acceptor medium i.e. an acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, is provided here, which has the technical effect of increased solubility of a gaseous compound, in particular carbon dioxide.
- solubility refers to the dissolution of water-soluble gases that react chemically with water when they come into contact with water, such as acid gases that form an acid or a weak acid when dissolved in water.
- a method is preferred in which an aqueous acceptor solution is provided which contains at least one acceptor compound which has at least one free guanidino and/or amidino group and is brought into contact with a gas or gas mixture.
- the present invention therefore relates in particular to a method in which an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group is provided and the aqueous acceptor solution is brought into contact with a gas or gas mixture containing carbon dioxide in order to to bind the carbon dioxide from the gas or gas mixture.
- a method is preferred in which an aqueous acceptor medium, ie an acceptor solution and a gas/gas mixture containing at least one gaseous component which dissolves in water to form an acid or anion, are brought into contact with one another, the at least one gaseous Compound which dissolves in water with the formation of an acid and/or an anion, through which at least one acceptor compound which is present in the acceptor medium, ie in the acceptor solution, is bound.
- a method is preferred for increasing the solubility and binding of gases which form an acid/anionic compound in water and/or are present in anionic form, ie acidic gases, in an aqueous acceptor medium in which at least one acceptor compound is present is a hydrophilic organic compound containing at least one amidino and/or guanidino group.
- a method is preferred in which gaseous compounds in an aqueous acceptor medium are bonded anionically to the acceptor compound.
- Anionic means that the bound gaseous compound dissociates in the acceptor solution and is present as an anion in the aqueous solution and the acceptor compound is profaned and forms the counter ion.
- the acceptor compound has a free guanidino and/or amidino group which can be profaned so as to provide the cation as a counter-ion to the anion of the gaseous compound in the acceptor solution.
- the method of the present invention therefore comprises at least the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; and b) contacting a gas containing carbon dioxide with the acceptor solution from step a).
- a method is preferred in which at least one hydrophilic organic compound containing at least one amidino and/or guanidino group is present in an aqueous acceptor medium in order to convert gaseous compounds which form acids on contact with water or are present therein in anionic form, to solve, neutralize and bind and / or to contact and react with other compounds or to release the bound gaseous compound selectively as a gas.
- a method is preferred in which at least one hydrophilic organic compound containing at least one amidino and/or guanidino group is present in an aqueous acceptor medium in order to dissolve, neutralize and bind acidic gases, in particular carbon dioxide.
- the aqueous acceptor medium containing the bound acidic gases, in particular carbon dioxide can be brought into contact with other compounds in order to convert the bound acidic gases, in particular carbon dioxide, for example in the case of carbon dioxide into carbonates or bicarbonates that are insoluble in water or poorly soluble in water, or to convert the bound acid gases, in particular carbon dioxide, selectively release as a gas, in particular as gaseous carbon dioxide.
- the present invention therefore relates to a method for selectively binding and storing carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b).
- Preferred embodiments include step c): c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b) at atmospheric pressure.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium.
- the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting carbonate/bicarbonate anions in the acceptor solution of step b) through a separating membrane into an aqueous uptake and release medium.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium. c2) Releasing carbon dioxide as a gas phase from the absorption and release medium containing bound carbon dioxide/the carbon dioxide derivatives from step c).
- the present invention therefore relates to a method for selectively binding, transporting and storing carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting carbonate/bicarbonate anions in the acceptor solution of step b) through a separating membrane into an aqueous uptake and release medium. c2) Releasing carbon dioxide as a gas phase from the uptake and release medium containing carbonate/bicarbonate anions from step c).
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) adding a reaction compound to the acceptor solution from step b) containing bound carbon dioxide/carbon dioxide derivatives.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; and d2) adding a reaction compound to the uptake and release medium containing bound carbon dioxide/carbon dioxide derivatives from step c).
- the present invention therefore relates to a method for selective binding, Transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting carbonate/bicarbonate anions in the acceptor solution of step b) through a separating membrane into an aqueous uptake and release medium. d2) adding a reaction compound to the uptake and release medium containing carbonate/bicarbonate anions from step c).
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- the present invention therefore preferably relates to methods for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- step c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and c2) releasing carbon dioxide as a gas phase from the uptake and release medium containing bound carbon dioxide/the carbon dioxide derivatives from step c); or d2) adding a reaction compound to the uptake and release medium containing bound carbon dioxide/carbon dioxide derivatives from step c).
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- step c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; and c2) releasing carbon dioxide as a gas phase from the uptake and release medium containing bound carbon dioxide/the carbon dioxide derivatives from step c); or d2) adding a reaction compound to the uptake and release medium containing bound carbon dioxide/carbon dioxide derivatives from step c).
- a method for dissolving carbon dioxide in an aqueous medium with the formation of carbonate/bicarbonate anions is preferred, in which stable physicochemical bonding of the carbonate/bicarbonate anions formed in the aqueous acceptor medium takes place at the same time.
- a method is preferred in which the dissolution of carbon dioxide and the binding of the resulting carbonate/bicarbonate anion through/to free guanidino and/or amidino groups takes place in an aqueous acceptor medium.
- water-soluble acceptor compounds are compounds which carry free guanidino and/or amidino groups which, when dissolved in water, accept or can accept at least one proton.
- water-soluble acceptor compounds are amino acids which carry at least one guanidino and/or amidino group and bind or can bind at least one proton in aqueous solution.
- a method is preferred in which the water-soluble acceptor compounds for dissolving carbon dioxide and for binding and transporting carbon dioxide or its derivatives in water and the resulting carbonate/bicarbonate anions, arginine and/or arginine derivatives.
- the at least one acceptor compound which has a free guanidino and/or amidino group is an arginine derivative or, most preferably, arginine.
- Acceptor solutions containing at least one arginine derivative or particularly preferably arginine have proven to be particularly advantageous and effective for binding and storing carbon dioxide in an aqueous medium.
- the contacting of the gas or gas mixture with the aqueous acceptor medium can be carried out in various process embodiments which are known in the prior art.
- the two phases can thus be brought into contact by introducing the gas phase into the liquid phase, or the gas phase is passed over a surface which is wetted with the liquid phase.
- processes for contacting gas and liquid phases are used which result in a very large interface between the phases. These are devices such.
- a method in which a gas/gas mixture is brought into contact with an acceptor medium is preferred.
- a method is preferred in which, by bringing a gas/gas mixture into contact with an acceptor medium, the proportion of carbon dioxide present therein completely dissolves in the acceptor medium and is bound therein.
- a method is preferred in which, by bringing a gas/gas mixture into contact with an acceptor medium, the proportion of carbon dioxide present therein and/or the reaction products of carbon dioxide with water is/are completely bound by an acceptor compound.
- a method is preferred in which a large interface is produced between the aqueous acceptor medium and the gas phase containing carbon dioxide.
- a method is preferred in which the dissolving and binding of carbon dioxide and its derivatives takes place without pressurization of the acceptor solution.
- a method is preferred in which the dissolving and binding of carbon dioxide takes place at atmospheric pressure.
- a method is preferred in which the dissolving and binding of carbon dioxide takes place without excess pressure.
- a method in which the dissolving and binding of carbon dioxide takes place at normal pressure is preferred.
- a method is preferred in which the dissolving and binding of carbon dioxide takes place at atmospheric pressure of 101.325 kPa.
- a method is preferred in which the dissolving and binding of carbon dioxide takes place without pressure.
- Preferred embodiments of the method according to the invention include step b): b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) taking place at normal pressure or atmospheric pressure.
- Preferred embodiments of the method according to the invention comprise step b): b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) taking place at atmospheric pressure.
- Preferred embodiments of the method according to the invention comprise step b): b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) taking place at atmospheric pressure.
- Preferred embodiments of the method according to the invention include step b): b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) being carried out without pressurization.
- Preferred embodiments of the method according to the invention comprise step b): b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) taking place without pressure.
- contacting under normal pressure or at atmospheric pressure or without pressurization means that the acceptor solution is provided under normal pressure or atmospheric pressure or without pressurization.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- step b) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b), the contacting in step b) taking place at atmospheric pressure and/or the acceptor solution from step c) being stored at atmospheric pressure.
- the contacting in step b) takes place at atmospheric pressure; and wherein the acceptor solution of step c) is stored at atmospheric pressure.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- This aspect of the invention results in further particularly advantageous effects for further method versions. It is thus possible to store the carbon dioxide absorbed in the acceptor solution, or its reaction products with water, without pressure, ie without excess pressure or at atmospheric pressure or normal pressure, over a period of >6 months without loss.
- transporting means transferring the acceptor solution containing bound carbon dioxide into a transportable vessel, such as a large container, container or barrel, etc. Suitable transport containers for transporting liquids are well known to those skilled in the art.
- safe storage and transport does not refer to the transport of the bound carbon dioxide/the carbon dioxide derivatives containing bound carbon dioxide in the acceptor solution through a separating membrane into an aqueous absorption and release medium.
- the transport of the bound carbon dioxide/the carbon dioxide derivatives in the acceptor solution containing bound carbon dioxide through a separating membrane into an aqueous uptake and release medium can therefore also be referred to herein as membrane transport.
- a method is preferred in which the dissolving and binding of gaseous carbon dioxide and its reaction products with water takes place without pressurization of the acceptor solution.
- a method is preferred in which the dissolving and binding of gaseous carbon dioxide and its reaction products with water in the acceptor solution takes place at atmospheric pressure or at standard pressure.
- a method is preferred in which a gas containing carbon dioxide is brought into contact with the acceptor solution without pressure.
- a method is preferred in which a gas containing carbon dioxide is brought into contact with the acceptor solution at atmospheric pressure.
- a method is preferred in which the storage and/or transport (in a transport container) of the acceptor solution containing dissolved and bound carbon dioxide or its reaction products with water takes place without pressure.
- a method is preferred in which the storage and/or transport (in a transport container) of the acceptor solution containing dissolved and bound carbon dioxide or its reaction products with water takes place at atmospheric pressure.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing and/or transporting the acceptor solution containing bound carbon dioxide from step b) in a storage container and/or transport container, it being preferred here that the contacting in step b) takes place at atmospheric pressure and/or the acceptor solution from step c) is stored or transported at atmospheric pressure in the storage container and/or the transport container.
- Embodiments are also preferred in which the contacting in step b) takes place at atmospheric pressure and in which the acceptor solution from step c) is stored or transported at atmospheric pressure in the storage container and/or the transport container.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the Acceptor solution according to step b) through a separating membrane into an aqueous uptake and release medium; or
- the contacting in step b) takes place at atmospheric pressure and/or the acceptor solution from step c) at atmospheric pressure in a storage container and /or is stored or transported in a transport container.
- the contacting in step b) takes place at atmospheric pressure and in which the acceptor solution from step c) is stored or transported at atmospheric pressure in the storage container and/or the transport container.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing and/or transporting the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- the contacting in step b) takes place at atmospheric pressure and/or the acceptor solution from step c ) is stored or transported at atmospheric pressure in a storage container and/or a transport container.
- the contacting in step b) takes place at atmospheric pressure and in which the acceptor solution from step c) is stored or transported at atmospheric pressure in the storage container and/or the transport container.
- the amount of carbon dioxide that is dissolved and bound per unit of time can be increased by contacting the acceptor medium with the gas/gas mixture containing carbon dioxide, which takes place while the gas/gas mixture is pressurized.
- the aqueous acceptor solution containing compounds bearing guanidino and/or amidino groups is enriched or saturated with dissolved carbon dioxide in an enrichment device which enables pressurization. This enables the accumulation to be accelerated or the point in time at which saturation has occurred to be reached.
- the presence of saturation of the acceptor medium with carbon dioxide can be recognized, for example, by the fact that the concentration of carbon dioxide in the gas mixture that has been passed through the enrichment device and exits increases.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group in an enrichment device , which allows pressurization; b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) being carried out under pressurization, preferably until the acceptor solution is saturated with carbon dioxide.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- step b) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b), the acceptor solution from step a) being provided in an enrichment device which enables pressurization; and the contacting in step b) is carried out under pressurization, preferably until the acceptor solution is saturated with carbon dioxide.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- step b) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step a) being provided in an enrichment device which enables pressurization; and the contacting in step b) is carried out under pressurization, preferably until the acceptor solution is saturated with carbon dioxide.
- a method is preferred in which a gas/gas mixture containing carbon dioxide is contacted with the acceptor solution until a carbon dioxide concentration of the gas of ⁇ 100 ppm is reached.
- a method is preferred in which a gas/gas mixture containing carbon dioxide is contacted with the acceptor solution until a carbon dioxide concentration of the gas of ⁇ 100 ppm is reached, the contacting taking place under pressure.
- Preferred is a method in which a gas containing carbon dioxide with the acceptor solution in in relation to the number of carbon dioxide molecules present in the gas/gas mixture, there is an excess of free guanidino and/or amidino groups of the acceptor compounds, until a carbon dioxide concentration of the gas of ⁇ 100 ppm is reached.
- the process can also be used to convert the extracted and bound carbon dioxide and its derivatives.
- concentration/content of carbon dioxide and/or carbon dioxide derivatives in water is as high as possible. Therefore, it is preferred to contact an acceptor medium with a gas/gas mixture containing or consisting of carbon dioxide until no further uptake therein occurs, i.e. until the acceptor medium is saturated with carbon dioxide.
- a gas/gas mixture containing or consisting of carbon dioxide until no further uptake therein occurs, i.e. until the acceptor medium is saturated with carbon dioxide.
- the carbon dioxide content in the gas/gas mixture that has been brought into contact with the acceptor medium increases again, e.g. increases to >100 ppm.
- the absorption capacity of the acceptor medium is exhausted and the acceptor medium is saturated with carbon dioxide.
- an acceptor medium saturated with carbon dioxide is preferred.
- an acceptor solution which is saturated with carbon dioxide is obtained in step b) of the process according to the invention.
- gaseous compounds which do not correspond to carbon dioxide are removed from an aqueous acceptor medium Relaxing to atmospheric pressure and/or applying a negative pressure to the aqueous acceptor medium.
- gases/gas fractions that do not correspond to carbon dioxide or its reaction products with water are removed from the aqueous acceptor medium by depressurization or application of a reduced pressure.
- the selective separation of carbon dioxide preferably takes place after the expansion phase.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group in an enrichment device which enables pressurization; b) contacting a gas containing carbon dioxide with the acceptor solution from step a), the contacting in step b) being carried out under pressurization, preferably until the acceptor solution is saturated with carbon dioxide; and b') decompression of the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b) at atmospheric pressure or at reduced pressure.
- the present invention therefore relates to a method for selectively binding and storing carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group in an enrichment device , which allows pressurization; b) contacting a gas containing carbon dioxide with the acceptor solution from step a) under pressurization; and b') leaving the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b) at atmospheric pressure or at reduced pressure.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- step b) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b), the acceptor solution from step a) being provided in an enrichment device which enables pressurization; and the contacting in step b) takes place under pressurization, preferably until the acceptor solution is saturated with carbon dioxide, the method further comprising step b') after step b): b') depressurizing the acceptor solution from step b) containing bound bound carbon dioxide/ Carbon dioxide derivatives at atmospheric pressure or at reduced pressure.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- step b) Transporting bound carbon dioxide / carbon dioxide derivatives in the acceptor solution according to step b) through a separating membrane in an aqueous recording and Release medium, wherein the acceptor solution of step a) is provided in an enrichment device that allows pressurization; and the contacting in step b) takes place under pressurization, preferably until the acceptor solution is saturated with carbon dioxide, the method further comprising step b') after step b): b') depressurizing the acceptor solution from step b) containing bound bound carbon dioxide/ Carbon dioxide derivatives at atmospheric pressure or at reduced pressure.
- the carbon dioxide dissolved in the aqueous acceptor medium, or its reaction products with water is released as a gas phase.
- electrolysis a direct electric current is passed through two electrodes into a conductive liquid (electrolyte solution).
- electrolysis produces reaction products from the substances contained in the electrolyte at the electrodes.
- a DC voltage to an aqueous acceptor medium to which carbon dioxide has been applied, carbon dioxide is released in the form of gas bubbles at both electrodes. It has been found that this allows the entire content of (bound) carbon dioxide, or its reaction products with water, to be removed from the aqueous acceptor medium.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c1) releasing carbon dioxide as a gas phase from the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b).
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c1) releasing carbon dioxide as a gas phase from the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b) by applying a DC voltage to the acceptor solution from step b).
- a preferred embodiment therefore relates to a method for the selective binding and release of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c1) containing carbon dioxide as a gas phase from the acceptor solution bound carbon dioxide/carbon dioxide derivatives from step b) by means of electrolysis.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; and c2) releasing carbon dioxide as a gas phase from the absorption and release medium containing bound carbon dioxide/the carbon dioxide derivatives from step c) by applying a DC voltage to the absorption and release medium from step c).
- a method is preferred in which an aqueous acceptor medium is brought into contact with and loaded with carbon dioxide and then the carbon dioxide dissolved/bound in the acceptor medium, or its reaction products with water, is released as carbon dioxide gas by applying a DC voltage to the acceptor medium will.
- carbon dioxide can be made available as a highly pure gas phase by spatially separating the carbonate/bicarbonate anions in the acceptor solution using an electrophoretic process and then releasing carbon dioxide by water separation.
- open-pored membranes are suitable for enabling dissolved carbon dioxide or carbonate/bicarbonate anions to be passed through electrophoretically.
- the electrophoretic transport of dissolved carbon dioxide or carbonate/bicarbonate anions takes place towards the anode. If an electrical DC voltage is applied to the electrodes, anions migrate to the anode and the anions can pass through a positively charged anion exchange membrane.
- cathode chamber/chamber for receiving the acceptor solution hereinafter referred to as the acceptor chamber
- the absorption and release chamber in which the release of carbon dioxide in the form of a gas phase takes place
- anode chamber is particularly suitable for obtaining gaseous carbon dioxide in its purest form.
- the acceptor chamber To carry out an electrophoretic separation of dissolved carbon dioxide and its derivatives from the acceptor solution, the acceptor chamber must be connected to the receiving and release chamber on the anode side by an electrically conductive medium, in which the transported compounds are preferably received and/or here a release or conversion of these can be done.
- the medium present in the uptake and release chamber is preferably an aqueous solution and is hereinafter referred to as uptake and/or release medium.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step b) being located in or being introduced into an acceptor chamber of an electrodialysis device ; and the transport of the carbon dioxide/the carbon dioxide derivatives according to step c) takes place by means of an electrical gradient which is produced between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting carbonate/bicarbonate anions from the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step b) being in or being introduced into an acceptor chamber of an electrodialysis device ; and the transport of the carbonate/bicarbonate anions according to step c) takes place by means of an electrical gradient which is produced between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane.
- water-soluble organic compounds which carry one or more acid groups are particularly suitable for removing dissolved carbon dioxide/carbonate/bicarbonate anions which/which have passed through a separation membrane into the chamber containing the receiving and/or or release medium, to convert into a gaseous state or to demix. It is particularly advantageous if this organic compound is not transported in the electric field and/or cannot leave the chamber containing the absorption and/or release medium through the separation membrane due to its molecular size.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives from the acceptor solution from step b) through a separation membrane into an aqueous uptake and release medium, wherein the aqueous uptake and release medium contains an organic or inorganic acid.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives from the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, wherein the aqueous uptake and release medium contains an organic or inorganic acid and has a pH in the range between 1 and 7, more preferably between 2 and 6 and more preferably between 3 and 5.
- a further preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group ; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxides/carbon dioxide derivatives from the Acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, wherein the aqueous uptake and release medium contains an organic acid and preferably has a pH in the range between 1 and 7, more preferably between 2 and 6 and more preferably between 3 and 5.
- the organic acid is preferably a compound which carries at least one acid group and has an isoelectric point in the pH range between 3 and 5, preferably between 3.5 and 4.5.
- the organic acid is preferably selected from the group consisting of citric acid, tartaric acid and ascorbic acid.
- the organic acid is citric acid.
- the aqueous uptake and release medium contains citric acid.
- the aqueous uptake and release medium contains an organic acid, wherein the organic acid is an acidic amino acid having a carboxylic acid group (-COOH) on the side chain.
- the aqueous uptake and release medium contains an organic acid, in which case the organic acid is an amino acid bearing acid groups.
- the aqueous uptake and release medium contains an organic acid, the organic acid being selected from the group comprising or consisting of aspartic acid and glutamic acid.
- the aqueous uptake and release medium contains an organic acid, the organic acid being selected from the group comprising or consisting of citric acid, tartaric acid and ascorbic acid. Tartaric acid is particularly preferred.
- the aqueous uptake and release medium contains an inorganic acid, the inorganic acid preferably being selected from the group comprising or consisting of sulfuric acid or diphosphoric acid.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium containing citric acid, the acceptor solution from step b) being in an acceptor chamber of an electrodialysis device or into this is initiated; and the transport of the carbon dioxide/the carbon dioxide derivatives according to step c) takes place by means of an electrical gradient which is produced between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane.
- the pH of the uptake and/or release medium preferably adjusts itself through the dissociation of the dissolved amino acids.
- Amino acids do not exhibit electrophoretic mobility at the isoelectric point. Therefore, it is particularly advantageous if aqueous dissolved amino acids are present at their isoelectric point in the acceptor medium and the uptake and/or release medium. This results in the particularly advantageous effect that the compounds that are responsible for the solution, the transport on the one hand and for the demixing/degassing of carbon dioxide/bicarbonate anions on the other hand, do not mix or are consumed because they are in remain with the respective solutions.
- the absorption medium according to the invention fulfills the condition that carbon dioxide or carbonate/bicarbonate anions are absorbed and bound in the medium and the absorbed/bound carbon dioxide or carbonate/bicarbonate anions can be removed and transported by the separation medium, so that the release of carbon dioxide can take place spatially remote from the separation medium or the receiving and release chamber.
- a method is preferred in which a solution, the electrophoretic transport and the demixing/degassing of carbon dioxide/carbonate/bicarbonate anions are carried out by basic amino acids in an aqueous acceptor medium and acid-group-bearing in an aqueous uptake and/or release medium Amino acids are at their isoelectric point.
- a method is preferred in which a gas or gaseous compounds and their derivatives are bound in an aqueous acceptor medium and the gas/the gaseous compound or their derivatives are transported in water through a separation medium (separation membrane) by means of an electrophoretic process and thereby into a receptacle - and release medium reach.
- a separation medium separation membrane
- a method is preferred in which a gas or gaseous compounds and derivatives thereof are bound in an aqueous acceptor medium and the gas/gaseous compound or derivatives thereof are transported in water through a separation medium by means of an electrophoretic method and thereby reach an absorption and release medium , in which they are released as a gas phase and/or chemically converted.
- a method is preferred in which the carbon dioxide/carbon dioxide derivatives transported through the separation medium (separation membrane) are released in the receiving and releasing chamber in the form of a pure carbon dioxide gas.
- the preferred basic amino acids are arginine and lysine.
- the preferred acid group-bearing amino acids are aspartic acid and glutamic acid.
- carbon dioxide is therefore released as a gas from the absorption and release medium in a release device into which the absorption and release medium is introduced from an absorption and release chamber (cf. FIG. 1).
- a release device into which the absorption and release medium is introduced from an absorption and release chamber (cf. FIG. 1).
- the provision of interfaces in a release device for separating carbon dioxide is preferred. Hydrophobic interfaces are preferred.
- Suitable devices for increasing interfaces are, for example, random packings.
- a method is preferred in which, after the uptake of carbon dioxide/carbonate/bicarbonate anions in an uptake and release medium in an uptake and release chamber, this is introduced into a release device and carbon dioxide is released therein as a gas.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step b) being in or introduced into an acceptor chamber of an electrodialysis device will; and the transport of the carbon dioxide/the carbon dioxide derivatives according to step c) takes place by means of an electrical gradient which is established between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane; wherein the method after step c) comprises step c3): c3) releasing carbon dioxide
- carbon dioxide is released as a gas phase by applying a DC voltage to the uptake and release medium from step c3).
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step b) being in or introduced into an acceptor chamber of an electrodialysis device will; and the transport of the carbon dioxide/the carbon dioxide derivatives according to step c) takes place by means of an electrical gradient which is established between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane; wherein the method after step c) comprises step c3'): c3')
- the method comprises step c3) after step c3'): c3) releasing carbon dioxide as a gas phase from the uptake and release medium containing bound carbon dioxide/the carbon dioxide derivatives from step c3') in the release chamber.
- a preferred embodiment of the present invention therefore relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution from step b) through a separating membrane into an aqueous uptake and release medium, the acceptor solution from step b) being in or introduced into an acceptor chamber of an electrodialysis device will; and the transport of the carbon dioxide/the carbon dioxide derivatives according to step c) takes place by means of an electrical gradient which is established between the acceptor chamber and an uptake and release chamber, the acceptor chamber and the uptake and release chamber being separated from one another by the separating membrane; wherein the method after step c) comprises the steps c3') and c3):
- the gas released in the release chamber/release device or from the receiving and release medium exclusively or almost consists exclusively of carbon dioxide. It was able to be documented that when the method is carried out according to the invention with a release of carbon dioxide as a gas phase in a release device, there is no increase in the electrical resistance during the electrophoretic transport of carbon dioxide/carbonate/bicarbonate anions within the electrodialysis device by gas separation at the Separation membrane or gas bubble formation inside the receiving and releasing chamber.
- a method for obtaining and obtaining a pure carbon dioxide gas is preferred.
- a clean gas contains less than 0.5% by volume of impurities from other compounds.
- ionic liquids are used as the release medium.
- Ionic liquids are particularly advantageous because they are generally not water-soluble and there is no electron-optical transport of the anionic and cationic compounds that make up the ionic liquid. Therefore, an application of ionic liquids as a release medium in connection with an open-pored membrane, which separates the acceptor chamber from the receiving and release chamber, is a particularly preferred embodiment of the method.
- a method is preferred in which a gas or gaseous compounds and their derivatives are bound in an aqueous acceptor medium and the gas/the gaseous compound or their derivatives are transported in water through a separation medium (separation membrane) by means of an electrophoretic process and thereby into a receptacle - Get and release medium, wherein the recording and release medium is an ionic liquid.
- a separation medium separation membrane
- a method is preferred in which a gas or gaseous compounds and their derivatives are bound in an aqueous acceptor medium and the gas/gaseous compound or their derivatives are transported in water by means of an electrophoretic process through a separation medium (separation membrane) and thereby into a receiving and release medium that is an ionic liquid, in which they are chemically reacted.
- a separation medium separation membrane
- the separation of carbon dioxide from a gas/gas mixture takes place semicontinuously or continuously.
- a device is preferred for this purpose in which carbon dioxide is dissolved/dissociated in one of the aqueous acceptor solutions according to the invention and at the same time the dissolved carbon dioxide or the carbonate/bicarbonate anions are separated from the acceptor solution.
- the selective separation of the bound carbon dioxide/carbonate/bicarbonate anions preferably takes place by transport through a separation medium (separation membrane).
- separation medium separation medium for separating dissolved carbon dioxide or carbonate-bicarbonate anions is preferred.
- Electrophoretic separation is preferred.
- the use of an electro-dialysis unit is particularly preferred.
- the chambers containing the acceptor solution are gassed with a gas/gas mixture containing carbon dioxide.
- the carbon dioxide-reduced gas/gas mixture emerging from this chamber is then fed into the next chamber containing the acceptor solution.
- This arrangement can be repeated as often as you like.
- the gassing can take place both in the chambers containing the acceptor solution of the respective dialysis cell and in a container outside of this, with circulation being set up between the container and the respective chamber of the dialysis unit.
- the finest possible distribution of the gas/gas mixture in the acceptor medium is preferred. Techniques from the prior art can be used for this.
- a gas scrubbing column can be set up with such a process arrangement, so that the carbon dioxide-containing gas stream is in multiple sequential contact with the acceptor medium is brought.
- a method is preferred in which an acceptor medium is reused without loss, following a separation of carbon dioxide/carbonate/bicarbonate anions from this medium, in order to dissolve and bind carbon dioxide again therein.
- a process for removing carbon dioxide from gas or gas mixtures is preferred.
- a method can be provided with which complete or almost complete removal of carbon dioxide from a gas or gas mixture is made possible by bringing it into contact with an aqueous acceptor medium at atmospheric pressure and in which gaseous carbon dioxide is subsequently selectively recovered in the purest or purest form can be made available.
- pure means a carbon dioxide content of >99.5% by volume and pure a carbon dioxide content of >98.5% by volume.
- the method is also aimed at the selective separation and extraction and production of pure carbon dioxide.
- a process for the selective separation, recovery and production of carbon dioxide which is pure or ultra-pure is preferred.
- Pre-cleaning of a gas stream in which carbon dioxide is to be bound or bound and recovered is therefore preferred.
- a method is preferred in which, before the gas/gas mixture containing carbon dioxide is brought into contact with an acceptor medium, liquid and solid components and gas components which do not correspond to carbon dioxide and which dissolve in water or on contact are separated/adsorbed form water-soluble reaction products with water.
- a method for the adsorption, transport and selective release of carbon dioxide can thus be provided in which no corrosive or health-hazardous compounds are used and in which the aqueous acceptor medium is completely recirculated after the separation of the carbon dioxide bound therein and used for renewed absorption of carbon dioxide can.
- a method is preferred in which an aqueous acceptor medium is provided for the absorption, transport and selective release of carbon dioxide, in which no corrosive or harmful compounds are used and in which the aqueous acceptor medium is completely recirculated after the separation of the carbon dioxide bound therein and used for re-adsorption of carbon dioxide can be used.
- a method is preferred for the reversible binding of gaseous compounds to an acceptor compound dissolved in water in an aqueous acceptor medium.
- Preferred is a method in which the reversible binding between a gaseous compound and a water-soluble acceptor compound present in an aqueous acceptor medium occurs via a reaction product of the gaseous compound with water.
- a method is preferred in which the reaction product of a gaseous compound with the water phase of an aqueous acceptor medium is reversibly bound by a dissolved acceptor compound.
- a method is preferred in which gaseous compounds are bound in an aqueous acceptor medium by an acceptor compound and in which the bound gaseous compounds can be released again as gas by changing the pH of the acceptor solution, displacing the gaseous compound by an additive of anionic compounds or by an electrophoretic separation.
- a method is preferred in which gaseous compounds are bound in an aqueous acceptor medium and the gaseous compound is subsequently released again, with the acceptor compound being regenerated and the acceptor medium then being made available for binding a gaseous compound again.
- the gas/gas mixture that is collected after being brought into contact with the acceptor medium can be passed through a medium that is suitable for binding and/or separating hydrogen therein and recovering and/or converting it directly or in a secondary circuit be able.
- the method is also aimed at the production and production of hydrogen.
- a method is preferred in which hydrogen is produced by bringing a gas/gas mixture containing carbon dioxide into contact with an acceptor medium and the hydrogen produced is adsorbed and/or separated and recovered.
- Preferred is a method for Production and extraction of hydrogen, in which a gas/gas mixture is brought into contact with an acceptor medium.
- Acceptor media for the production and production of hydrogen are preferred.
- a method is preferred in which gaseous compounds are bound in an acceptor medium and are brought into contact with one or more compounds therein, with a physico-chemical or chemical reaction between the gaseous compound bound to the acceptor compound or the anionic form of the gaseous Connection and the at least one further connection takes place.
- a method is preferred in which gaseous compounds are bound in an acceptor medium by an acceptor compound which enables and/or catalyzes a reaction between the bound gaseous compound or the anionic form of the gaseous compound with one or more other compounds.
- salts of alkali and alkaline earth metals can be dissolved very easily in an aqueous acceptor medium according to the invention. Surprisingly, there was no exothermic reaction or, compared to a dissolution process in water, a very slight exothermic reaction. This applies in particular to the dissolving of calcium, iron and aluminum salts such as calcium, iron or aluminum chloride. Surprisingly, this results in further particularly advantageous possibilities in the production of carbonates and bicarbonates.
- a compound (reaction compound) with which a chemical conversion with carbon dioxide and/or carbonate and/or hydrogen carbonate anions is to take place can be carried out in an acceptor medium containing at least one acceptor compound in a very advantageous manner, easily, quickly and without causing an exothermic reaction in the aqueous medium, can be completely dissolved and contacted with carbon dioxide/carbonate/bicarbonate anions without liberation of carbon dioxide. It has been found that these advantageous effects also result when a reaction compound is provided in the same way in an uptake and release medium or a reaction medium for chemical conversion.
- Preferred is a method in which at least one reaction compound is brought into solution together with an acceptor compound and the reaction compound(s) dissolved therein is/are contacted with carbon dioxide and/or carbonate and/or bicarbonate anions in order to convert them react chemically with carbon dioxide and/or carbonate and/or bicarbonate anions.
- gaseous compounds can be chemically converted in an aqueous acceptor medium by binding them in the form of the reaction product with water to a dissolved acceptor compound and bringing them into contact with other compounds in this form.
- cations/cationic compounds which can form carbonates or bicarbonates are introduced by selectively introducing them into the acceptor solution using an electrophoretic method.
- This is preferably done in a process arrangement in which an electrolyte solution in which the cation or cations/cationic compounds suitable for producing carbonate or bicarbonate are dissolved are introduced into an electrodialysis device in an electrolyte chamber, which instead of a receiving and Release chamber is connected to one of the acceptor chamber containing the acceptor solution, with a cation-selective membrane being located between the electrolyte chamber and the acceptor chamber, through which the chambers are electrically coupled to one another.
- an acceptor solution can be present in the acceptor chamber that is already saturated with carbon dioxide or is continuously exposed to carbon dioxide during the dialysis process.
- chemical conversion of carbon dioxide and/or carbonate and/or bicarbonate with other compounds is also possible.
- reaction compounds Compounds that react or can be reacted with carbon dioxide and/or carbonate and/or bicarbonate by being in or being transported into an acceptor medium or reacting outside the acceptor medium with carbon dioxide and/or carbonate and/or bicarbonate Anions dissolved and transported by means of an acceptor medium are hereinafter referred to as reaction compounds.
- reaction compounds Compounds that react or can be reacted with carbon dioxide and/or carbonate and/or bicarbonate by being in or being transported into an acceptor medium or reacting outside the acceptor medium with carbon dioxide and/or carbonate and/or bicarbonate Anions dissolved and transported by means of an acceptor medium are hereinafter referred to as reaction compounds.
- a reaction process could be presented with which it is possible to bring reaction compounds with carbonate/bicarbonate anions into contact and chemically react them with one another.
- the conversion process can be designed in various embodiments and can be carried out with various reaction compounds.
- Carbonates or hydrogen carbonates produced in this way are chemically pure and are present directly in the form of very small particles of ⁇ 1 m or can be divided into very small particles with little energy expenditure.
- anions of the dissolved salt in the acceptor solution such as chloride ions
- the anions of a salt are separated by electrodialysis, which takes place after introducing a salt or a solution of the salt into the aqueous acceptor medium or after bringing the aqueous acceptor medium into contact with a gas/gas mixture containing carbon dioxide.
- Preferred is a method in which the acceptor compound present in an acceptor medium is regenerated following the binding of a gaseous compound or the anionic form of the gaseous compound, by the acceptor medium by means of electrodialysis, contacting with ion exchange compounds or adsorbents, of anionic Compounds, except for hydroxide anions, are cleaned up.
- the process is also aimed at the production of chemically pure carbonates and hydrogen carbonates, which are available in powder form.
- the carbonates and bicarbonates are preferably in amorphous form.
- a process for the production of carbonates and bicarbonates is preferred.
- carbonates and hydrogen carbonates can be produced by an inventive absorption and dissolution of carbon dioxide which is released from a regenerative raw material source, such as in a fermentation to form a biogas or the combustion of wood. If regenerative cations/cationic compounds, which can be obtained, for example, by one of the processes for regenerating organic and inorganic compounds, and regenerative energy are used to carry out the process, it is now possible to use regenerative carbonates and hydrogen carbonates to manufacture.
- a process for the production of regenerative carbonates and hydrogen carbonates is preferred.
- Regenerative carbonates and bicarbonates are preferred.
- the method is also aimed at providing carbon dioxide or carbonate/bicarbonate anions in a high concentration in an aqueous acceptor medium and chemically reacting it with other compounds.
- a method is preferred in which carbon dioxide or carbonate/bicarbonate anions are provided in a high concentration in an aqueous acceptor medium and chemically reacted therein with other compounds.
- the method is therefore also aimed at a conversion process with which reaction products can be obtained from a conversion of organic and/or inorganic compounds with dissolved or dissolved and transported gases/gaseous compounds and/or their derivatives.
- a conversion process in which organic and/or inorganic compounds are brought into contact with dissolved or dissolved and transported gases/gaseous compounds and/or derivatives thereof and are reacted is preferred.
- Reaction products obtainable by reacting organic and/or inorganic compounds with a dissolved or dissolved and transported gas/gaseous compounds and/or their derivatives are preferred.
- a method for the selective binding, transport, reaction activation, conversion and/or release of carbon dioxide is preferred.
- the object is thus achieved by a method in which carbon dioxide is dissolved in an aqueous medium containing dissolved compounds bearing guanidino and/or amidino groups and stored with and/or in it and/or transported and/or converted and/or released will.
- solubility of carbon dioxide in an aqueous medium is significantly increased compared to pure water by compounds dissolved therein that contain free guanidino and/or amidino groups, and that the carbon dioxide remains bound in the aqueous solution. Also surprising was the observation that the solubility of compounds bearing guanidino and/or amidino groups can be increased as the amount of bound carbon dioxide increases. For example, for arginine, whose solubility limit in water is 0.6 mol/l at 20°C (or, depending on the source, approx.
- carbon dioxide or carbonate/bicarbonate anions can be released without pressure (at atmospheric pressure or standard pressure) in a concentration of preferably >0.5 mol /l, more preferably of >1.0 mol/l, more preferably of >1.5 mol/l, more preferably of >2.0 mol/l, more preferably of >2.5 mol/l, more preferably of >3.0 mol/l and even more preferably >3.5 mol/l.
- the aqueous solution for absorbing, transporting, converting, releasing and/or storing carbon dioxide is provided in the form of a acceptor solution.
- the acceptor solution is preferably provided in an acceptor chamber or acceptor device.
- the acceptor device contains a device which is suitable for producing the largest possible exchange surface between a gas/gas mixture and the acceptor medium and/or for bringing a gas/gas mixture into contact with the acceptor medium. Methods for this are known from the prior art.
- One form is a gas washing device (see also FIG. 1) or gas washing column.
- a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) in a gas washing device or gas washing column is therefore preferred.
- the gas containing carbon dioxide is filtered and/or washed before contact with an acceptor solution according to the invention in order to remove non-gaseous components.
- these can be scrubbed out of the carbon dioxide-containing gas in an upstream gas scrubbing column.
- a gas mixture is preferably first subjected to washing using an acidic solution. Surprisingly, it was found that the carbon dioxide concentration of a gas/gas mixture can be reduced significantly more quickly when it is subsequently brought into contact with an acceptor solution than without prior activation of the gas mixture by bringing it into contact with an acidic solution.
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) storing and/or transporting the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives from step b); and or
- a method is preferred in which a gas mixture is activated by bringing it into contact with an acidic solution, which improves the solubility of carbon dioxide in an acceptor medium.
- the gas containing carbon dioxide is scrubbed with an acidic solution before being brought into contact with an acceptor solution according to the invention.
- any acid or acid-forming compound can be used for this purpose.
- the preferred acids are HCl (hydrochloric acid), sulfuric acid or phosphoric acid.
- the gas containing carbon dioxide is washed by means of an acidic solution selected from hydrochloric acid, sulfuric acid or phosphoric acid before being brought into contact with an acceptor solution according to the invention.
- a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) by means of a membrane contactor is therefore preferred.
- a membrane contactor In a membrane contactor, the phases to be brought into contact with one another are separated from one another by a membrane.
- an aqueous acceptor medium is brought into contact with a gas/gas mixture by means of a membrane contactor.
- a membrane contactor allows a complete extraction of carbon dioxide to be achieved in a membrane contactor device, which has significantly smaller spatial dimensions than a gas washing device equipped with random packings.
- a flat membrane module can be provided which on the one hand has very flat channels for the gas and liquid phase and at the same time only comparatively small ones has channel lengths. This allows the design of membrane contactors that can be optimally adapted in terms of flow technology to individual gases/gas compositions and volume flows.
- Various designs are known in the prior art, such as wound modules or hollow-fiber modules or tubular modules.
- the preferred membranes/solid separation media for the step of contacting the gas containing carbon dioxide with an acceptor solution according to the invention have a low structural height (membrane thickness). This is preferably ⁇ 300 pm, more preferably ⁇ 200 pm, further preferably ⁇ 150 pm, further preferably ⁇ 100 pm, further preferably ⁇ 50 pm and even more preferably ⁇ 25 pm.
- a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a gas-liquid separating membrane with an average pore size of 200 ⁇ m at atmospheric pressure is therefore preferred.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with a membrane thickness of ⁇ 300 pm, more preferably ⁇ 200 pm, more preferably ⁇ 150 pm, more preferably ⁇ 100 pm, more preferably ⁇ 50pm and more preferably ⁇ 25pm.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with an average pore size of 200 ⁇ m at atmospheric pressure, the membrane having a membrane thickness of ⁇ 300 ⁇ m, more preferably ⁇ 200 ⁇ m, more preferably ⁇ 150 pm, more preferably ⁇ 100 pm, more preferably ⁇ 50 pm and even more preferably ⁇ 25 pm.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with an average pore size of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferred > 200pm, more preferably > 250pm and most preferably > 300pm.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with an average pore size of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferred > 200pm, even more preferably > 250pm and most preferably > 300pm at atmospheric pressure, the membrane having a membrane thickness of ⁇ 300pm, more preferably ⁇ 200pm, more preferably ⁇ 150pm, more preferably ⁇ 100pm, more preferably ⁇ 50pm and even more preferably ⁇ 25pm having.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with an average pore size of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferred > 200 pm, even more preferably > 250 pm and most preferably > 300 pm, the membrane having a membrane thickness of ⁇ 300 pm, more preferably ⁇ 200 pm, more preferably ⁇ 150 pm, more preferably ⁇ 100 pm, more preferably ⁇ 50 pm and even more preferably ⁇ 25 pm.
- the membrane/foil can be attached to or connected to a carrier material.
- the average channel diameter or the average pore size is specified.
- the preferred membranes/solid separation media have open channels with a mean channel diameter or mean pore size of >10pm, more preferably >50pm, more preferably >100pm, more preferably >150pm, more preferably >200pm, even more preferably >250pm and most preferably > 300pm on.
- Membranes/solid separation media which have a high porosity (number of pores per unit area) are preferred.
- membranes/solid separation media with a porosity of >50%, more preferably >60%, more preferably >70%, more preferably >80% and even more preferably >90%.
- any material with the prior art Technology Membranes/solid separation media that can be produced are suitable for carrying out the process according to the invention.
- the selection is preferably made according to the individual application.
- a hot gas/gas mixture eg >130° C.
- a heat-resistant material should preferably be selected.
- Suitable materials here are, for example, PTFE (polytetrafluoroethylene) or PC (polycarbonate) or ceramic membranes.
- Preference is therefore given to a method comprising the step of contacting a gas containing carbon dioxide with the acceptor solution from step a) using a membrane with an average pore size of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferred > 200 pm, even more preferably > 250 pm and most preferably > 300 pm, the membrane having a membrane thickness of ⁇ 300 pm, more preferably ⁇ 200 pm, more preferably ⁇ 150 pm, more preferably ⁇ 100 pm, more preferably ⁇ 50 pm and even more preferably ⁇ 25 pm, wherein the membrane is selected from a polytetrafluoroethylene (PTFE) membrane, a polycarbonate (PC) membrane or a ceramic membrane.
- PTFE polytetrafluoroethylene
- PC polycarbonate
- Particularly suitable materials from which the membranes/solid separation media are made can be selected for different applications.
- a membrane is preferably used which has hydrophobic surface properties, measurable by a water contact angle of >90°.
- This membrane preferably also has lipophilic surface properties, measurable, for example, by a contact angle with oleic acid of ⁇ 10°.
- the membranes/solid separation media according to the invention are used, which are additionally given a hydrophilic surface coating.
- the hydrophilic surface coating preferably has hygrostatic properties at the same time.
- gases/gas components other than carbon dioxide can also be removed from a gas/gas mixture with membrane contactors, provided they are water-soluble and are absorbed by the acceptor medium according to the invention.
- high overflow rates of the liquid phase and/or the gas phase are set at the membranes/solid separating media of the membrane contactor in a membrane contactor.
- the acceptor solution contains at least one acceptor compound that is readily soluble in water. This acceptor compound can be completely or incompletely dissolved.
- the acceptor solution is taken up and mixed by/with carbon dioxide while a gas/gas mixture is passed through/brought into contact with/through the acceptor solution.
- the at least one dissolved/soluble compound of the acceptor solution preferably causes the solution to have a basic pH.
- the pH of the acceptor solution is preferably between 7 and 14, more preferably between 8 and 13 and even more preferably between 9 and 12.5. In other words, when the acceptor compound is dissolved, a pH of between 7 and 14, more preferably between 8 and 13 and more preferably between 9 and 12.5, is established.
- the preferred water-soluble acceptor compounds have at least one guanidino and/or amidino group. Acceptor compounds which have a guanidino and/or amidino group are preferred, and acceptor compounds which have a free guanidino and/or amidino group are more preferred. In some embodiments, acceptor compounds are preferred which have an amidino group, more preferably have a free amidino group. In some embodiments, acceptor compounds are preferred which have a guanidino group, more preferably have a free guanidino group. Water-soluble compounds which carry free guanidino groups are particularly preferred. The particularly preferred compound bearing guanidino groups is the amino acid arginine.
- the preferred concentration of the acceptor compound in the acceptor solution is between 10 pmol and 10 mol/l, more preferably between 10 mmol/l and 5 mol/l and more preferably between 0.1 mol/l and 3 mol/l. It should be noted that the solubility of the acceptor compound can be increased by binding carbon dioxide. The acceptor compound can therefore be added during the contacting of the gas containing carbon dioxide with the acceptor solution.
- the temperature of the acceptor solution at which contact is made with a gas/a gas phase can in principle be between 0 and 100°C.
- the preferred temperature at which the gas/gas mixture is brought into contact with the acceptor solution is between 1 and 60°C, more preferably between 10 and 35°C and even more preferably between 15 and 30°C.
- the acceptor solution is particularly suitable for storing dissolved carbon dioxide without pressure (at atmospheric pressure or standard pressure). It could be shown that acceptor solutions containing dissolved and bound carbon dioxide remain stable even over the course of 12 months; in particular, there is neither segregation of carbon dioxide nor microbial colonization of the medium.
- even at high concentrations of arginine e.g. 3 mol/l, there is no crystallization of arginine or formation of a precipitate, not even when stored at a temperature of 3°C.
- the aqueous acceptor solutions according to the invention are preferably solutions of one, two or more amino acid(s) and/or peptide(s), which in the individual and/or total concentration range from 10 mmol/l to 15 mol/l, more preferably between 100 mmol/l and 10 mol/l and more preferably between 0.1 mol/l and 5 mol/l.
- the compounds can be L or D forms or racemates.
- the amino acid arginine is preferred, and their derivatives are also preferred.
- Basic amino acids and peptides with cationic groups (positively charged functional groups) are particularly preferred.
- the peptides that can be used according to the invention can be di-, tri- and/or polypeptides.
- the peptides of the invention have at least one functional group that binds or can bind a proton.
- the preferred molecular weight is below 500kDa, more preferably ⁇ 250kDa, further preferably ⁇ 100kDa and particularly preferably ⁇ 1000Da.
- the preferred functional groups are in particular a guanidine, amidine, amine, amide, hydrazine, hydrazone, hydroxyimine or nitro group.
- the amino acids can have a single functional group or contain several of the same compound class or one or more functional group(s) of different compound classes.
- amino acids and peptides according to the invention preferably have at least one positively charged group (cationic groups/positively charged functional groups) or have a positive overall charge.
- Particularly preferred peptides contain at least one of the amino acids arginine, lysine, histidine in any number and in any sequential order.
- Amino acids and/or derivatives thereof which contain at least one guanidino and/or amidino group are particularly preferred. However, other acceptor compounds which contain at least one guanidino and/or amidino group are also preferred.
- the chemical residue H 2 NC(NH)—NH—and its cyclic forms are referred to as the guanidino group, and the chemical residue H 2 NC(NH)—and its cyclic forms are referred to as the amidino group.
- These guanidino compounds and amidino compounds preferably have a partition coefficient K ow between n-octanol and water of less than 6.3 (KO w ⁇ 6.3). Arginine derivatives are particularly preferred.
- Arginine derivatives are defined as compounds having a guanidino group and a carboxylate group or an amidino group and a carboxylate group, where guanidino group and carboxylate group or amidino group and carboxylate group are substituted by are at least one carbon atom apart, ie at least one of the following groups is located between the guanidino group or the amidino group and the carboxylate group: -CH2-, -CHR-, -CRR'-, where R and R' independently represent any chemical radical.
- Examples of compounds with more than one guanidino group and more than one carboxylate group are oligoarginine and polyarginine. Other examples of compounds falling under this definition are guanidinoacetic acid, creatine, glycocyamine.
- Preferred compounds have the general formula (I) or (II) as a common feature.
- X represents -NH-, -NR””-, or -CH 2 - or a substituted carbon atom
- L represents a C 1 to C 8 linear or branched and saturated or unsaturated carbon chain having at least one substituent selected from the group comprising or consisting of
- the carbon chain L is in the range of Ci to C 7 , more preferably in the range of Ci to C 6 , further preferably in the range of Ci to C 5 , and most preferably in the range of Ci to C 4 .
- L represents -CH(NH 2 )-COOH, -CH 2 -CH(NH 2 )-COOH,
- Preferred compounds which have a free guanidino and/or amidino group have the general formula (III) as a common feature: whereby
- X represents -NH-, -NR””-, or -CH 2 - or a substituted carbon atom
- L represents a C 1 to C 8 linear or branched and saturated or unsaturated carbon chain having at least one substituent selected from the group comprising or consisting of It is preferred that the carbon chain L is in the range of Ci to C 7 , more preferably in the range of Ci to C 6 , further preferably in the range of Ci to C 5 , and most preferably in the range of Ci to C 4 .
- L represents -CH(NH 2 )-COOH, -CH 2 -CH(NH 2 )-COOH,
- Preferred compounds which have a free guanidino and/or amidino group have the general formula (I) as a common feature.
- X represents -NH-, or -CH 2 - or a substituted carbon atom
- L represents a C 1 to C 8 linear or branched and saturated or unsaturated carbon chain having at least one substituent selected from the group consisting of or consisting of
- the carbon chain L is in the range of Ci to C 7 , more preferably in the range of Ci to C 6 , further preferably in the range of Ci to C 5 , and most preferably in the range of Ci to C 4 .
- L represents -CH(NH 2 )-COOH, -CH 2 -CH(NH 2 )-COOH,
- the present invention preferably relates to a method for the selective binding, transport and storage of carbon dioxide in aqueous media, comprising the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group; b) contacting a gas containing carbon dioxide with the acceptor solution from step a); and c) transporting bound carbon dioxide/carbon dioxide derivatives in the acceptor solution after step b) through a separating membrane into an aqueous uptake and release medium; or
- X represents -NH-, -NR””-, or -CH 2 - or a substituted carbon atom
- acceptor solutions according to the invention can contain further compounds which do not have a guanidino and/or amidino group and which have an advantageous effect on the execution of the process.
- These can be, for example, base-forming compounds such as lysine and histidine.
- the acceptor solution can contain compounds which, for example, have an antimicrobial effect or change the surface tension of the medium.
- a method in which the acceptor compound is an amino acid and the pH of the acceptor solution is in the range between 8 and 13 is preferred.
- the aqueous acceptor medium contains further compounds or additives.
- Preferred further compounds are in particular potassium and sodium hydroxide.
- Alkaline solutions of potassium (KOH) or sodium (NaOH) improve the electrical conductivity (electrolysability) of water depending on the concentration.
- the voltage from which electrolysis of the water takes place is also reduced; it is between 0.6 and 2 volts depending on the electrode configuration selected. It was found that a mixture of a solution containing arginine as an acceptor compound with a potassium or sodium hydroxide solution did not lead to electrolysis of the water, while this was the case with aqueous potassium or sodium hydroxide solutions with an identical concentration without arginine.
- the electrolyzer produced 18.2 ml of oxygen at the anode and 6.4 ml of hydrogen at the cathode when a voltage of 12 V was applied with a 3% NaOH solution.
- a 2 molar arginine solution containing 3% by weight NaOH With the same test device, no gas formation could be observed within 30 minutes with a 2 molar arginine solution which had been saturated with carbon dioxide when a voltage of 12 V was applied.
- NaOH was added to this solution to make a 3 wt% solution, under the same conditions (12V), there was gas evolution of 7.8 mL at the cathode and no gas evolution at the anode.
- the gas formed at the cathode was carbon dioxide. It was thus possible to show that when a DC voltage is applied, hydrogen carbonate/carbonate anions, which are bound in the acceptor medium, can be separated to form carbon dioxide due to the presence of hydroxide ions at the cathode. It was shown for DC voltages of over 40V that even with a 4% by weight solution of NaOH or KOH in an aqueous solution containing arginine and dissolved carbon dioxide/bicarbonate/carbonate anions, there was no electrolysis of the water which led to the formation of oxygen has. However, with higher DC voltage, a significant amount of carbon dioxide could be released at the cathode.
- adding sodium hydroxide or potassium hydroxide to the aqueous acceptor medium is a particularly preferred embodiment of the method according to the invention.
- an aqueous acceptor solution containing potassium or sodium hydroxide solution is provided, with a pH between 12 and 14.
- a method is preferred in which the aqueous acceptor medium containing a dissolved acceptor compound additionally contains a potassium and/or sodium hydroxide solution.
- the preferred concentration of sodium or potassium salts in an acceptor solution according to the invention is between 0.1 and 25% by weight, more preferably between 1 and 20% by weight and even more preferably between 2 and 15% by weight.
- the preferred counterions of the salts are: sulfate SO 4 2 ', phosphate PO 4 3 ', acetate, citrate, tartrate, oxalate.
- the salts can be used individually or in any combination Combination of the acceptor solution are added.
- the pH of the acceptor solution containing dissolved sodium and/or potassium salts is preferably between 8.0 and 13.5, more preferably between 8.5 and 13 and more preferably between 9 and 12.5.
- the preferred acceptor solutions containing sodium and/or potassium salts are non-corrosive.
- a method is preferred in which an aqueous acceptor solution containing at least one dissolved acceptor compound and at least one dissolved sodium and/or potassium salt is provided for absorbing carbon dioxide and carbon dioxide or its derivatives are/are dissolved/bound therein.
- a method is preferred in which carbon dioxide can be bound without pressure (at atmospheric pressure or standard pressure) by means of an aqueous acceptor solution over the course of more than 12 months.
- a method is preferred in which the acceptor solution, with carbon dioxide/carbon dioxide derivatives bound therein, is transported and/or stored.
- a method for the selective binding, transport and storage of carbon dioxide in aqueous media which is characterized by the steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, b) contacting a gas containing carbon dioxide with the acceptor solution from step a) until a carbon dioxide concentration of ⁇ 100 ppm is reached in the gas, c) transporting and/or storing the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives according to step b) .
- a method in which the acceptor compound is an amino acid and the pH of the acceptor solution is in the range between 8 and 13 is preferred.
- the acceptor solutions are preferably prepared using deionized water (VE water).
- VE water deionized water
- the one or more acceptor compound(s) is/are preferably completely dissolved in the water.
- the solution can be heated in order to increase the solubility of the one or more compound(s).
- the solubility of the acceptor compounds can be significantly increased by bringing part of the acceptor compound into contact with carbon dioxide during or after a heat-induced dissolving process
- the dissolving process of acceptor compounds is carried out with the introduction of carbon dioxide accomplished.
- undissolved acceptor compounds can be dissolved/dissolved, or a further increase in the concentration of the acceptor compound(s) is possible.
- concentrations of 5 mol/l and more can be achieved.
- these solutions remain stable, i.e. there is no crystallization of the acceptor compound(s).
- a method is preferred in which the solubility of an acceptor compound is increased by mixing the acceptor medium, in which the acceptor compound is present in dissolved and/or undissolved form, with a gas/gas mixture consisting of or containing carbon dioxide with the acceptor -Medium is brought into contact.
- Preferred is a method in which contacting the acceptor medium with a Gas/gas mixture containing at least one gaseous compound which forms a water-soluble compound on contact with water and in which the water-soluble compounds are present in ionic or ionizable form in the acceptor medium, forming a reversible bond between the dissolved compound and the dissolved acceptor compound .
- the gas phase is brought into contact with the acceptor medium until the content of the gas/gaseous compound dissolved in the acceptor medium is ⁇ 100 ppm.
- a method for producing a pure methane gas is preferred
- a method for producing a pure bio-methane gas is preferred
- the acceptor solutions according to the invention allow gases/gaseous compounds which form an acid form on contact with water to be bound in an aqueous acceptor solution. If selective extraction and/or recovery of carbon dioxide is desired, it is advantageous to remove other gases/gaseous compounds, which can also form an acid form in water and thus compete with the absorption of carbon dioxide, from a gas/gas mixture before this is brought into contact with one of the acceptor compounds according to the invention.
- gases/gas mixtures such compounds, such as SO 2 , H 2 S, NO, NO 2 and other nitrogen oxides or Cl 2 or HCl, are preferably removed or reduced.
- the gas/gas mixture to be contacted with the acceptor solution preferably has a temperature between 0 and 100°C, more preferably between 10 and 85°C and even more preferably between 15 and 70°C.
- the acceptor solution can also be used to cool a gas/gas mixture, so that higher temperatures of a gas/gas mixture are also possible.
- the solution should preferably be cooled in this case.
- the gas/gas mixture that is obtainable after being brought into contact with an aqueous acceptor medium can, depending on the temperature, composition, the volume flow or the type of contacting, contain water vapor and water in droplet form. It is possible that the acceptor solution and thus the acceptor connections are lost as a result. Therefore, the most complete possible removal of water from the treated gas/gas mixture should preferably be undertaken. This can be done using methods known in the art, such as a device for condensate removal. The separated water phase is then returned to the acceptor solution.
- the acceptor compounds according to the invention are not consumed when carrying out the process according to the invention and are not subject to any autocatalytic process. The method is therefore aimed at economical process management, in which the acceptor compound is reused without loss in a circuit.
- a process-economic method in which the acceptor compound is reused without loss is preferred.
- a gas stream containing at least one water-soluble gas component which has a temperature of up to 350° C. is brought into contact with an aqueous acceptor medium in a membrane contactor. Therefore, in a preferred embodiment of the method, a membrane contactor is used to bring an acceptor liquid (acceptor solution) into contact with a gas stream which has or consists of at least one water-soluble gas fraction and preferably in a temperature range between 10 and 400 °C, more preferably between 50 and 350°C and more preferably between 70 and 300°C is introduced into the membrane contactor.
- a method is preferred in which a gas stream which contains at least one water-soluble gas component and which has a temperature of up to 350° C. is brought into contact with an aqueous acceptor medium in a membrane contactor.
- Completely dissolved means that in a closed vessel containing the dissolved carbon dioxide/carbonate/bicarbonate anions at 20° C. no vapor pressure of more than 2 kPa develops due to carbon dioxide.
- degassing can be carried out, for example by lowering the pH of the acceptor medium. This can be done, for example, by adding an acid.
- organic acids can be organic or inorganic acids.
- Preferred organic acids are formic acid or acetic acid.
- Preferred inorganic acids are hypochlorous acid (HCl) or sulfuric acid.
- the concentration of the acid and the volume ratio in which it is added to the acceptor liquid can be freely selected. Concentrated acids are preferred.
- the addition of the acid adjusts the pH of the acceptor liquid which is preferably in the range between 2 and 7, more preferably in the range 3 to 6 and more preferably in the range between 3.5 and 5. This achieves a removal of carbon dioxide dissolved/bound in the acceptor liquid or its water-soluble derivatives of preferably >70% by weight, more preferably >80% by weight and more preferably >90% by weight and available as a pure carbon dioxide gas phase.
- a method is preferred in which an aqueous acceptor medium is saturated with a water-soluble gas and then the water-soluble gas bound in the acceptor liquid (acceptor solution) is released by adjusting the pH of the acceptor medium to a range between 2 and 7 will.
- a method is preferred in which an aqueous acceptor medium is saturated with a water-soluble gas and then the water-soluble gas bound in the acceptor liquid (acceptor solution) is released by adjusting the pH of the acceptor medium to a range between 2 and 7 by adding an acid will.
- the addition of an acid to the acceptor medium causes the introduction of anions, the retention of which in the acceptor liquid has a disadvantageous effect on the ability of the acceptor compounds to absorb water-soluble gases or their derivatives again.
- the acceptor liquid (acceptor solution) is subjected to renewed exposure to a water-soluble gas/gas fraction, a separation of the added anions.
- anions such as CP (chloride) or SO 4 2 ' (sulphate) can be removed by means of electrodialysis. With such electrophoretic methods, however, organic acid residues can also be removed, as a result of which regeneration of the acceptor liquid (acceptor solution) can also be achieved.
- an alkaline solution such as, for example, potassium hydroxide or sodium hydroxide solution
- an alkaline solution such as, for example, potassium hydroxide or sodium hydroxide solution
- the lye is preferably metered in such a way that the addition produces an equimolar ratio between the anions added to the acceptor medium on the one hand and the cations supplied by adding the lye on the other.
- a separation of the salt formed preferably takes place here. This can preferably be done by means of an electrophoretic method, e.g., electrodialysis.
- the acceptor liquid (acceptor solution) regenerated in this way can then be used to take up water-soluble gases/gas components or their water-soluble derivatives again.
- a method is preferred in which an aqueous acceptor medium is saturated with a water-soluble gas and then the liquid in the acceptor is released (Acceptor solution) bound water-soluble gas is accomplished by adding an acid and then the acceptor liquid (acceptor solution) is regenerated by adding alkali and then separating the resulting salt by electrophoretic separation.
- the pH of the acceptor liquid (acceptor solution) saturated with a water-soluble gas/gas component or its water-soluble derivatives is lowered by means of an electrochemical method.
- an electrochemical method This can be accomplished, for example, by introducing the acceptor liquid (acceptor solution), which contains a dissolved water-soluble gas/gas component or derivatives thereof, into an electrodialysis device.
- An arrangement of the electrodialysis chambers is preferably selected in which an electrolyte chamber is connected to the acceptor chamber on the anode side.
- a cation-selective membrane is preferably located between the chambers. The water-soluble derivatives of carbonic acid are then released as carbon dioxide in the acceptor chamber.
- a method is preferred in which an aqueous acceptor medium is saturated with a water-soluble gas and the water-soluble gas bound in the acceptor liquid is then released by adjusting the pH of the acceptor medium to a range between 2 and 7 using an electrochemical process.
- a method is preferred in which, after contacting a gas containing carbon dioxide with the acceptor solution until a carbon dioxide concentration of the gas has reached ⁇ 100 ppm, or after transport and/or storage of the acceptor solution containing bound carbon dioxide/carbon dioxide derivatives, the process step takes place: release of the carbon dioxide bound in the acceptor medium as a gas phase.
- the release of the water-soluble gas/gas fraction dissolved and bound in the aqueous acceptor medium, or its derivatives takes place following spatial separation from the acceptor medium.
- the dissolved and bound carbon dioxide/carbonate/bicarbonate anions are transported into an uptake and release medium by an electrophoretic process. It was able to be shown that a gas phase spontaneously forms in an uptake and/or release medium according to the invention into which carbonate/bicarbonate anions have been transported. Only carbon dioxide could be detected in the gas phase that formed. It is thus possible, without applying pressure, to selectively remove carbon dioxide from a gas mixture and release it in isolated form in a collecting vessel.
- open-pored membranes are particularly suitable for separating dissolved carbon dioxide/carbonate/bicarbonate anions from the aqueous media according to the invention.
- Microporous or mesoporous membranes are preferred.
- macroporous and nanoporous membranes can also be used.
- the outer and inner membrane surfaces can be hydrophilic or hydrophobic. Hydrophobic membrane surfaces are preferred. It could be shown that compared to Anion exchange membranes or bipolar membranes, which consist of a closed polymer film, a significantly larger mass / volume flow of / the electrophoretically transported carbon dioxide / carbonate / bicarbonate anions is possible.
- a method is preferred in which the separation of dissolved carbon dioxide/carbonate/bicarbonate anions takes place by means of open-pored membranes.
- the open-pored membranes are preferably microporous and/or mesoporous and have hydrophobic surface properties.
- the preferred forms of transport for carbon dioxide/carbonate/bicarbonate anions are based on a diffusive process, a concentration gradient or a thermal or electrical gradient and combinations of these.
- Preferred are open-pored membranes, i.e. a solid or semi-solid separation medium (separation membrane) capable of retaining an aqueous medium without pressure and having open pores connecting both sides of the membrane and being permeable to a gas and/or anions.
- the open pores preferably have an average diameter of between 10 nm and 1 mm, more preferably between 100 nm and 500 micrometers and more preferably between 1 micrometer and 200 micrometers.
- the preferred membranes have hydrophilic or hydrophobic electrostatic properties on their inner and/or outer surfaces.
- the receiving device for the receiving and/or release medium can be open to atmospheric pressure.
- both the receiving devices (chambers) for the acceptor medium and for the receiving and/or release medium are open to atmospheric pressure.
- a process is preferred in which carbon dioxide/carbonate/hydrocarbonate anions are separated from an aqueous acceptor medium by a separating medium (separating membrane) and are thereby taken up and/or released in an uptake and release medium.
- a method is preferred in which carbon dioxide/carbonate/hydrocarbonate anions are separated from an aqueous acceptor medium by a separation medium (membrane), which is based on a diffusive, osmotic and/or electrophoretic process.
- a separation medium membrane
- the separation medium is used to separate carbon dioxide/carbonate/hydrocarbonate anions from an aqueous acceptor medium is a solid or semi-solid separation medium (separation membrane) that retains an aqueous medium without pressure (atmospheric pressure) and has open pores that connect both sides of the membrane and are permeable to a gas and/or anions.
- a method is preferred in which the solid or semi-solid separation medium (separation membrane) for separating carbon dioxide/carbonate/hydrocarbonate anions is a separation membrane.
- a method is preferred in which the separation membrane for the separation of carbon dioxide/carbonate/hydrocarbonate anions is an anion-selective or bipolar polymer membrane.
- dissolved carbon dioxide or carbonate/bicarbonate anions can be separated very efficiently from the acceptor solution according to the invention by means of electrophoretic processes.
- electrodialysis it is preferred to carry out electrodialysis to separate dissolved carbon dioxide/bicarbonate anions.
- the electrodialysis can be carried out using methods and devices from the prior art.
- carbon dioxide/carbonate/hydrocarbonate anions are separated from an aqueous acceptor medium by the acceptor medium containing carbon dioxide/carbonate/hydrocarbonate anions being filled into an acceptor chamber which is Separation medium (separation membrane) is separated from an adjoining receiving and release chamber.
- An absorption and/or release medium is preferably located in the absorption and release chamber. This is preferably an aqueous medium. This preferably has a pH in the range between 1 and 7, more preferably between 2 and 6 and more preferably between 3 and 5.
- compounds bearing acid groups are dissolved in the uptake and/or release medium.
- Amino acids bearing acid groups in particular aspartic acid and glutamic acid, are particularly preferred.
- the preferred concentration is in a range between 1mmol/l and 3mol/l.
- organic acids which carry more than one acid group and have good solubility in water, such as citric acid or ascorbic acid.
- inorganic acids are also suitable, such as sulfuric acid or diphosphoric acid.
- aqueous solutions of these acids with a concentration between 1 and 50% by weight are preferred. Mixtures of different acids are also preferred.
- the temperature range in which the absorption and release medium is used can be freely selected between 1 and 99°C.
- a temperature range between 30 and 80°C is preferred, more preferably between 40 and 75°C and even more preferably between 50 and 70°C.
- the uptake and release chamber contains an uptake and/or release medium containing at least one compound which carries at least one acid group and has an isoelectric point in the range between 3 and 5.
- a method is preferred in which the uptake and/or release medium is an aqueous solution of an organic and/or inorganic acid.
- this embodiment of the method is suitable for selectively transporting carbon dioxide or carbonate/bicarbonate anions into the uptake and release chamber or the uptake and/or release medium allow the carbon dioxide to separate from the uptake and/or release medium and gaseous carbon dioxide to form from the carbonate/bicarbonate anions with the elimination of water, so that a gas phase is formed that contains only carbon dioxide. It is thus possible to selectively bind carbon dioxide, transport it and release it selectively at any location.
- the absorption and release medium flows through the absorption and release chamber continuously or discontinuously, with a high overflow speed preferably taking place at the surface of the separating medium (separation membrane), which means that outgassing at the surface of the separating medium (separation membrane) is complete or can be almost completely prevented and an uptake of bicarbonate-carbonate anions into the absorption and release medium takes place, with which these are preferably introduced into a separate container in which the outgassing is then completed.
- carbon dioxide/carbonate/bicarbonate anions are separated from the aqueous acceptor medium by an electrodialysis process.
- the acceptor solution in which carbon dioxide or its reaction products with water are dissolved, is fed to an acceptor chamber of an electrodialysis unit.
- the electrodialysis unit consists of an acceptor chamber and an uptake and release chamber, which are separated from one another by a separating medium (separating membrane).
- the electrodes can be located directly in the process media, i.e. the anode can be located in the absorption and/or release medium and the cathode can be located in the acceptor solution. More preferred are electrodialysis devices in which the electrodes are located in an anode or cathode chamber (electrode chambers) and in which the acceptor chamber or receiving and releasing chamber are separated from the electrode chambers by an ion-selective membrane, the anode and cathode chamber are filled with a medium suitable for electron transport, for example an electrolyte solution (see FIG. 1).
- a medium suitable for electron transport for example an electrolyte solution (see FIG. 1).
- multiple chamber units consisting of acceptor chambers and receiving and release chambers, are assembled in a repeated arrangement, with the chamber stacks being closed at both ends by the anode or cathode chamber and being electrically conductively connected thereto.
- the first acceptor chamber is adjacent to the cathode chamber and the last receiving and releasing chamber is adjacent to the anode chamber.
- the acceptor chambers are each separated from the receiving and release chambers by a bipolar membrane.
- Carbon dioxide or carbonate/bicarbonate anions are preferably transported by applying an electrical DC voltage between the cathode and the anode.
- the voltage and current at which electrodialysis according to the invention takes place is dependent of specific process parameters, such as the distance between the electrodes, the number of chamber units, the resistance of the membranes and the process solutions as well as the cross-sectional area and can therefore be determined individually.
- the carbon dioxide transported through the separation medium is released as a gas in the uptake and release chamber containing the uptake/release medium.
- the carbon dioxide or carbon dioxide derivatives transported through the separation medium is absorbed in the absorption/release medium and released as a gas in a release device.
- step c1) or d1) takes place after step b) or c): release of the carbon dioxide bound in the acceptor medium as a gas phase.
- a method is preferred in which the acceptor medium from step b) is located in an acceptor chamber of an electrodialysis device or is introduced therein and the transport of carbon dioxide/carbon dioxide derivatives according to step c) by means of an electrical gradient between the acceptor chamber and a Uptake and release chamber is produced, wherein the acceptor chamber (s) and the uptake and release chamber (s) are separated from each other by a separating medium (separation membrane).
- a method is preferred in which carbon dioxide/carbon dioxide derivatives is/are transported through a separation medium (separation membrane), the separation medium being a membrane which is permeable to ions and/or gas molecules.
- Preferred is a method for electrodialysis of an acceptor medium and transport of carbon dioxide/carbon dioxide derivatives according to step c) by means of an electrical gradient that is established between the acceptor chamber and an uptake and release chamber, in which the separation medium is a membrane that is permeable for ions and/or gas molecules.
- a method is preferred in which the carbon dioxide/carbon dioxide derivatives transported through the separation medium (separation membrane) are released in the form of a pure carbon dioxide gas in the uptake and release chamber.
- a method is preferred in which the carbon dioxide/carbonate/hydrocarbonate anions transported through the separation medium (separation membrane) are released in the form of a pure carbon dioxide gas in the uptake and release chamber.
- step b) or c) is followed by step b2) or c2): Separation of carbon dioxide/carbonate/hydrocarbonate anions from the acceptor medium by a separating medium (separating membrane) by means of a diffusive, osmotic or electrophoretic method and Transport into an uptake/release medium, carbon dioxide being released as a pure gas phase in the uptake/release medium.
- a separating medium separating membrane
- step b) or c) is followed by step b3) or c3): Separation of carbon dioxide/carbonate/hydrocarbonate anions from the acceptor medium by a separating medium (separating membrane) by means of a diffusive, osmotic or electrophoretic method and Transport into an uptake/release medium, where the release of carbon dioxide takes place as a pure gas phase from the uptake/release medium in a release device.
- a separating medium separation membrane
- step c) is followed by steps c3') and c3): c3') introducing the aqueous uptake and release medium containing bound carbon dioxide/carbon dioxide derivatives from step c) into a release device; and c3) releasing carbon dioxide as a gas phase from the absorption and release medium containing bound carbon dioxide/carbon dioxide derivatives from step c3') in the release chamber.
- the chambers in which carbon dioxide is or can be released are equipped with a trapping device for a gas, which preferably makes it possible that there is no pressure build-up in this chamber.
- the carbon dioxide that is released again after being bound in an acceptor medium according to one of the methods and collected in a gas collecting device and is supplied from there for further use (see FIG. 1).
- a method is preferred in which carbon dioxide is released again as a gas phase following binding/transport or storage in an acceptor medium and is put to further use.
- a method arrangement according to the invention is used in order to produce hydrogen and oxygen in addition to the separation of water-soluble gases/gas components and the selective release.
- electrolysis of water occurs in the electrode chambers, since a voltage usually has to be applied, which causes electrolysis in the selected electrolyte solutions. It has been found that a chamber arrangement consisting of an acceptor chamber and an uptake and release chamber can be introduced into a method arrangement for electrolysis, as a result of which the energy efficiency of the method according to the invention can be significantly increased. Due to the additional availability of hydrogen and oxygen, a very high energy efficiency of the process can be achieved, which is preferably >90%, more preferably >95% and more preferably >98%.
- the water-soluble gas/gas component dissolved in an aqueous acceptor medium is released at a cathode.
- the acceptor solutions according to the invention are suitable for suppressing electrolysis of water, which leads to the formation of oxygen and hydrogen, when a DC voltage is applied, although there is a current flow due to the conductivity of the acceptor solution. This phenomenon was found in particular when using arginine as an acceptor compound. Thus, a molecular charge transfer takes place. It has been found that molecular charge transfer occurs in preference to electrolysis as the distance between anode and cathode increases.
- a method is preferred in which an aqueous solution containing dissolved arginine causes suppression of electrolysis of the water, which leads to the formation of hydrogen or oxygen, when a DC voltage is applied to the aqueous solution.
- a method is preferred in which a solution containing dissolved arginine brings about a molecular charge transfer when a DC voltage is applied to the aqueous solution.
- a method is preferred in which, by providing an acceptor solution, electrolysis can be suppressed when a DC voltage is applied.
- a method is preferred in which a gas dissolved in an aqueous acceptor solution, or its water-soluble derivatives, can be released as a gas phase at a cathode by applying a DC voltage, with no electrolysis occurring leading to the formation of hydrogen or oxygen .
- a method can thus be provided in which water-soluble derivatives of water-soluble gases are deposited as a gas phase at a cathode, with application of a DC voltage and without electrical loss by electrolysis, which leads to the formation of oxygen or hydrogen.
- this embodiment of the method can be carried out using devices for electrodialysis from the prior art. It has been shown that, depending on the energy density that arises at the electrodes when a DC voltage is applied, the distance between the electrodes should be large enough so that no oxygen is formed (recognized by the absence of gas formation at the anode ) comes.
- the voltage can be selected such that there is no gas formation at the electrodes when an uncharged acceptor solution is subjected to the electrical voltage.
- the use of large-area electrodes is advantageous. It is also advantageous if the surface area of the anode is larger than that of the cathode.
- the anode and the cathode space are separated by a separating medium (membrane), as a result of which an anode and cathode chamber electrically connected to one another are created. It is advantageous if the separating medium (membrane) has the lowest possible electrical resistance.
- the separating medium should be open-pored, but prevent gas passage.
- the electrode chambers are flowed through by introducing the acceptor liquid, to which a water-soluble gas has been applied, into the cathode chamber and the solution being conducted consecutively through the anode chamber. In this case, the conduction takes place through the open connections and/or the separating medium (separating membrane) through which a liquid can pass, which is located between the electrode chambers. It has been found that in this way the separation of a gas phase of the gases dissolved in the aqueous acceptor medium, or their water-soluble derivatives, can be significantly increased.
- the electrode material can be freely selected. If, in addition to the acceptor compounds according to the invention, potassium hydroxide or sodium hydroxide solution is present in the acceptor medium, the selection must be adapted accordingly.
- Preferred electrode materials are graphite, nickel, stainless steel, platinum or gold. Combinations of the materials for the anode and cathode and mixed alloys are also preferred.
- the electrical direct voltage, which is preferably between applied to the anode and cathode depends on the electrode configuration and the distance between the electrodes and must therefore be determined individually. The maximum possible voltage that does not lead to the formation of hydrogen and oxygen can be determined by testing the formation of oxygen at the anode; the selected voltage should be below the voltage at which oxygen is formed as a gas phase.
- the method according to the invention is also aimed at a cathodic separation of carbon dioxide or other water-soluble gases as a pure gas phase from an aqueous acceptor medium.
- a method is preferred in which a cathodic deposition of a water-soluble gas takes place from an aqueous acceptor medium.
- a method is preferred in which a gas dissolved in an aqueous acceptor medium, or its water-soluble derivatives, is separated in the form of a pure gas phase by cathodic deposition in the aqueous acceptor medium.
- the uptake and/or release medium contains one or more compounds which react with the carbon dioxide or carbonate/bicarbonate anions transported from the acceptor solution and/or bind this/these.
- These compounds hereinafter referred to as reaction compounds, can be in a liquid, solid or gaseous state.
- reaction-promoting compounds such as catalysts can be present in the uptake and release medium.
- the uptake and release medium can have a different temperature than the acceptor medium.
- carbon dioxide/carbonate/bicarbonate anions dissolved in the acceptor medium react and/or bind with/to suitable compounds present therein.
- the use of reaction compounds for the reaction and/or binding of carbon dioxide and/or carbonate/bicarbonate anions which are present in the acceptor solution and/or the absorption and release medium is preferred.
- a method is preferred in which one or more reaction compounds for reacting and/or binding carbon dioxide and/or carbonate/bicarbonate anions are/are present in the acceptor solution and/or the uptake and/or release medium.
- the reaction conditions in an acceptor solution in which carbon dioxide or carbonate/bicarbonate anions is/are present in a high concentration are particularly suitable for the synthesis of carbon compounds.
- syntheses of carboxylic acids can be accomplished. Examples of this are a reaction with the Grignard reagent or a telomerization with a palladium catalyst.
- Preferred carbon compounds include, but are not limited to, formic acid, methanol, carbon monoxide (CO), and formalaldehyde. It could be shown that the enrichment of carbon dioxide and its water-soluble derivatives, which is possible with the process, enables chemical synthesis of organic compounds under normal pressure conditions.
- carboxylic acids which are synthesized in an aqueous acceptor medium, can be continuously separated by electrodialysis.
- the electrophoretically separated carboxylic acids are preferably taken up in an aqueous medium and released from it again.
- a solution containing dissolved arginine is excellently suited to be used in this embodiment of the method as a medium for taking up and/or releasing the transported carboxylic acids.
- a method is preferred in which one or more reaction compounds for reacting and/or binding carbon dioxide and/or carbonate/bicarbonate anions are/are present in the acceptor solution and/or the uptake and/or release medium.
- a method is preferred in which, after step b), the carbon dioxide bound in the acceptor solution is converted to a carbon compound by means of a reaction compound.
- an anion exchange membrane which is permeable to anions with a molecular weight of up to 400 Da is used for the selective electrophoretic transport of short-chain carboxylic acids.
- a method is preferred in which, after step b), the carbon dioxide bound in the acceptor solution is converted to a carbon compound by means of a reaction compound.
- a method is preferred in which, after step c), the carbon dioxide bound in the absorption and/or release medium or the carbon dioxide transported and released is converted to a carbon compound by means of a reaction compound.
- a solution containing guanidino or amidino group-bearing compounds which are dissolved in an uptake and release medium, are suitable for uptake and transport of carboxylic acids that have arisen from the previous conversion and by means Electrodialysis have been transported.
- a process for the production of carbon compounds from carbon dioxide is preferred.
- the carbon dioxide bound in the aqueous acceptor medium in the form of carbonate/bicarbonate anions is chemically converted to carbonates.
- the carbon dioxide dissolved in the aqueous acceptor medium and the carbonate and bicarbonate anions can be converted directly in the acceptor solution or with it to form carbonates.
- a solution in which cationic compounds suitable for the production of carbonates are present in dissolved (ionized) form is added to the acceptor solution in which carbon dioxide or its water-soluble derivatives are already dissolved/bound. The chemical conversion takes place when the solution containing reaction compounds is introduced into the preferably saturated acceptor solution.
- the carbonate is produced while the acceptor solution, in which the salt of the cation/cationic compound used to produce the carbonate/bicarbonate is already dissolved, is brought into contact with carbon dioxide.
- the acceptor solution in which carbon dioxide or its water-soluble derivatives are already dissolved/bound, is fed to a solution in which Cations / cationic compounds that are suitable for the production of carbonates are present in dissolved (ionized) form.
- the chemical conversion takes place when the saturated acceptor solution is introduced.
- phase separation can also be carried out using filtrative or centrifugal methods from the prior art.
- cations/cationic compounds suitable for the production of carbonates/bicarbonates are introduced into the acceptor solution during the contacting of the acceptor solution with the water-soluble gas/gas fraction, such as carbon dioxide, or subsequently by means of an electrophoretic procedure.
- This is preferably done by electrodialysis.
- This preferably takes place in a process arrangement in which the acceptor chamber borders an electrolyte chamber towards the anode and is separated from this by a cation-selective membrane.
- the electrolyte chamber there are cations/cationic compounds in dissolved (ionized) form that are suitable for the production of carbonates/bicarbonates.
- cations/cationic compounds are transported electrophoretically through the cation-selective membrane into the acceptor solution, where they are then spontaneously converted to the corresponding carbonate.
- the acceptor solution can already be saturated with carbon dioxide or is brought into contact with carbon dioxide during or after the electrodialysis.
- a cation/cationic compound which is/are suitable for the production of carbonates/bicarbonates, is present in ionic form in an uptake and release medium.
- Carbon dioxide/carbonate/bicarbonate anions are transported through an anion-selective separation medium (separation membrane) from the acceptor chamber into the absorption and release medium. In this, the corresponding carbonates are formed. It has been found that this reaction mostly takes place directly at the separation medium (separation membrane). Surprisingly, this reaction proceeded more quickly and homogeneously in the aqueous uptake and release medium when one of the acceptor compounds according to the invention was present dissolved therein. It was shown that bipolar membranes can also be used for this. In this embodiment of the method, it is advantageous if no inorganic acids and only a low content of organic acids are present in the uptake and release medium.
- carbon dioxide and/or carbonate and/or bicarbonate anions are chemically converted in the uptake and release medium, with carbon dioxide and/or carbonate and/or bicarbonate anions from an acceptor chamber passing through a separation medium (separation membrane) is/are transported into the receiving and release chamber and on the other hand cations/cationic compounds which are suitable for the production of carbonates/bicarbonates from an electrolyte chamber in which at least one cation/cationic compound in ionic or ionizable form is present, is transported into the receiving and release chamber.
- the receiving and release chamber is adjacent to the acceptor chamber on the cathode side and to an electrolyte chamber on the anode side.
- the transport of substances preferably takes place electrophoretically, with a bipolar or anion-selective membrane being used as the separating medium (separating membrane) between the acceptor chamber and the uptake and release chamber and a cationic membrane between the uptake and release chamber and the electrolyte chamber. selective membrane are used.
- a bipolar or anion-selective membrane being used as the separating medium (separating membrane) between the acceptor chamber and the uptake and release chamber and a cationic membrane between the uptake and release chamber and the electrolyte chamber. selective membrane are used.
- Counterions (anions) of the compounds used which are used to provide cations/cationic compounds for the production of carbonates, are preferably removed during or after the implementation of one of the conversion processes. These are, for example, CI" or SO ⁇ '.
- the chamber unit in which the counterion accumulates is connected on the anode side by means of an anion-selective membrane either to the anode chamber or to a rinsing chamber.
- the rinsing chamber contains an aqueous electrically conductive Medium that takes up the counterions and either adsorbs them there or the rinsing liquid is recirculated through the anode chamber.
- this creates an acid in the anode chamber, such as hydrochloric acid or sulfuric acid, which may be further concentrated and used to produce a solution containing cations/cationic compounds which are suitable for carbonate production,
- aluminum chloride or iron(II) sulfate can be produced from metallic aluminum or iron in this way, which can then be used for further carbonate/bicarbonate production.
- Carrying out conversion processes 2 and 3 is particularly advantageous since no solid aggregates are formed in the acceptor medium and no further anions are introduced which can compete with the uptake of carbonate/bicarbonate anions.
- the acceptor solution can be circulated for absorbing and releasing carbon dioxide and/or carbonate and/or bicarbonate anions, which are chemically converted in a secondary circulation process.
- anions that do not correspond to carbonate and/or bicarbonate anions can be separated continuously or discontinuously by adsorptive processes or an electrodialysis process. In this way, circulation of the acceptor solution can also be ensured in conversion process 1.
- the conversion processes according to the invention are preferably carried out in a temperature range between 5 and 70.degree. C., more preferably between 10 and 60.degree. C. and further preferably between 15 and 50.degree.
- the pH of the aqueous solution in which the carbonate/bicarbonate is produced is preferably in a range between 5 and 13, more preferably between 6 and 12.5 and more preferably between 7 and 12.
- the carbonate/bicarbonate is preferably produced under normal pressure conditions .
- a chemical conversion takes place according to one of the conversion processes, in that the conversion takes place at elevated pressure and/or elevated temperature and/or in the presence of a catalyst.
- reaction processes are also suitable for bringing other compounds into contact with carbon dioxide and/or carbonate and/or bicarbonate anions and chemically reacting them with one another. Therefore, in a preferred embodiment of the method, one or more compounds, which are also referred to below as reaction compounds, are/are added to the aqueous acceptor medium in order to react them with carbon dioxide and/or carbonate and/or bicarbonate anions before and/or during and/or in To bring connection to an absorption of carbon dioxide in the acceptor solution with the one or more reaction compound (s) in contact and react with each other.
- reaction compounds which are also referred to below as reaction compounds
- carbon dioxide and/or carbonate and/or bicarbonate anions are chemically converted in a parallel to the absorption process for carbon dioxide and/or carbonate and/or bicarbonate anions carried out according to the invention or subsequently via a Transport of carbon dioxide and/or carbonate and/or bicarbonate anions into an uptake and release medium in which the one or more reaction compound(s) are contained or transported into.
- a method is preferred in which at least one reaction compound is present in an aqueous acceptor medium and conversion with carbon dioxide and/or carbonate and/or bicarbonate anions takes place during and/or after the absorption of carbon dioxide in the acceptor solution.
- a method is preferred in which at least one reaction compound is present in the medium for absorbing and releasing carbon dioxide and/or carbonate and/or bicarbonate anions and conversion with carbon dioxide and/or carbonate and/or bicarbonate anions takes place therein, which /which has been transported through a separating medium (membrane) between the acceptor chamber and the uptake and release chamber(s).
- a separating medium membrane
- a method is preferred in which at least one reaction compound and at least one acceptor compound are present in the uptake and release medium and chemical conversion with carbon dioxide and/or carbonate and/or bicarbonate anions, which occurs through a separating medium (membrane) between the Acceptor chamber and the uptake and release chamber was transported, takes place in the uptake and release medium.
- Preferred is a method in which an absorption of carbon dioxide in the acceptor solution takes place by means of an aqueous acceptor medium and in which the absorbed carbon dioxide and/or carbonate and/or bicarbonate anions pass through a separating medium (membrane) into a reaction chamber is transported containing at least one dissolved reaction compound and is reacted therein with the reaction compound.
- a separation medium membrane
- the residual amounts of acceptor compounds and/or anions of the reaction compounds used which are present in the solid which can be obtained by phase separation can be completely removed, for example, by a washing process.
- the solid which can be obtained can be dried very easily. This can be achieved, for example, on a porous ceramic membrane, where the water is very quickly removed from the membrane and transported.
- the carbonates or bicarbonates dried in this way are then immediately available as a fine powder or can be very easily produced into such a powder by a grinding process.
- the average diameter of the particles is ⁇ 1 m.
- the carbonates or hydrogen carbonates that can be obtained in this way are immediately available in chemically pure and amorphous form. Pure means that the carbonates or bicarbonates are present in a purity of >95% by weight, more preferably >98% by weight and more preferably >99.5% by weight.
- the process according to the invention can also be used to produce carbonates with metal ions, such as iron, aluminum and copper ions.
- the pasty material was convectively dried and then mechanically comminuted to obtain an off-white powder.
- the powder could be completely decomposed by concentrated hydrochloric acid, producing carbon dioxide and a solution of aluminum chloride. Surprisingly, no gas formation or heating occurred either during the dissolution of the aluminum chloride salt in the acceptor solution or during the contacting of the solutions.
- ammonia is added to the solution in which carbonates/bicarbonates are produced. This can take place before, during or after the solution has been brought into contact with a water-soluble gas/gas component. This method is preferably carried out with an acceptor solution according to the invention. But an addition can also be carried out in conversion processes 2 and 3, with the addition taking place in the reaction chamber and/or the receiving and releasing chamber.
- the preferred concentration of ammonia in the solution in which hydrogen carbonate/carbonate production takes place is between 0.001 and 5.0% by weight, more preferably between 0.005 and 3.0% by weight and more preferably between 0.01 and 1. 5 wt%. Since the preferential formation of hydrogen carbonates depends on the concentration of the introduced anions (eg CP or SO 4 2 '), which are bound by ammonium ions, the optimal concentration of ammonia has to be determined individually. The resulting bicarbonates are separated and purified using the same separation technique as described herein.
- the production of bicarbonates or carbonates takes place at a process temperature which is preferably ⁇ 50°C, more preferably ⁇ 35°C, further preferably ⁇ 20°C and even more preferably ⁇ 10°C.
- the ammonium salts present in the acceptor or reaction solution are separated. This can preferably be done by electrodialysis.
- anions or anionic compounds by means a reaction with ammonium to separate. It has been found that, in addition to a higher conversion rate and conversion amount of cations or cationic compounds to form carbonates or bicarbonates, impurities that may be present in an electrolyte solution can also be removed very easily as a result. This could be shown, for example, with aluminum materials (including aluminum foil) that were recycled and contained organic compounds. Acidic hydrolysis was carried out using concentrated hydrochloric acid. A gray solid formed with a pH of 1, which could be completely dissolved in water.
- a regenerated liquid (pH 7) from a cation exchanger used to produce deionized water was examined. The regeneration took place with a NaCl solution. It was found that mixing in ammonia resulted in flocculation which could be separated by centrifugation. The clear supernatant (pH 9) was added to an acceptor solution saturated with carbon dioxide, during which solid formation occurred. In the Solids analysis documented a mixture of calcium and magnesium hydrogen carbonates.
- a preferred method for producing hydrogen carbonates is one in which ammonium ions are added to an electrolyte solution and the mixture is then brought together and mixed with an aqueous acceptor solution which is saturated with carbon dioxide or its water-soluble derivatives.
- carbonates and bicarbonates can be produced from carbon dioxide or its derivatives, which are present in a reactive form in an acceptor solution or are brought into a reactive form by acceptor compounds, or are present in a reactive form bound to such a solution, by bringing them into contact are brought with elements or compounds that are present as a cation/cationic compound, ie in ionic form, with a chemical reaction taking place.
- carbonates hydrogen carbonates
- carbonates such as sodium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, cobalt carbonate, iron carbonate, copper carbonate, aluminum carbonate, silicon carbonate, zinc carbonate, silver carbonate, lead carbonate and ammonium carbonate. and the corresponding hydrogen carbonates.
- the preferred hydrogen carbonates and carbonates that are produced using a method according to the invention have an average particle diameter of preferably ⁇ 2 pm, more preferably ⁇ 1.5 pm, further preferably ⁇ 1 m and even more preferably ⁇ 0.5 pm.
- a process for the low-energy production of carbonates and/or bicarbonates is preferred.
- a process for the low-energy production of carbonates and/or bicarbonates from renewable raw materials is preferred.
- Regenerative carbonates and bicarbonates produced by a process according to the invention, are preferred.
- a process for the production of aluminum carbonate is preferred.
- Aluminum carbonate produced by a process according to the invention is preferred.
- a process for the production of aluminum bicarbonate is preferred.
- Aluminum bicarbonate produced by a process according to the invention, is preferred.
- Preferred is aluminum carbonate produced by a process according to the invention, where the reaction compound is an aluminum salt, preferably aluminum chloride.
- reaction compound being an aluminum salt, preferably aluminum chloride.
- the reaction compound in the form of an aluminum salt for the production of aluminum carbonate and/or aluminum hydrogen carbonate is itself not aluminum carbonate and/or aluminum hydrogen carbonate.
- the pH of the acceptor solution which is preferred for the production of carbonates or bicarbonates according to one of the embodiments of the invention, is in the range between 7 and 13.5, more preferably between 8 and 12.5 and more preferably between 8.5 and 12.
- aqueous solutions of salts of the cations/cationic compounds to be used for carbonate/bicarbonate production are prepared and added to an acceptor solution saturated with carbon dioxide.
- the concentration of the salt solution can be freely selected.
- the pH of the acceptor solution should preferably not be lowered below 4 by adding the saline solution, otherwise bound carbon dioxide will be released.
- the solution with the dissolved salt is introduced under pressure.
- the introduction of the saline solution should preferably be carried out with agitation.
- the anion of the salt can be chosen freely.
- a compound that is as low in molecular weight as possible should preferably be used.
- Preferred anions are chloride, hydroxyl, sulfate and citrate ions.
- the introduction of the salt into the acceptor solution accumulates the anions used, which are electrostatically bound to a guanidino or amidino group of the acceptor compound.
- the anions are therefore advantageously removed from the acceptor solution using methods from the prior art. This can be done continuously, e.g., by means of electrodialysis, or batchwise, e.g., with an anion exchange compound, or an adsorbent/complexing agent.
- a method is therefore preferred which is characterized by the following steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, b) contacting a gas containing carbon dioxide with the acceptor solution Step a), c) Conversion of the carbon dioxide contained and bound in the acceptor solution and/or the carbon dioxide derivatives according to step b), which is achieved by
- At least one cationic compound is added to the acceptor solution from step b) and dissolved and mixed therein, or by d2) - the carbon dioxide and/or carbon dioxide derivatives contained and bound in the acceptor solution are electrophoretically converted into a Uptake and release chamber or a reaction chamber is/are transported and is/are brought into contact with at least one cationic compound and mixed therein, d) obtaining the reaction product with the carbon dioxide and/or the carbon dioxide derivatives from step c) in the chamber , in which the conversion takes place is available, and after the conversion product is separated and dried by means of a separation process.
- a method is therefore preferred which is characterized by the following steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, b) contacting a gas containing carbon dioxide with the acceptor solution Step a) until a carbon dioxide concentration of the gas of ⁇ 100 ppm is reached, c) conversion of the carbon dioxide contained and bound in the acceptor solution and/or the carbon dioxide derivatives according to step b), which is achieved by - the acceptor solution Step b) at least one cationic compound is added and dissolved and mixed therein, or by d2)- electrophoretically introducing the carbon dioxide and/or carbon dioxide derivatives contained and bound in the acceptor solution into an uptake and release chamber or a reaction chamber is/are transported and is brought into contact and mixed therein with at least one cationic compound, d) obtaining the conversion product with the carbon dioxide and/or the carbon
- the process versions described here can also preferably be used in other types of process, in particular: preference is given to a process in which the conversion in step c) is a chemical conversion with a reaction compound; preferred is a method in which the reaction compound is dissolved in an aqueous solution containing an acceptor compound and/or an uptake and release compound to prepare a reaction solution; preference is given to a method in which the conversion in step c) takes place in the acceptor solution obtainable from step b) and/or in an uptake and release medium and/or in a reaction medium; preference is given to a process in which a reaction medium contains at least one acceptor compound; preference is given to a method in which the conversion in step c) in the acceptor solution obtainable from step b) or in an uptake and release medium after transport of carbon dioxide and/or the carbon dioxide derivatives from the acceptor medium according to step b) into the uptake and release medium, through contact with dissolved or undissolved reaction compounds; a method is preferred in which the conversion in step c), which takes
- conversion process 3 is used for this purpose.
- this takes place in an electrodialysis device in which one or multiple chamber sequences are stacked one behind the other between a cathode and an anode chamber, with the arrangement: acceptor chamber/reaction chamber/electrolyte chamber.
- the electrolyte chamber preferably has the electrolyte solution flowing through it, which is circulated through the anode chamber.
- at least one compound that facilitates or catalyzes electrolysis is present in the electrolyte solution.
- a medium is preferably present in the reaction chamber which is suitable for taking up and reversibly binding anions and cations.
- ionic liquids are used for this purpose.
- compounds which can bind hydrogen ions (proton) are dissolved in the ionic liquid.
- the ionic liquid contains compounds which have a catalytic or reaction-promoting property.
- the electrolyte solution circulates between the electrolyte chambers and the cathode chamber.
- An open-pored or a bipolar membrane is preferably located between the acceptor chamber and the reaction chamber and a cation-selective membrane is located between the electrolyte chamber and the reaction chamber. It could be shown that with such an arrangement, methane is formed in the reaction chamber between the anode and cathode during a DC voltage system, which spontaneously escapes from it.
- the hydrogen produced during or after carrying out the method according to the invention can be made available immediately for one of the reactions of the conversion method disclosed therein and converted in the process.
- a method is therefore preferred which is characterized by the following steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, b) contacting a gas containing carbon dioxide with the acceptor solution Step a), c) Conversion of the carbon dioxide contained and bound in the acceptor solution and/or the carbon dioxide derivatives after step b) or
- a method is therefore preferred which is characterized by the following steps: a) providing an aqueous acceptor solution containing at least one acceptor compound which has a free guanidino and/or amidino group, b) contacting a gas containing carbon dioxide with the acceptor solution Step a) until the acceptor medium is saturated with carbon dioxide, c) conversion of the carbon dioxide contained and bound in the acceptor solution and/or the carbon dioxide derivatives after step b) or
- an acceptor solution containing at least one dissolved acceptor compound containing at least one guanidino or amidino group can take place at normal pressure and room temperature.
- Carbon dioxide bound in the acceptor medium and carbonate and/or hydrogen carbonate anions remain unpressurized (at normal pressure) over a period of at least 6 months and can be transported in this form.
- a reaction solution can be provided in which a chemical conversion of the carbon dioxide and carbonate and/or bicarbonate anions can take place directly.
- the acceptor medium is suitable for dissolving and transporting carboxylic acids resulting from the conversion of carbon dioxide.
- the acceptor solution can be saturated with carbon dioxide any number of times and this can then be removed again without consumption or loss of the acceptor compound.
- acceptor medium refers to a liquid or solvent in which is present at least one dissolved compound capable of binding carbon dioxide/carbon dioxide derivatives. This compound is also referred to herein as an “acceptor compound”.
- the acceptor compound has at least one free guanidino and/or amidino group.
- the acceptor medium can contain reaction compounds and also other compounds. If the liquid or solvent in which at least one dissolved compound is present is water, the “acceptor medium” is also referred to herein as an “aqueous acceptor medium” or as an “acceptor solution”.
- aqueous acceptor medium and “acceptor solution” or also "aqueous acceptor solution” are used synonymously herein.
- acceptor solution is understood here as meaning an aqueous medium in which at least one dissolved compound is present which is capable of binding carbon dioxide, carbon dioxide derivatives. This compound is also referred to herein as an “acceptor compound”.
- the acceptor compound has at least one free guanidino and/or amidino group.
- the acceptor solution can contain reaction compounds and also other compounds. acceptor compound
- acceptor compound refers to a chemical compound that has a free guanidino and/or amidino group.
- the acceptor compound is particularly preferably arginine.
- cationic groups refers to functional chemical groups capable of accepting a proton having a positive electronic charge. “Cationic groups” therefore represent positively charged functional groups. “Cationic groups” are also referred to herein as positive “charged groups”. Preferred chemical compounds that have “cationic groups” here are preferably amino acids and/or derivatives of these that contain at least one guanidino and/or amidino group.
- cationic compounds refers to substances that have a positive electronic charge.
- salts of alkali metals and alkaline earth metals are referred to herein as “cationic compounds”.
- alkali metals and alkaline earth metals that can form carbonates or bicarbonates.
- Preferred “cationic compounds” are inorganic and organic salts of alkali metals and alkaline earth metals, which form carbonates or bicarbonates that are practically insoluble or sparingly soluble in water.
- alkali metal and alkaline earth metal salts can also be used for conversion with carbonate anions or bicarbonate anions, as disclosed herein.
- preferred "cationic compounds" herein include, but are not limited to, calcium chloride, ferric chloride, and aluminum chloride.
- substances with which carbonates or hydrogen carbonates such as sodium carbonate, calcium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, cobalt carbonate, iron carbonate, copper carbonate, aluminum carbonate, silicon carbonate,
- Zinc carbonate, silver carbonate, lead carbonate and ammonium carbonate, as well as the corresponding hydrogen carbonates, as well as aluminum carbonate or aluminum hydrogen carbonate can be obtained include, but are not limited to, sodium, calcium, barium, magnesium, lithium, cobalt, iron, copper, aluminum, silicon , Zinc, Silver and Lead. Salts of sodium, calcium, barium, magnesium, lithium, cobalt, iron, copper, aluminum, silicon, zinc, silver and lead can be used as the cationic compound herein. Particularly preferred cationic compounds herein are aluminum salts such as aluminum chloride. carbon dioxide derivatives
- carbon dioxide derivatives refers here to all compounds that are formed or can be formed as a result of a process of dissolving carbon dioxide in water.
- these include H 2 CO 3 , HCO 3 ', CO 3 2 '.
- Carbon dioxide (CO 2 ) forms carbonic acid in water.
- Carbonic acid (H 2 CO 3 ) is an inorganic acid and the reaction product of its acid anhydride, carbon dioxide (CO 2 ), with water.
- reaction compounds is understood to mean those compounds which carry out or bring about a reaction with carbon dioxide and/or carbon dioxide derivatives. In this case, carbon dioxide and/or the carbon dioxide derivatives are chemically converted and/or bound.
- reaction compounds herein are the "cationic compounds” defined above. absorption and release medium
- uptake and release medium means a gas, a liquid or a solid which adsorbs, absorbs, physiosorbs or binds carbon dioxide and/or carbon dioxide derivatives or which converts and/or releases them .
- This medium preferably contains compounds which bring about one or more of the aforementioned properties.
- the uptake and release medium can contain reaction compounds, acceptor compounds and also other compounds. Aqueous uptake and release media are particularly preferred herein.
- uptake and release medium refers to a medium in which the bound carbon dioxide can be released. The release of carbon dioxide can take place directly when the carbon dioxide derivatives, such as carbonate/bicarbonate anions, enter the absorption and release medium. It is preferred that the release of carbon dioxide from the absorption and release medium takes place after this has been introduced into a release device or release chamber.
- element refers to the known chemical elements arranged in order of increasing atomic number in the periodic table (PSE).
- elemental molecules are molecules that are made up of just two or more atoms of a single chemical element. Unlike element molecules, all other molecules consist of at least two atoms of different chemical elements (such as carbon dioxide (CO 2 ) made of carbon and oxygen).
- CO 2 carbon dioxide
- gaseous elements gaseous element molecules
- molecular compounds refers to molecules made up of at least two atoms of different chemical elements (such as carbon dioxide (CO 2 ) from carbon and oxygen).
- gaseous molecular compounds or “gaseous compounds” for short refers to molecular compounds that are gaseous under normal conditions.
- gas or "gas phase” are understood herein to mean a gaseous phase of an element or a chemical compound, which is present as a pure substance or as a mixture.
- a clean gas are gaseous carbon dioxide, methane or hydrogen.
- gas mixtures are air, combustion/flue gas, biogas, sewage gas or acidic natural gas.
- gas is one of the three classic states of matter.
- the standard conditions temperature 20 °C, pressure 101,325 Pa
- air refers here to the gas mixture of the earth's atmosphere. Dry air mainly consists of the two gases nitrogen (around 78.08% by volume) and oxygen (around 20.95% by volume).
- argon 0.93% by volume
- carbon dioxide 0.04% by volume or 400 ppm
- other trace gases in concentrations of less than 0.002% by volume or 20 ppm, such as neon (Ne), helium (He), methane (CH 4 ), krypton (Kr), nitrous oxide (N 2 O), carbon monoxide (CO), xenon (Xe), various chlorofluorocarbons (CFCs) such as dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, trichlorotrifluoroethane , 1,1-dichloro-1-fluoroethane, 1-chloro, 1-1-difluoroethane, as well as carbon tetrachloride, sulfur hexafluoride, bromochlorodifluoromethane and bromotrifluoromethane.
- CFCs chlorofluorocarbons
- solubility refers to a coefficient that indicates the amount of gas dissolved in the liquid at a specific pressure of the gas when the gas is in diffusion equilibrium between the gas space and the liquid, i.e. exactly as much diffuses in as out. Solubility depends on temperature, pressure and, for some compounds, pH.
- water-soluble gases means in this context that the gaseous molecular compound reacts chemically with water, e.g. B. to form an acid anhydride or an acid. It is then present in water as an organic or inorganic acid or as an anion.
- water-soluble gases are, in particular, the gases that fall under the term “acid gases”, which form an acid or a weak acid when dissolved in water.
- the gases falling under the term “water-soluble gases” are to be distinguished here from gases which do not chemically react with water when they come into contact with water.
- methane (CH 4 ) has a solubility of 36.7 ml/l in water at normal pressure and at 20°C. Methane (CH 4 ) does not react with water and is therefore not a "water-soluble gas”.
- water-soluble gas fraction includes all gaseous compounds that are present in a gas phase and that form a water-soluble compound with water when they come into contact with and/or mix with water. Examples are carbon dioxide, sulfur dioxide, hydrogen sulfide, nitrogen monoxide, nitrous oxide, hydrogen chloride or chlorine dioxide.
- the "water-soluble gas fraction” therefore includes “water-soluble gases” and in particular "acid gases”.
- the term "acidic gas” as used herein refers to a gas or gas mixture which, when dissolved in water, forms an acid or a weak acid. Acid gases are often corrosive and caustic as well as toxic and as such pose a risk to humans and the environment. Acid gases can be of natural origin or they can arise as desirable or undesirable reaction gases in industrial processes.
- acidic gases include, but are not limited to, carbon dioxide (CO 2 ) (forms carbonic acid and bicarbonates in water), sulfur dioxide (SO 2 ) (forms sulphurous acid in water), hydrogen sulfide (H 2 S), hydrogen chloride (HCl) (forms hydrochloric acid in water), nitrogen dioxide (N 2 O) (forms nitric acid in water), hydrogen cyanide (HCN) (forms hydrocyanic acid in water), hydrogen bromide (HBr) (forms hydrobromic acid in water), selenium dioxide (SeO 2 ) (forms selenium acid in water).
- basic amino acids refers to amino acids that have an amino group or N-atoms with lone pairs of electrons in the amino acid residue (side chain). If these N atoms accept a proton, a positively charged side chain is formed.
- the amino acids histidine, lysine and arginine belong to the basic amino acids. According to the invention, preference is given here to basic amino acids which carry at least one guanidino and/or amidino group, and the basic amino acid arginine is particularly preferred.
- electrochemical separation refers to an electrochemical separation using a separation membrane in an electrochemical process such as electrodialysis.
- electrolysis is carried out in an electrolysis cell.
- An electrolytic cell consists of two electrodes, e.g. made of carbon or platinum, and a conductive liquid.
- the electrode connected to the positive pole is called the anode
- the electrode connected to the negative pole is called the cathode.
- the cations then migrate to the negatively charged cathode and the anions migrate to the positively charged anode.
- the "electrophoretic separation cell” used herein in the "electrophoretic separation” consists of at least two chambers separated by a separating membrane.
- the “acceptor chamber” contains the aqueous acceptor solution according to the invention, containing at least one acceptor compound which has a free guanidino and/or amidino group.
- the bound carbon dioxide/carbon dioxide derivatives are transported via the separating membrane into an absorption and release medium in the "absorption and release chamber".
- the “electrophoretic separation” is based on the principle of the electrodialysis process.
- Electrodialysis is a process for separating ions in salt solutions. The necessary separation of the ions takes place via an electrical field applied via the anode and cathode as well as ion exchange membranes or semi-permeable, ion-selective membranes. Electrodialysis is an electrochemically driven membrane process in which ion exchange membranes are used in combination with an electrical potential difference to separate ionic species from uncharged solvents or contaminants.
- One of the most common membrane materials is polystyrene (PS).
- ion selectivity it can be modified on the surface by incorporating quaternary amines for anion-selective membranes and carboxylic acid or Sulfonic acid groups are modified for cation-selective membranes.
- Some membrane types are mechanically reinforced with polyvinyl chloride (PVC), polypropylene (PP) or polyethylene terephthalate (PET).
- separation medium refers to a medium through which selective mass transport can take place.
- a “separation medium” as used herein can therefore also be referred to as a separation membrane or transport membrane.
- membranes are used as the separating layer.
- Membranes can be permeable in different ways: impermeable, selectively permeable, unidirectionally permeable or omnipermeable.
- the majority of commercial membranes are made of polymers.
- a large number of different plastics are used, which are subject to very different requirements depending on the area of application.
- the two most common forms are coiled membranes and hollow fibers. Lipophilic polymer membranes can allow the passage of some gases or organics, but are impermeable to water and aqueous solutions.
- ionic groups in a polymer can also prevent the passage of ions through the membrane.
- membranes are used, for example, in electrodialysis. Other membranes are only permeable to water and certain gases. Commonly used membrane materials are: polysulfone, polyethersulfone (PES) cellulose, cellulose ester (cellulose acetate, cellulose nitrate), regenerated cellulose (RC), silicone, polyamide ("nylon", more precisely: PA 6, PA 6.6, PA 6.10, PA 6.12, PA 11 , PA 12), polyamideimide, polyamide urea, polycarbonates, ceramics, stainless steel, silver, silicon, zeolites (aluminosilicates), polyacrylonitrile (PAN), polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), Polyvinyl chloride (PVC), polypiperazinamide. Ceramic membranes are mainly used in areas that place high chemical
- separation membrane refers to a separation medium used in electrophoretic separation or electrolysis.
- the separating membrane is preferably an open-pored membrane, more preferably an open-pored mesoporous membrane.
- the separation membrane is a ceramic filter plate.
- the separation membrane is an anion selective membrane. All suitable separating membranes from the prior art can be used as the separating membrane. Well known in the art of ion selective separation membranes and bipolar separation membranes.
- separation media for contacting carbon dioxide-containing gas with acceptor medium refers to "separation membranes" capable of mass transfer between a gas and liquid phase. These separation media are also referred to herein as a "gas-liquid separation membrane”. Contacting carbon dioxide-containing gas with acceptor medium is also referred to herein as “indirect contacting”.
- the gas-liquid separation membrane can be provided in the form of a membrane contactor. Membrane contactors are preferably used herein for indirectly bringing a carbon dioxide-containing gas into contact with an acceptor medium.
- a membrane film that is attached to a carrier material can also be provided as a gas-liquid separation membrane. Such gas-liquid separation membranes are known from the prior art.
- Preferred Gas-Liquid Separation membranes have an average pore size of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferably >200 pm. Gas-liquid separation membranes with an average pore size of 200 ⁇ m are particularly preferred. Preferred gas-liquid separation membranes have a membrane thickness of ⁇ 300 pm, more preferably ⁇ 200 pm, more preferably ⁇ 150 pm, more preferably ⁇ 100 pm, more preferably ⁇ 50 pm and even more preferably ⁇ 25 pm.
- Preferred gas-liquid separation membranes have open channels with a mean channel diameter of >10 pm, more preferably >50 pm, more preferably >100 pm, more preferably >150 pm, more preferably >200 pm, even more preferably >250 pm and most preferably >300 pm.
- Preferred gas-liquid separation membranes have a porosity of >50%, more preferably >60%, more preferably >70%, more preferably >80% and even more preferably >90%. Porosity is defined as the number of pores per unit area.
- Suitable gas-liquid separation membrane materials include, but are not limited to, PTFE (polytetrafluoroethylene) or PC (polycarbonate) or ceramic.
- gas scrubbing or absorption If a stream of gas or air is passed through a scrubbing liquid, this is referred to as gas scrubbing or absorption.
- the gas components to be absorbed are bound in the scrubbing liquid (absorbent - unloaded, absorbate - loaded).
- salts refers to chemical compounds made up of positively charged ions (cations) and negatively charged ions (anions). Ionic bonds exist between these ions.
- inorganic salts the cations are often formed by metals and the anions are often formed by non-metals or their oxides.
- Organic salts are all compounds in which at least one anion or cation is an organic compound; with the exception of the carbonates, which are derived from carbonic acid (H 2 CO 3 ), which is inorganic by definition.
- atmospheric pressure refers to the air pressure at any point in the earth's atmosphere.
- atmospheric pressure and “standard pressure” are used interchangeably herein.
- non-pressurized as used herein also refers to the terms “atmospheric pressure” and “standard pressure”. If it is described in this application that a process step is carried out “without pressure”, this corresponds to a process being carried out under “atmospheric pressure” and “normal pressure”.
- no pressurization as used herein also refers to the terms “atmospheric pressure” and “standard pressure”. If it is described in this application that a process step is carried out “without pressurization”, this corresponds to a process being carried out under “atmospheric pressure” and “normal pressure”.
- a gas scrubber, scrubber or absorber is a process engineering apparatus in which a gas flow is brought into contact with a liquid flow in order to absorb components of the gas flow in the liquid.
- the components of the gas stream that are transferred can be solid, liquid or gaseous substances.
- Gas washing devices known from the prior art can be used for separating CO 2 from flue gases or biogases will.
- a scrubber may include a pre-scrubber column. A distinction is made between fixed bed columns, packed columns, tray columns and spray columns.
- clean gas results from the division into the following cleanliness classes:
- Technical gas - The gas is used for general technical purposes, is usually produced on a large scale and can have an extraneous smell and colour.
- Gas for synthesis contains small amounts of impurities, which usually do not interfere with synthesis, since purification takes place during the production of the synthesis product.
- Purest gas (purissimum, puriss.) - particularly pure quality with a substance content of at least >99.5% by volume. No foreign substances can be detected with common analysis methods. Appearance and characteristic data correspond to the relevant literature.
- the method is particularly suitable for the selective removal of a proportion of carbon dioxide from a gas or gas mixture.
- Gases/gas mixtures with a high proportion of carbon dioxide such as flue gases/combustion gases, are preferred.
- digester gases which are produced, for example, during the decomposition of sewage residues.
- the process is also suitable for purifying mineral or industrial gases. The process is therefore suitable for purifying gases/gas mixtures that contain water-soluble gas components.
- the extraction of the water-soluble components of a gas/gas mixture that can be achieved with the method can also be used to clean anaerobic gas phases, such as digester gas or biogas, from water-soluble gas components in order to obtain a technically pure or ultra-pure gas, e.g. as methane or bio -Methane.
- anaerobic gas phases such as digester gas or biogas
- technical gases/gas mixtures can be produced with the method.
- the process is also suitable for the production and extraction as well as for the conversion of hydrogen.
- the method is also suitable for extracting, transporting, storing and making available gas components from gases/gas mixtures.
- pure gaseous carbon dioxide can be obtained with the method, which can be used in a large number of industrial sectors.
- the carbon dioxide obtained can be used as a technical gas, as a propellant (e.g. for beer pumps), to enrich carbon dioxide (e.g. in food or concrete) or for dry ice production. Therefore, the process is suitable for the production of pure and high-purity carbon dioxide.
- the method makes it possible to obtain regenerative carbon dioxide, with which/through which regenerative products can be produced.
- applications are plant breeding or the production of a regenerative carbon cycle economy, whereby cycle components can be produced, such as synthetic fuel compounds or synthetic carbon compounds.
- the process is therefore suitable for the production of regenerative carbon dioxide.
- the method is also suitable for storing the bound carbon dioxide over long periods of time or to transport it.
- the process enables the chemical conversion of the bound carbon dioxide directly and without further energy input, which means that important starting materials for organosynthesis (production of carbon compounds) can be produced directly and separated with simple means.
- the method is suitable for the production of organic compounds.
- Carbonates and hydrocarbonates can be obtained in pure form with little technical effort.
- the process is therefore suitable for the production of carbonates and hydrocarbonates.
- Carbonates and hydrogen carbonates are important raw materials, for example as fillers in building materials or in the paper industry, but also as food supplements for humans and animals, as well as ingredients in tablets or dentifrices.
- process embodiments according to the invention are suitable for producing regenerative and sustainable products.
- Figure 1 Scheme of a device for the adsorption, transport and release of water-soluble gases.
- any gas/gas mixture containing a water-soluble gas or gaseous component, 1a) represents the inlet device for the gas/gas mixture to be purified 1); 2) represents a scrubber in which the gas 1) is contacted with the acceptor solution; through the outlet 3) the gas 1) escapes after the extraction of the water-soluble gas component; 4) represents the receiver for the acceptor solution contacted with the gas 1) in the scrubber 2); 5) represents a circulation circuit of the acceptor medium, which consists between the gas washing device and the acceptor chamber 7) of the electrodialysis device, where from 4) the acceptor solution saturated with the soluble gas is fed to the acceptor chamber 7) via an inlet, and where the acceptor solution containing the dissolved gas has been withdrawn and exits an outlet of the acceptor chamber and is introduced through a conduit into the scrubber 2);
- the electrodialysis device consists of the individual components: 6) the cathode chamber, 7) the acceptor chamber, 8) the receiving and release chamber, 9) the anode
- DI water deionized water
- a 0.5 molar arginine solution is prepared with deionized water and filled into a gas washing device.
- the device is over 10 hours with a constant Flows through carbon dioxide gas stream, the pH of the solution being determined continuously.
- arginine in powdered form was added to the liquid and dissolved by means of a mixing unit introduced into the device. This is repeated until the total molar concentration of arginine in the solution is 3 mol/l.
- a pH of 8 was reached and a clear liquid without solids was present at the same time, the introduction of gas was stopped.
- a part of the solution was taken out for long-term experiments and stored in a closed gas-retaining device under ambient pressure conditions (101.3 kPa) at a temperature of 20°C.
- the volume of the gas that had escaped from the solutions that had been stored for a period of 3 and 6 months was determined. After the end of the long-term tests and the sample that was available after the end of the test, these were filled into a gas collection device and HCl was added and mixed in until a pH of 1 was reached molar mass is determined and the relation to the molar concentration of the arginine present in the solution is calculated. The experiments were repeated 3 times. The solutions were then cleaned of the chloride and hydrogen ions present in an electrodialysis unit until the pH of the solution was 12.5. These solutions were used for further repeat experiments, with the acceptor solution being loaded with carbon dioxide until the solution reached a pH of 8. The amount of carbon dioxide gas bound in the solution was then determined on 3 samples using the method described above Proceedings.
- Flue gases from cement production and from a wood chip CHP with a carbon dioxide content of 11.2 and 16.9% by volume were passed through a gas scrubbing column.
- the flue gases were passed through a soot filter.
- the first section of the scrubbing column contained a 50% strength ammonium nitrate solution which was acidified to a pH of 5 with nitric acid as the scrubbing medium.
- the gas stream is then passed through an aerosol filter.
- the 2nd section of the gas washing column had a gas inlet device, which was filled with an arginine solution and the gas exit into the acceptor liquid took place through a nanoporous ribbed ceramic membrane (Kerafol, Germany) with a total surface area of 60m 2 , which was placed at the bottom of the chambers and through which the flue gases were introduced, with the mean size of the exiting gas bubbles being in the range from 1 to 20 pm.
- This column section consisted of 10 consecutively arranged chamber segments, in each of which the gas phase that collected above the liquid level was fed via a pipeline to the inlet of the gas inlet device of the next chamber segment.
- the acceptor solution in the wash column was passed through the segments in a countercurrent process.
- the cleaned gas mixture was collected and the concentration of carbon dioxide was determined.
- the experiment was carried out with different concentrations of arginine between 0.1 and 0.5 mol/l and volume flows from 100 ml to 1,000 ml/min. Furthermore, the volume flow of the flue gas to be cleaned was varied between 200 cm 3 and 1 m 3 /minute. It became the Calculated contact time within which a depletion of carbon dioxide to a concentration range of ⁇ 0.01% by volume (100ppm) was achieved. The contact time was calculated for an average gas bubble size of 10 pm.
- a continuous separation of carbon dioxide from gas mixtures was carried out by a process arrangement consisting of a carbon dioxide separation unit and a carbon dioxide release unit.
- a flue gas, a gas mixture from biogas production and technical gases with carbon dioxide concentrations between 3.5 and 65% by volume were used. These were passed through the wash column described in Example 2 at a volume flow rate of between 500 cc and 1.5 m 3 / hour. The gas passed through was collected and the concentration of carbon dioxide was determined.
- Arginine was dissolved in the acceptor solution in a concentration of 0.5 mol/l (deionized water was used for the solution).
- the acceptor solution enriched in carbon dioxide in the scrubbing column was fed into an electrodialysis unit which was composed of 12 consecutive dialysis chamber units, each consisting of an acceptor chamber and an uptake and release chamber. The introduction took place in the cathode chamber, in which the cathode was located. The acceptor liquid was passed consecutively through the subsequent acceptor chamber. The acceptor liquid discharged on the anode side was fed back to the gas scrubbing column to the inlet of the acceptor liquid. A circulation was thus set up between the gas scrubbing column and the electrodialysis unit, with a volume flow between 500 ml and 1.5 l/min.
- the uptake and release chambers of the electrodialysis unit were connected to each other, so that the chambers could be constantly filled with the uptake and release medium.
- a reservoir for escaping gas existed above the liquid level of the absorption and release medium, which was diverted into a large-volume external gas reservoir.
- Mesoporous ceramic separation membranes with hydrophobic surface coating were located between the cathode chamber and the acceptor chamber and between the uptake and/or release chamber.
- the subsequent dialysis chamber unit was separated in a pressure-stable manner by an electron-conducting membrane (bipolar membrane), which was clamped between the acceptor chamber and the receiving and release chamber. The remaining chamber units were arranged accordingly.
- A) glutamic acid (10 g/l) or b) citric acid (100 g/l) was present in dissolved form in the uptake and release medium.
- the pH of the uptake and release medium was monitored during electrodialysis.
- a DC voltage of 20 V was applied between the cathode and the anode.
- the volume of gas released in the intake and release chambers was determined and an analysis of the gaseous compounds contained therein was performed.
- the carbon dioxide concentration present in the gas mixture which had flowed through the gas-collecting device was also determined.
- the contact times required to achieve a reduction in the carbon dioxide concentration to ⁇ 100 ppm in the gas mixture that had been passed through the gas scrubbing column in the respective test arrangements were calculated. The tests were carried out at 20°C and under normal pressure conditions.
- the carbon dioxide concentration could be reduced to ⁇ 100ppm.
- the contact time required for this was between 0.5 seconds and 2 minutes and was essentially dependent on the carbon dioxide concentration of the starting gas mixture and the flow rate of the acceptor liquid through the electrodialysis unit.
- the gas released in the uptake and release chambers of the electrodialysis unit had a carbon dioxide content of >99% by volume.
- the calculated mass of carbon dioxide that was in the separated gas volume corresponded to the calculated mass of carbon dioxide that had been removed from the source gas mixtures.
- the chemical convertibility of carbon dioxide or carbonate/bicarbonate anions that were dissolved or bound in an acceptor medium was investigated.
- aqueous solutions containing the acceptor compounds arginine and lysine or histidine in a concentration of 0.1 to 0.5 mol/l were used as acceptor solutions, the solution being made with deionized water.
- Carbon dioxide was introduced by means of a gas scrubbing column according to example 2, a flue gas having a carbon dioxide content of 22% by volume being used for the extraction of carbon dioxide.
- the acceptor compounds used were added in solid (powder) form with continuous recording of the pH if the pH of the acceptor solution had fallen by more than 1 compared to the starting point due to the uptake of carbon dioxide. The addition was terminated when a total of 3 mol/l of the respective acceptor compound had completely dissolved and a clear solution was present.
- a catalyst ruthenium complex immobilized on MCM-41) was fixed on PU meshes using an adhesive. These nets were clamped into the acceptor chambers of the electrodialysis units according to example 3, so that the acceptor medium flowing through the acceptor chambers washed around them.
- Example 3 Deviating from Example 3, an anion exchange membrane with a cut-off of 400 Da was used as the separating membrane between the acceptor chamber and the receiving and release chamber. In this experiment, an arginine solution with a concentration of 0.3 mol/l was used as the absorption and release medium. Furthermore, in contrast to Example 3, the uptake and release medium was circulated in a secondary circuit, in which the medium ran through a separating device in which calcium carbonate was added to the solution and then passed into a settling tank in which complexes from the into the uptake and release medium transported carboxylic acid and calcium complexes. After passage through a column of cation exchange resin, the solution was returned to the anode compartments.
- the carbon dioxide content in the flue gas was cleaned to a level of ⁇ 100ppm.
- the absorption and transport took place by means of acceptor solutions in which basic amino acids were dissolved, the concentration of which in the solution could be increased significantly above the respective solubility limit of the amino acids used in neutral water by the absorption of carbon dioxide in the solutions. This allowed high concentrations of carbon dioxide and carbonate / bicarbonate anions in the produce aqueous acceptor solutions.
- Formic acid which was present in high concentrations, could be detected by means of an alcoholic extraction from the precipitated calcium complexes of the secondary circuit. It was thus possible to show that, on the one hand, the carbon dioxide present in the acceptor solution and its derivatives were chemically converted and, on the other hand, the resulting carboxylic acids were transported into the absorption and release medium by means of electrodialysis.
- a gas washing device containing packing which was continuously sprayed with an acceptor solution, was used (Fig. 1: 2)).
- a partial flow of a biogas with a volume flow of 100m 3 /h was passed through (Fig. 1: 2)).
- the packing bodies were subjected to a volume flow of the acceptor solution of 100 l/min.
- the acceptor solution from a storage tank 1 was used (Fig. 1: 4)).
- the acceptor solution used for the gas scrubbing was fed from the gas scrubbing device to an electrodialytic unit for desorption of the carbon dioxide bound in the acceptor solution (Fig.1: 5)). This consisted of a catholyte (Fig.
- the acceptor solution warmed up to a temperature between 34 and 56°C.
- a 10% by weight citric acid solution was used as the uptake and release medium.
- the volume ratio between the acceptor medium and the release medium flowing through the dialysis unit was 2:1.
- a DC voltage of 20 V was applied between the anode and the cathode.
- the chamber devices for receiving the absorption and release medium were provided with an outlet for gases, which were connected to an initially evacuated gas collection device.
- the storage vessel for the absorption and release medium was also connected to this collection device, so that a gas flow that was produced could be taken up there without pressure.
- the CO2 content of the gas stream that had passed through the gas scrubber and of the gas that was collected in the gas collection device were continuously determined.
- the treated biogas had a CO2 content of 48% by volume.
- the gas that had passed through the gas scrubber had a CO2 content of 0.002% by volume and a methane content of 99.1% by volume.
- CO2 was released both in the absorption and release chambers and in the storage vessel for the absorption and release medium.
- the CO2 content of the released and collected gas was > 98.5 vol%, methane was not detected here. Continuous operation was possible for more than 8 hours without any problems. A relevant heating of the process media did not occur.
- the centrifugate was suspended in 3 liters of deionized water and stirred for one hour. In each case, a phase separation was carried out by means of centrifugation.
- the brown-reddish mass was spread on ceramic filter plates with an average pore size of 200 ⁇ m.
- the filter plates were stored on an absorbent material until the feed material was completely dry.
- the crumbly brown material was crushed in a mortar. 480 g of a brown powder were obtained.
- a sample was suspended in water and agitated therein. Subsequent sedimentation of the powder. The supernatant was then clear and colorless, the pH was unchanged from the initial 6.8.
- a 10% HCl solution was added to another sample of the powder. Foaming occurred, releasing CO2.
- the solution was then red-brownish, and there was no longer any solid in it. No nitrogen could be detected in the analysis of this decomposition solution.
- the powder obtained corresponded to iron carbonate.
- the WP1 was passed through an electrodialysis unit.
- the donor chambers were sealed on the anode side with an anion-selective membrane, and on the cathode side with a cation-selective membrane.
- a DC voltage of 10V was applied. It could be shown that chlorine gas was released in the anode chamber and hydrogen in the cathode chamber.
- the solution was gassed with CO2. After gassing, the CO2 bound in the solution could be released again by changing the pH using an acid (HCL).
- a partial flow (10m 3 /h) of the gas from a bioreactor of a municipal sewage treatment plant was sucked in by means of a water jet pump device and brought into contact with the aqueous acceptor medium.
- the water/gas mixture was piped to a static mixer and passed through it. The mixture then entered a holding tank from which the gas was free to escape into the atmosphere.
- the aqueous acceptor medium was a 2 molar arginine solution.
- the acceptor medium loaded with carbon dioxide was pumped continuously from the collecting tank into a secondary circuit.
- the secondary circuit consisted of an electrodialysis device consisting of an anode chamber, a cathode chamber and 10 consecutive chamber units in the arrangement:
- acceptor chamber/reaction chamber/electrolyte chamber The acceptor chambers were successively flowed through by the acceptor medium and then fed to the water jet pump device.
- the reaction medium and the electrolyte solution were each taken from a storage container and passed through the reaction chambers and the electrolyte chambers.
- the acceptor chambers were separated from the reaction chambers towards the anode by an anion-selective membrane. On the cathode side, these were separated from the electrolyte chambers by a bipolar membrane.
- the reaction chambers and the electrolyte chambers were separated by a cation selective membrane.
- the chamber units for the reaction medium bordered the electrolyte chambers on the anode side.
- Various reaction media were examined.
- reaction solutions were prepared from a 1 molar arginine solution: a) 30% magnesium chloride solution, b) 20% copper chloride solution, c) 15% aluminum chloride solution.
- the reaction medium was continuously recirculated through the reaction chambers from a settling tank.
- the reaction chambers were designed in such a way that the reaction medium flowed vertically through the chamber and was directed through a conical bottom outlet into the collection tank, which also discharged the solids formed.
- no further agitation of the reaction medium was carried out for 12 hours.
- the aqueous supernatant was then drained off through an outlet placed above the solid phase, and the solid was then removed and rinsed twice with deionized water and then dried on a contact belt dryer.
- the electrolyte solution was fed in a tertiary circuit to a further electrodialysis unit, in which the chloride ions were separated.
- the temperature range of the acceptor medium was between 45 and 75°C.
- the sewage gas had a carbon dioxide content of 26% by volume. By bringing the sewage gas into contact with the acceptor medium, the carbon dioxide content was reduced to ⁇ 0.01% by volume. After the acceptor medium began to be passed through the electrodialysis unit, the reaction solutions quickly became milky and solids continuously precipitated out. Analysis of the rinsed and dried solids showed that they were the carbonates of the cations used in the electrolyte. Thus, magnesium carbonate, copper carbonate and aluminum carbonate were produced.
- Used aluminum cans (100 g) are completely decomposed in a crushed form in 200 ml of concentrated sulfuric acid by adding deionized water in portions in the amount in which hydrogen and water vapor escaped.
- the vapour/gas mixture was collected and the hydrogen available therein was separated.
- the solution obtained was grey-brownish and very cloudy.
- the solution is filtered using a glass frit and mixed with 600 ml of a 1 molar arginine solution. This mixture is stirred in portions into a 3 molar arginine solution which was saturated with carbon dioxide from the gas mixture of a biogas plant. After the mixing process, the suspension was centrifuged and the centrifugate rinsed twice with deionized water and dried after centrifugation.
- the solid forming in the reaction chamber was separated and rinsed twice with deionized water and convectively dried after centrifugation.
- the electrolyte solution in the anode chamber which was available at the end of the test, was concentrated by means of a membrane distillation and used for another test procedure.
- the acceptor solution was also added to the carbon dioxide absorption test after the test related to the decomposition of bones. During the investigations, the energy supply was provided by solar power.
- the solid fractions obtainable in the two process embodiments were aluminum carbonate and calcium carbonate. These were in chemically pure powder form in the form of amorphous particles.
- the compounds (acids) used to decompose the starting materials could be regenerated in a secondary circuit and used for a new experiment.
- the acceptor solution could also be regenerated and reused. It was thus possible to recycle inorganic residues using regenerative carbon dioxide and regenerative energy, enabling sustainable recycling of the compounds used.
- a 2-molar arginine solution (prepared with deionized water) is circulated through a static mixing device, in which carbon dioxide is added as a gas phase to the solution upstream of the static mixer.
- the gas is applied without pressure until the acceptor solution has reached a pH of 8.
- the chemical reaction is carried out by mixing each of the clear and colorless electrolyte solutions 1A, 1 Ü, 2A and 2Ü into 1000ml of the acceptor solution using a dosing pump until a pH of 7 is reached. The mixing process was continued with fresh, saturated acceptor solution. 15 minutes after the completion of the mixing, the reaction mixtures were centrifuged. The supernatants were decanted and pooled (V1). The centrifuges obtained for the respective test series were suspended in 1000 ml of deionized water and agitated therein for 15 minutes. Then phase separation by centrifugation. This process was repeated 2 more times. The centrifugates were spread on mesoporous ceramic membranes and left at room temperature for 24 hours. The subsequently dry material was weighed and samples were taken for analysis, which was carried out according to Examples 5 and 6.
- the arginine concentration is determined spectroscopically after addition of a ninhydrin reagent.
- a clear solution could be prepared from the hydrolyzate of an aluminum foil (experimental procedure 1).
- the addition of ammonia caused flocculation.
- the resulting solid could be completely centrifuged off.
- the centrifugal had 2 parts with different colors: below pure white somewhat glassy mass, above grey-brown solid mass.
- flocculation also occurred, but the centrifugal was uniformly white and gel-like in consistency.
- a white solid could be produced by mixing with the saturated acceptor solution.
- the centrifugate phases did not differ visually from one another.
- the supernatants after the first centrifugation were cleaned of electrolytes contained therein by means of electrodialysis.
- the liquid volume was then reduced by means of a membrane distillation so that the initial concentration of the arginine solution was restored. This was used to absorb carbon dioxide again and repeat the test procedure.
- Aluminum carbonate and aluminum bicarbonate could be obtained with the same efficiency.
- a 2 molar arginine solution was prepared with deionized water. Of this, 2 liters were separated and stored in the absence of air (A0). The remaining acceptor solution was treated according to Example 7 with a gas stream of carbon dioxide. The degree of loading with carbon dioxide or its water-soluble derivatives was monitored by means of a conductivity measurement. The acceptor medium was exposed to carbon dioxide until a conductivity of 150mSi was reached (A1).
- KOH (K) and NaOH (N) were prepared as the stock solution. From each of these, 2 liters of a) 1% by weight, b) 2% by weight, c) 3% by weight and d) 4% by weight solution were prepared.
- KOH (A1 K) and NaOH (A1N) were added as a solid and dissolved in 2 liters each of A1 so that these were present as a) 1% by weight, b) 2% by weight, c) 3% by weight and d) 4% by weight solution.
- a rectangular glass vessel was manufactured to hold 500 ml of liquid, in which a separating device could be placed in the middle, as a result of which 2 chambers in the vessel were separated from one another.
- a perforated disc made of polycarbonate was introduced as the separating device, the perforations of which had a diameter of 2 mm and a porosity of 70%.
- a graphite electrode was placed in a holder in each of the chambers, which enabled the electrodes, which were arranged parallel to the separating device, to be moved axially.
- the vessel was sealed gas-tight at the top, with a lid-side outlet for each chamber. These outlets were each connected to a gas-collecting device, which enabled a gas that had formed in the respective chamber to be discharged without pressure. The respective gas volume could hereby be quantified.
- the vessel had an inlet and outlet on both ends for filling and for the passage of liquids.
- the electrodes were connected to a rectifier.
- the vessel was filled consecutively with the different test solutions so that no air remained in it.
- solutions K) and N) were each filled into the vessel in concentrations a)-d).
- the electrical direct voltage was determined for each solution, above which a current flow occurred (Smin). The voltage was then determined at which gas bubbles formed at both electrodes, which led to the separation of a gas volume.
- the solutions A0 and A1 as well as A1 K and A1 N in the concentrations a) - d) examined consecutively.
- a constant voltage of at least 1 volt higher than Smin and a multiple of 2 was applied to each of the solutions for 10 minutes.
- the voltage was increased by 2 V every 10 minutes up to a voltage of 32 V.
- the formation of gas bubbles on the electrodes, the respective current flow (mA) and the amount of gas that was generated during the current delivery were recorded.
- test series II the test was repeated for each of the solutions with the voltage that had previously been determined for the respective solution at which there had been no gas formation at the cathode, with the vessel being perfused with the respective solution. so that there was a flow from the cathode chamber through the separation medium into the anode chamber. The gas released and collected in the cathode chamber was applied to the chemical
- solutions K and N electrolysis led to hydrogen and oxygen bonding from a voltage of 2 - 4V.
- solution AO there was no current flow up to 24 V and up to 32 V there was no electrolysis which led to the formation of a gas phase.
- solution A1 there was a current flow from 12V; Gas formation at the cathode occurred from a voltage of 20V. Gas formation at the anode did not occur even at a voltage of 32 V.
- the solutions A1 K and A1 N the Smin decreased as the concentration increased. Furthermore, the required voltage, which led to the formation of gas at the cathode, decreased as a function of the concentration. With these solutions, too, no measurable amount of oxygen was formed at the anode.
- the gas that formed at the cathode in solutions A1 and A1 K and A1 N corresponded to carbon dioxide.
- the amount of gas that could be obtained with an identical voltage system was significantly larger for A1 K and A1 N than for A1 and increased with the concentration of the electrolyte added.
- the amount of carbon dioxide released at the cathode increased by 20-40% by volume due to the perfusion of the vessel with the solutions A1, A1K and A1N.
- AL -CO2 acceptor solution loaded with carbon dioxide
- NaOH concentration of sodium hydroxide in the acceptor solution in wt%
- KOH concentration of potassium hydroxide in the acceptor solution in wt%
- K gas volume that has formed in the cathode chamber within the test period in ml at normal pressure
- A
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KR1020237006456A KR20230044466A (ko) | 2020-07-27 | 2021-07-27 | 수용성 가스의 결합, 수송, 반응 활성화, 전환, 저장 및 방출을 위한 방법 |
BR112022026014A BR112022026014A2 (pt) | 2020-07-27 | 2021-07-27 | Método para ligar, transportar e armazenar seletivamente dióxido de carbono em meio aquoso e carbonato de alumínio e/ou hidrogenocarbonato de alumínio obtenível pelo método |
US18/007,014 US20230264141A1 (en) | 2020-07-27 | 2021-07-27 | Method for the bonding, transport, reaction activation, conversion, storage and release of water-soluble gases |
EP21759023.1A EP4153343A1 (de) | 2020-07-27 | 2021-07-27 | Verfahren zur bindung, transport, reaktionsaktivierung, umsatz, speicherung und freisetzung von wasserlöslichen gasen |
MX2023001128A MX2023001128A (es) | 2020-07-27 | 2021-07-27 | Metodo de union, transporte, activacion de reacciones, conversion, almacenamiento y liberacion de gases solubles en agua. |
JP2023505994A JP2023537291A (ja) | 2020-07-27 | 2021-07-27 | 水溶性気体の結合、輸送、反応活性化、変換、保存および放出のための方法 |
IL299145A IL299145A (en) | 2020-07-27 | 2021-07-27 | A method for binding, transferring, converting, storing and releasing water-soluble gases |
CA3182886A CA3182886A1 (en) | 2020-07-27 | 2021-07-27 | Method for binding, transport, reaction activation, conversion, storage and release of water-soluble gases |
CN202180060246.6A CN116669836A (zh) | 2020-07-27 | 2021-07-27 | 水溶性气体的结合、输送、反应活化、转化、储存和释放的方法 |
AU2021314895A AU2021314895A1 (en) | 2020-07-27 | 2021-07-27 | Method for the bonding, transport, reaction activation, conversion, storage and release of water-soluble gases |
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WO2023166188A3 (de) * | 2022-03-03 | 2023-11-23 | Greenlyte Carbon Technologies Gmbh | Verfahren zur abtrennung von kohlendioxid aus einem luftstrom und regenerierung des absorptionsmittels in einer drei-kammer-elektrolysezelle |
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US20040219090A1 (en) * | 2003-05-02 | 2004-11-04 | Daniel Dziedzic | Sequestration of carbon dioxide |
WO2013036859A1 (en) | 2011-09-07 | 2013-03-14 | Carbon Engineering Limited Partnership | Target gas capture |
US20170072361A1 (en) * | 2014-03-07 | 2017-03-16 | Korea Institute Of Energy Research | Carbon dioxide collecting apparatus and method using independent power generation means |
EP3685904A1 (de) * | 2019-01-24 | 2020-07-29 | Axiom Angewandte Prozeßtechnik Ges. m.b.H. | Verfahren und anlage zur abtrennung von kohlendioxid aus der luft |
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US20040219090A1 (en) * | 2003-05-02 | 2004-11-04 | Daniel Dziedzic | Sequestration of carbon dioxide |
WO2013036859A1 (en) | 2011-09-07 | 2013-03-14 | Carbon Engineering Limited Partnership | Target gas capture |
US20170072361A1 (en) * | 2014-03-07 | 2017-03-16 | Korea Institute Of Energy Research | Carbon dioxide collecting apparatus and method using independent power generation means |
EP3685904A1 (de) * | 2019-01-24 | 2020-07-29 | Axiom Angewandte Prozeßtechnik Ges. m.b.H. | Verfahren und anlage zur abtrennung von kohlendioxid aus der luft |
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WO2023166188A3 (de) * | 2022-03-03 | 2023-11-23 | Greenlyte Carbon Technologies Gmbh | Verfahren zur abtrennung von kohlendioxid aus einem luftstrom und regenerierung des absorptionsmittels in einer drei-kammer-elektrolysezelle |
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JP2023537291A (ja) | 2023-08-31 |
KR20230044466A (ko) | 2023-04-04 |
EP4153343A1 (de) | 2023-03-29 |
CL2023000163A1 (es) | 2023-07-14 |
MX2023001128A (es) | 2023-02-22 |
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IL299145A (en) | 2023-02-01 |
AU2021314895A1 (en) | 2023-02-02 |
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