Device and method for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases

Abstract

Device (1) according to Figure 1 for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1), which, viewed in the direction of flow of the combustion exhaust gases (1.1), is connected (i) to a device for cooling (1.1) or (ii) to such a device and a catalyst for selective reduction (SCR) or (iii) to an SCR, a catalyst for selective oxidation (SCO) and a feed line (Z) for (1.1) to the device (1), wherein the device (1) is sealable and comprises a device (2) for alternately cooling and heating an adsorber material (1.3) by means of a halogen-free liquid (2.1), a device (3) for collecting the desorbed carbon dioxide and a pressure vessel (4) for storing the desorbed carbon dioxide, wherein the adsorber material (1.3) consists of platelet-shaped metal microparticles or metal microflakes fixed with a polymer or adhesive matrix (1.6). (1.4) contains and the fixed metal microflakes (1.4) are present in such a quantity that the adsorption capacity of the adsorber material (1.3) is reduced to 1% to 50% of the adsorption capacity of the native adsorber material (1.3.1) free of fixed metal microflakes (1.4; 1.6), and a method for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1).

Description

Field of invention

[0001] The present invention relates to a device for the reversible adsorption and subsequent desorption of carbon dioxide in combustion exhaust gases.

[0002] Furthermore, the present invention relates to a method for the reversible adsorption of carbon dioxide in combustion exhaust gases and for the subsequent desorption and collection of the desorbed carbon dioxide. State of the art

[0003] US 2008 / 0 237 131 A1 and WO 2011 / 155 058 A1 disclose a device for the reversible adsorption and desorption of, among other things, carbon dioxide from a gaseous environment. The device according to US 2008 / 0 2378 131 A1 comprises a water separator, and both disclosures include a temperature control system for the adsorber operated with a liquid heat transfer medium, wherein the heat transfer medium can be, for example, glycol or ethylene glycol.

[0004] In recent years, numerous research and development projects have been and continue to be conducted as part of climate protection efforts to reduce the carbon dioxide concentration in the atmosphere. One promising approach is the reversible adsorption of carbon dioxide in gas mixtures, particularly in the combustion exhaust gases of combustion engines, furnaces, and power plants, and its subsequent desorption.

[0005] Adsorbent materials for the reversible adsorption of carbon dioxide are known.

[0006] For example, the American patent US 7,795,175 B2 describes polyamine or polyamine-polyol adsorbent materials supported on nanoparticles such as nanosilicates.

[0007] US 2013 / 0 037 481 shows an adsorbent material with a species of metal microflakes with a particle size of less than 1000 µm.

[0008] The international patent application WO 2017 / 009241 discloses fibrillated cellulose functionalized with amino groups using aminosilanes as adsorbent materials.

[0009] American patent US 9,968,880 B2 describes polyamine aldehyde adducts supported on pyrogenic silica as adsorbent materials.

[0010] European patent EP 3 706 898 B1 reveals that the adsorbent material is activated carbon impregnated with sodium and / or potassium carbonate.

[0011] International patent application WO 2021 / 259760 A1 discloses inorganic or organic, non-polymeric and polymeric carrier materials with a specific BET surface area of ​​1 to 20 m² as adsorbent materials. 2 / g, which are functionalized on their surface with amino-functional groups.

[0012] International patent application WO 2022 / 013107 A1 discloses primary and / or secondary amino groups immobilized on a support material, which are substituted at the alpha-carbon atom with oxygen or a residue R, as adsorbent materials. The residues R can be, for example, alkyl, alkenyl, and arylalkyl groups with 1 to 12 carbon atoms. A typical example of such adsorbent materials are polystyrene beads containing alpha-methylbenzylamine.

[0013] According to international patent application WO 2022 / 109746 A1, zeolites, metal-organic frameworks (MOFs), silica or aluminium oxide can serve as adsorbent materials for carbon dioxide.

[0014] International patent application WO 2022 / 128431 A1 discloses cycloaliphatic amines such as aziridine, diaziridine, azetidines, 1,2- and 1,3-diazetidine, pyrrolidine, diazolidine, triazolidine, piperidine, 1,2- and 1,3-diazinane, piperazine, triazinans, tetrazinanes, azepanes, azocanes, and mixtures thereof, in particular piperazine, as adsorbent materials. The amines are used in mixtures with lithium, sodium, and / or potassium carbonate and are supported on activated carbon or fibers such as cellulose fibers.

[0015] International patent application WO 2022 / 183058 A1 describes zinc ion-containing zeolites as adsorbent materials.

[0016] According to international patent application WO 2022 / 235664 A2, sodium bicarbonate is suitable as an adsorbent material for the adsorption of carbon dioxide from water vapor-containing gas mixtures. The carbon dioxide is stored in the form of sodium sesquicarbonate.

[0017] The international patent application WO 2023 / 001810 A1 discloses the production of amino-functionalized polyacrylonitrile fibers that can be used as adsorbent materials.

[0018] International patent application WO 2023 / 088812 A1 discloses a method for the regeneration of amino-functional adsorbent materials. Benzylamino groups are converted into amide groups over time and thereby lose their absorbent properties. However, the amide groups can be converted back into amino groups by reducing the carbonyl group with hydrogen or lithium aluminum nitride.

[0019] The international patent application WO 2023 / 094386 A1 describes adsorbent materials with primary and / or secondary amino groups containing less than 1400 ppm of metallic impurities.

[0020] Adsorbent materials are used in systems and processes for the direct adsorption of carbon dioxide from gas mixtures, particularly from air (Direct Air Capture; DAC). The carbon dioxide is captured in a cyclic adsorption-desorption process. Corresponding processes and systems are described, for example, in German patent DE 10 2020 113 447 B3, US patent US 11,007,470 B2, US patent applications US 2021 / 0093998 A1 and US 2023 / 0233989 A1, international patent applications WO 2019 / 092288 A1 and WO 2020 / 148460 A1, and European patent EP 3 956 049 B1. These processes involve passing very large volumes of air through the systems.

[0021] Carbon dioxide can also be directly converted to methane and methanol as an adsorbate on the adsorbent material. International patent application WO 2022 / 256361 A2 describes adsorbent materials containing catalytically active transition metals such as ruthenium, copper, manganese, nickel, vanadium, silver, rhodium, platinum, or palladium and / or their catalytically active oxides, adsorbents such as sodium oxide, calcium oxide, potassium oxide, magnesium oxide, or lithium oxide, and support materials such as aluminum oxide, silicon dioxide, or zeolites. The carbon dioxide is desorbed at a higher temperature and reacts directly with hydrogen to form methane.

[0022] German patent DE 10 2012 020 141 A1 describes processes for the synchronous adsorption of carbon dioxide from flue gas and the synthesis of dialkyl carbonates and alkylene carbonates. In this process, carbon dioxide is reacted with ammonia and / or amines to form ammonium carbamates, ammonium hydrogen carbonate, or urea. These intermediates are then reacted with alcohols to produce organic carbonates, releasing the amines.

[0023] International patent application WO 2013 / 075981 A2 proposes a carbon dioxide extraction system for buildings. This extraction system also operates on the DAC principle and removes carbon dioxide exhaled by residents or visitors from individual rooms of the building. This eliminates the need for intensive fresh air supply.

[0024] In the publication by Shivom Sharma and Francois Maréchal, "Carbon Dioxide Capture from Internal Combustion Engine Exhaust Using Temperature Swing Adsorption," in Frontiers in Energy Research, 2019, Volume 7, Article 143, the energy balance of an adsorption system for trucks is examined in detail. The adsorption system is designed for one day of operation. The truck travels 250 km in 8 hours and consumes 50 liters of diesel. The combustion process produces 105.5 kg of carbon dioxide, 90% of which, corresponding to approximately 95 kg, is captured at 30°C. The absorption capacity is 0.1 kg of carbon dioxide per 1 kg of adsorption material. This means that 950 kg of adsorption material are required to capture the 95 kg of carbon dioxide. The carbon dioxide is desorbed and collected at 150°C. After this process, the adsorption material is ready for reuse. At atmospheric pressure of 1 bar and 30°C, 95 kg of carbon dioxide yields 51.41 standard cubic meters of gas or 80.88 liters of liquefied gas.Carbon dioxide emissions from car exhaust can therefore be significantly reduced, and carbon dioxide can be obtained as a raw material for the synthesis of organic compounds.

[0025] For this well-known temperature swing process of reversible adsorption of carbon dioxide in combustion exhaust gases with subsequent desorption and recovery of the carbon dioxide, porous adsorber and / or support materials are used. However, porous materials are extremely poor thermal conductors. Therefore, they are also used as thermal insulation materials. This has the consequence that the adsorber materials react only slowly to the temperature changes of the temperature swing process, which has a detrimental effect on the speed and energy balance of the process.

[0026] As is well known, metallic silver is a very good conductor of heat at both 20°C and 100°C. Its thermal conductivity λ is 429 W / mK and 426 W / mK, respectively.

[0027] The earlier German patent application with file number 10 2024 100 775.3, filed on January 11, 2024, describes filter materials protected against microbial contamination for the reversible adsorption of carbon dioxide from gas mixtures, in particular from air, which (A) an adsorber material for the reversible adsorption of carbon dioxide from gas mixtures, (B) platelet-shaped biocidal metal microparticles or metal microflakes of a medium particle size d fixed on and / or in the adsorbent material (A) and / or on and / or in a carrier material (D). 50from 0.6 µm to >1,000 µm, wherein the fixed metal microflakes are present in such an amount that the absorption capacity of the adsorber material (A) for carbon dioxide is reduced to at most 1% to 50% of the absorption capacity of the adsorber material (A) free of fixed metal microflakes, and (C) a polymer and / or adhesive matrix for fixing the metal microflakes (B) onto and / or in the at least one adsorbent material (A) and / or onto at least one type of carrier material (D). Furthermore, filters, filter systems and systems for the reversible adsorption of carbon dioxide containing these filter materials, as well as application devices for protecting filters installed in stationary large-scale plants and stationary and mobile plants, room fans, ventilation systems, air conditioning systems and heating systems from microbial contamination, are described. Object of the invention

[0028] The present invention aims to further improve the operation and energy efficiency of known devices for temperature swing processes involving the reversible adsorption of carbon dioxide in combustion exhaust gases at room temperature, followed by desorption and recovery of the carbon dioxide at a higher temperature. This will enable a further reduction in emissions of this greenhouse gas from land, water, and air transport, energy generation through the combustion of fossil and renewable resources, waste incineration, and cement production, particularly from motor vehicles. Furthermore, the desorbed and collected greenhouse gas should exhibit a high degree of purity and be directly usable as a raw material for the synthesis of organic compounds. The solution according to the invention

[0029] Accordingly, the device according to the invention for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases was found according to independent claim 1. Advantageous embodiments of the device according to the invention are the subject of dependent claims 2 to 12.

[0030] Furthermore, the inventive method for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases was found according to dependent claim 13. Advantageous embodiments of the inventive method are the subject of dependent claims 14 and 15. Advantages of the invention

[0031] In view of the prior art, it was surprising and not foreseeable for the person skilled in the art that the problem of the present invention could be solved by the device according to the invention for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases from combustion engines, combustion furnaces and power plants and by the method according to the invention.

[0032] The devices for temperature swing processes involving the reversible adsorption of carbon dioxide in combustion exhaust gases with subsequent desorption and recovery of the carbon dioxide (temperature swing process) are significantly improved and made more economical in their operation and energy balance by the device and process according to the invention. This will lead to a further reduction in greenhouse gas emissions from land, water, and air transport, energy generation through the combustion of fossil and renewable raw materials, and cement production. Furthermore, the desorbed and collected greenhouse gas exhibits a high degree of purity and can therefore be used directly as a raw material for the synthesis of organic compounds.

[0033] Further advantages of the invention will become apparent from the following description. Detailed description of the invention

[0034] The device according to the invention serves for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases from combustion engines, such as engines of cars, trucks or ship engines, from combustion furnaces, such as waste incineration plants or cement kilns, and from power plants in which energy is generated with fossil fuels.

[0035] Viewed in the direction of flow of the combustion gases, the device according to the invention includes at least one, in particular one, device for cooling the combustion gases to 10°C to 50°C, preferably to 15°C to 45°C, more preferably to 15°C to 40°C, particularly preferably to 15°C to 35°C, and particularly to 20°C to 30°C, and for condensing the water contained in the combustion gases. In this configuration, the cooled and water-depleted combustion gases are fed directly into the adsorption / desorption system of the device according to the invention, as described below.

[0036] To remove NOx from the combustion exhaust gases, at least one catalyst for the selective reduction (SCR) of NOx can be installed upstream of the at least one device for cooling the combustion exhaust gases, since the SCR only works at higher temperatures.

[0037] When using AdBlue® solution (32.5% aqueous urea solution), ammonia can form due to incomplete NOx conversion in the SCR, a phenomenon known as ammonia slip. To oxidize the ammonia, at least one catalyst for the selective oxidation (SCO) of ammonia can be installed downstream of the SCR.

[0038] These functional components are common and well-known in the field of combustion exhaust gas cleaning.

[0039] Subsequently, (i) the cooled, water-depleted combustion gases or (ii) the NOx-free, cooled and water-depleted combustion gases or (iii) the NOx and ammonia-free, cooled and water-depleted combustion gases are directed through at least one feed line into the at least one adsorption / desorption device of the device according to the invention.

[0040] The at least one device according to the invention for the reversible adsorption and desorption of carbon dioxide in combustion gases can be closed off against the at least one inlet for the cooled, water-depleted combustion gases and against the at least one outlet for the carbon dioxide-depleted or carbon dioxide-free combustion gases. For this purpose, conventional and known, gas-tight, manually operated or hydraulically, pneumatically, electrically, or electronically monitored, controlled, and actuated closing devices such as shut-off and through-flow valves or gate valves are used, which are gas-tight under both positive and negative pressure.

[0041] Preferably, the device according to the invention has a square, hexagonal, circular, or oval outline in cross-section, i.e., viewed vertically to the flow direction of the combustion gases. The device according to the invention with a square or hexagonal outline may have rounded corners and edges. Preferably, its cross-section is smaller than its length viewed in the flow direction.

[0042] The dimensions of the device according to the invention depend primarily on the amount of carbon dioxide to be adsorbed during an adsorption phase, since this amount determines the amount of adsorbent material.

[0043] The device according to the invention is constructed from heat- and corrosion-resistant materials, such as those commonly used for exhaust systems. Stainless steels are preferably used.

[0044] The device according to the invention can include mountings for its components and functional peripherals for its operation, consisting of mechanical, pneumatic, hydraulic, optical, electrical, and electronic computing, switching, measuring, and control devices, electric motors, pneumatically operated motors, energy storage devices, actuators, electrical, optical, hydraulic, and pneumatic lines, data transfer lines, level sensors, gas flow meters, temperature measuring devices, pressure measuring devices such as manometers, alarm devices, timers, and / or optical displays. Several devices according to the invention can be connected to a central electronic control and monitoring system via WLAN or cable.

[0045] Furthermore, the at least one device according to the invention for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases comprises at least one device that alternately serves to cool and heat at least one species of adsorbent material for the reversible adsorption and desorption of the carbon dioxide. At least one halogen-free liquid is used as a heat transfer medium, which has a melting point <20°C and a boiling point >150°C and is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, glycerol, glycol ethers, silicone oils, and ionic liquids.

[0046] Examples of suitable glycol ethers are: Ethylene glycol monomethyl ether (methyl glycol, 2-methoxyethanol, CH3-O-CH2CH2-OH), Ethylene glycol monoethyl ether (ethyl glycol, 2-ethoxyethanol, CH3CH2-O-CH2CH2-OH), Ethylene glycol monopropyl ether (2-propoxyethanol, CH3CH2CH2-O-CH2CH2-OH), Ethylenglykolmonoisopropylether (2-Isopropoxyethanol, (CH3)2CH-O-CH2CH2-OH), Ethylenglykolmonobutylether (2-Butoxyethanol, CH3CH2CH2CH2-O-CH2CH2-OH), Ethylenglykolmonohexylether (2-Hexyloxyethanol, C6H 11 -0-CH2CH2-OH), Ethylenglykolmonophenylether (2-Phenoxyethanol, C6H5-0-CH2CH2-0H), Ethylenglykolmonobenzylether (2-Benzyloxyethanol, C6H5CH2-0-CH2CH2-0H), Diethylenglykolmonomethylether [2-(2-Methoxyethoxy)ethanol, Methylcarbitol, CH3-O-CH2CH2-O-CH2CH2-OH], Diethylenglykolmonoethylether [2-(2-Ethoxyethoxy)ethanol, Carbitolcellosolve, CH3CH2-O-CH2CH2-O-CH2CH2-OH], Diethylenglykolmono-n-butylether [2-(2-Butoxyethoxy)ethanol, CH3CH2CH2CH2-O-CH2CH2-O-CH2CH2-OH], Diethylenglykolmono-n-hexylether, Propylenglykolmonomethylether (1-Methoxy-2-propanol), Propylenglykolmonoethylether (Ethoxypropanol), Propylene glycol monobutyl ether (1-butoxy-2-propanol), Propylene glycol monohexyl ether (1-hexoxy-2-propanol), Dipropylene glycol monomethyl ether (mixture of isomers), Dipropylene glycol monobutyl ether (mixture of isomers), Dipropylene glycol monohexyl ether (mixture of isomers), Polyethylene glycol ethers Polypropylene glycol ethers Ethylene glycol dimethyl ether (dimethoxyethane, CH3OCH2CH2OCH3), Ethylene glycol diethyl ether (diethyl glycol, diethoxyethane, CH3CH2OCH2CH2OCH2CH3), Ethylene glycol dibutyl ether (Dibutoxyethane, CH3CH2CH2CH2OCH2CH2OCH2CH2CH2CH3) and dipropylene glycol dimethyl ether.

[0047] Silicone oils are commercially available, long-known products of the general formula [R 5 R 6 SiO] n with R 5 and R 6= Alkyl, especially methyl [cf. W. Kaiser, R. Riedle: Silicones. In H. Harnisch, R. Steiner, K. Winnacker (eds.): Winnacker-Küchler: Chemical Engineering, Organic Technology II. 4th edition. Volume 6, Carl Hanser Verlag, Munich 1982, page 838].

[0048] Ionic liquids consist exclusively of ions (cations and anions). They can consist of organic cations and organic or inorganic anions, or of inorganic cations and organic anions.

[0049] In principle, ionic liquids are molten salts with low melting points. This category includes not only those liquid at ambient temperature, but also all salt compounds that melt preferably below 150°C, preferably below 130°C, and especially below 100°C. In contrast to conventional inorganic salts such as table salt (melting point 808°C), ionic liquids exhibit reduced lattice energy and symmetry due to charge delocalization, which can lead to freezing points as low as -80°C and below. Because of the numerous possible combinations of anions and cations, ionic liquids with very different properties can be produced (see also Römpp Online 2007, "ionic liquids").

[0050] Suitable organic cations are all cations commonly used in ionic liquids. Preferably, these are non-cyclic or heterocyclic onium compounds.

[0051] Preferably non-cyclic and heterocyclic onium compounds from the group consisting of quaternary ammonium, oxonium, sulfonium and phosphonium cations as well as uronium, thiouronium and guanidinium cations, in which the singly positive charge is delocalized over several heteroatoms, are used.

[0052] Quaternary ammonium cations are particularly preferred, and heterocyclic quaternary ammonium cations are especially preferred.

[0053] In particular, the heterocyclic quaternary ammonium cations from the group consisting of pyrrolium, imidazolium, 1H-pyrazolium, 3H-pyrazolium, 4H-pyrazolium, 1-pyrazolinium, 2-pyrazolinium, 3-pyrazolinium, 2,3-dihydroimidazolinium, 4,5-dihydroimidazolinium, 2,5-dihydroimidazolinium, pyrrolidinium, 1,2,4-triazolium (quaternary nitrogen atom in position 1), 1,2,4-triazolium (quaternary nitrogen atom in position 4), 1,2,3-triazolium (quaternary nitrogen atom in position 1), 1,2,3-triazolium (quaternary nitrogen atom in position 4), oxazolium, Isooxazolium, thiazolium, isothiazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, morpholinium, pyrazinium, indolium, quinolinium, isoquinolinium, quinoxalinium and indolinium cations selected.

[0054] The organic cations described above are known species per se, which are described, for example, in German and international patent applications as well as in the American patent application. - DE 10 2005 055 815A, page 6, paragraph

[0033] , to page 15, paragraph

[0074] , - DE 10 2005 035 103A1, page 3, paragraph

[0014] , to page 10, paragraph

[0051] , and - DE 103 25 050 A1, the paragraph

[0006] spanning pages 2 and 3 in conjunction with page 3, paragraph

[0011] , up to page 5, paragraph

[0020] , - WO 03 / 029329 A2, page 4, last paragraph, to page 8, second paragraph, - WO 2004 / 052340 A1, page 8, first paragraph, to page 10, first paragraph, - WO 2004 / 084627 A2, page 14, second paragraph, to page 16, first paragraph, and page 17, first paragraph, to page 19, second paragraph, - WO 2005 / 017252 A1, page 11, line 20, to page 12, line 19, - WO 2005 / 017001 A1, page 7, last paragraph, to page 9, fourth-to-last paragraph, - WO 2005 / 023873 A1, page 9, line 7, to page 10, line 20, - WO 2006 / 116126A2, page 4, line 1, to page 5, line 24, - WO 2007 / 057253 A2, page 4, line 24, to page 18, line 38, - WO 2007 / 085624 A1, page 14, line 27, to page 18, line 11, and - US 2007 / 0006774 A1 page 17, paragraph

[0157] , to page 19, paragraph

[0167] , are described in detail.

[0055] Of the organic cations described above, imidazolium cations are mainly used, in particular the 1-ethyl-3-methylimidazolium cation (EMIM) or the 1-butyl-3-methylimidazolium cation (BMIM), in which the quaternary nitrogen is in the 1 position.

[0056] Suitable inorganic cations include all cations that do not form crystalline salts with the organic anions of ionic liquids and whose melting point is above 150°C. Examples of suitable inorganic cations are the lanthanide cations.

[0057] Basically, all anions that do not form crystalline salts with the organic cations of the ionic liquids, whose melting point is above 150°C, and that do not undergo undesirable interactions with the organic cations, such as chemical reactions, are eligible as inorganic anions.

[0058] Preferably, the inorganic anions are selected from the group consisting of pseudohalide, sulfide, cyanometallate and carbonylmetallate anions, as well as the anions of the oxyacids of sulfur, nitrogen, phosphorus, carbon, silicon, boron and the transition metals.

[0059] Preferred pseudohalide anions include cyanide, cyanate, thiocyanate, isothiocyanate and / or azide anions; sulfide, hydrogen sulfide, polysulfide and / or hydrogen polysulfide anions; hexacyanoferrate(II) and / or (III) anions; tetracarbonylferrate anions; and sulfate, hydrogen sulfate, sulfite, hydrogen sulfite, thiosulfate, nitrite, nitrate, phosphinate, phosphonate, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate, glyoxylate, oxalate, deltaate, and square anions. Croconate, rhodizonate, silicate, borate, chromate, polyoxometallate (POM) and / or permanganate anions are used.

[0060] In the same way, basically all anions that do not form crystalline salts with the organic or inorganic cations of the ionic liquids, whose melting point is above 150°C, and that do not undergo any undesirable interactions with the organic or inorganic cations, such as chemical reactions, are considered organic anions.

[0061] Preferably, the organic anions of aliphatic, cycloaliphatic and aromatic acids are derived from the group consisting of carboxylic acids, sulfonic acids, acid sulfate esters, phosphonic acids, phosphinic acids, acid phosphate esters, hypodiphosphinic acids, hypodiphosphonic acids, hypodiphosphonic acids, acid boric esters, boric acids, acid silicic esters and acid silanes, or they are selected from the group consisting of aliphatic, cycloaliphatic and aromatic thiolate, alkoxide, phenolate, methide, bis(carbonyl)imide, bis(sulfonyl)imide and carbonylsulfonylimide anions.

[0062] Examples of suitable inorganic and organic anions can be found in international patent applications. - WO 2005 / 017252 A1, page 7, page 14, to page 11, page 6, and - WO 2007 / 057235 A2, page 19, line 5, to page 23, page 23, known. Acetate anions are particularly preferred.

[0063] In particular, 1-ethyl-3-methylimidazolium acetate (EMIM Ac) is used as an ionic liquid.

[0064] Preferably, the flow direction of the at least one halogen-free liquid is opposite to the flow direction of the combustion gases through the adsorber materials described below. Heat exchange therefore preferably takes place according to the countercurrent principle.

[0065] In a first preferred embodiment, the halogen-free liquid flows through at least one closed liquid circuit with a cooling device and a heating device for the alternating cooling and heating of the at least one halogen-free liquid and the adsorber material described below.

[0066] In a second preferred embodiment, at least two separate closed liquid circuits are provided, at least one of which is equipped with a cooling device for cooling the at least one halogen-free liquid and the adsorber material, and at least one of which is equipped with a heating device for heating the at least one halogen-free liquid and the adsorber material.

[0067] Furthermore, the at least one device according to the invention comprises at least one device for pumping out and compressing the carbon dioxide released during desorption, such as conventional and known compressors or compressors.

[0068] The at least one pumping and compression device is connected on its suction side to the device according to the invention or to the container in which the adsorbent material is located via a suction line. During the adsorption phase, the suction line is closed by a gas-tight, manually operated or hydraulically, pneumatically, electrically, or electronically monitored, controlled, and actuated closing device, such as a shut-off and through-flow valve or a gate valve, which is controlled and operated by actuators in both overpressure and underpressure conditions, and is opened during the desorption phase.

[0069] On the pressure side of the compressor, there is a pressure line leading to a removable pressure vessel, such as a conventional gas cylinder. The pressure line features a gas-tight, manually operated or hydraulically, pneumatically, electrically, or electronically monitored, controlled, and actuated shut-off and flow-through valve, preferably a check valve, which is open during the desorption phase to collect the desorbed carbon dioxide in the pressure vessel.

[0070] An outlet line branches off from the pressure line and features a gas-tight, manually operated or hydraulically, pneumatically, electrically, or electronically monitored, controlled, and actuated shut-off and flow-through valve, which is controlled under both positive and negative pressure. The outlet line serves to discharge any remaining combustion exhaust gas from the closed device according to the invention between the adsorption and desorption phases.

[0071] The at least one adsorbent material contains at least one species of platelet-shaped metal microparticles or metal microflakes of an average particle size d 50from 0.6 µm to <1,000 µm, preferably 0.6 µm to 950 µm, preferably 0.6 µm to 950 µm and particularly 0.6 µm to 900 µm. The metal microflakes are (i) fixed on and / or in at least one native adsorber material and / or (ii) fixed on and / or in at least one species of a carrier material for the native adsorber material by means of at least one species of a polymer and / or adhesive matrix.

[0072] The fixed components (i.e., metal microflakes + polymer and / or adhesive matrix) are present in such an amount that the absorption capacity of the adsorbent material to be used according to the invention for carbon dioxide at 30°C (303.15 K) is reduced to 1% to 50%, preferably 2% to 50%, preferably 3% to 50%, particularly preferably 4% to 50% and especially 5% to 50% of the absorption capacity of the native adsorbent material free of fixed metal microflakes.

[0073] The person skilled in the art can specify the desired or required quantity of fixed metal microflakes based on their general technical knowledge or determine it by means of simple comparative preliminary tests, without having to make an inventive effort.

[0074] Metal microflakes made of silver and / or copper and / or silver-copper alloys such as AgCu are particularly preferred. Specifically, metal microflakes made of silver and / or copper, especially silver, are used.

[0075] The plate-shaped metal microparticles or metal microflakes can have different geometric shapes, preferably selected from the group consisting of platelets or flakes with circular, oval, elliptical, square, triangular, quadrilateral, pentagonal, hexagonal, heptagonal, octagonal, or three-, four-, five-, or more-pointed star-shaped outlines, as well as platelets or flakes with circular, oval, elliptical, square, triangular, quadrilateral, pentagonal, hexagonal, heptagonal, octagonal, or three-, four-, five-, or more-pointed star-shaped outlines that are curved in at least one direction in space and / or have rounded edges and / or corners. Metal microflakes of the same or different geometries can also aggregate to form T- or Y-shaped metal microflakes.

[0076] The average particle size d 50The particle size of metal microflakes is determined by light microscopy, dry sieving, wet sieving, electron microscopy, centrifugation, Coulter counter, Fraunhofer diffraction, and Mie scattering. The longest imaginary path through the metal microflakes is considered the particle size.

[0077] The production of the preferably used silver microflakes and their dispersions is known, for example, from patents EP 2 942 128 A1, EP 3 578 283 A1, EP 3 693 109 A1, US 2008 / 0272344 A1, US 2009 / 0246358 A1, US 2009 / 0253848 A1, US 2015 / 0283175 A1, US 2017 / 0043396 A1, US 2019 / 0344354 A1, WO 2021 / 211305 A1, US 7,575,621 B2, US 8,293,142 B2 or US 8,486,310 B2. Silver microflakes of an average particle size d 50 of 5 µm and d 20 For example, 2 µm sheets can be obtained from ACS Material, Pasadena, California, USA. Other sources include: Micro Flakes - MST-Design Water Transfer Printing & Painting Accessories (mst-shop.com) MicroSilver BG™ (See also US EPA, Pesticides, Label, MICROSILVER BG-R, 7 / 16 / 2010) Silver flakes (silber-pulver.de) DODUCO's Silver-plated copper powder (silber-pulver.de) Metallic Micro Flakes | Kryolan - Professional Make-up (Silver Flakes) Silver powder (silber-pulver.de) The production of the copper microflakes B, which are preferred for use, is known, for example, from patents EP 1 787 742 B1 and EP 2 542 767 B1. Furthermore, copper microflakes with average particle sizes d 50 Sizes from 5 µm to 800 µm can be obtained from Merck. Other sources include: Copper Micro Flake - Flakes (kandydip.de) Micro Flakes - Micronic Orange-Copper Metallic Effect Paint - MST-Design Water Transfer Printing & Painting Accessories (mst-shop.com) Metallic Micro Flakes | Kryolan - Professional Make-up (Kupferflakes)

[0078] The metal microflakes have a monomodal or multimodal, particularly bimodal, particle size distribution. The particle size distribution is broad or narrow. The advantage of a broad monomodal or multimodal particle size distribution is that the smaller metal microflakes are embedded in the voids between the larger metal microflakes in the polymer and / or adhesive matrix described below, resulting in a denser surface layer. The advantage of a narrow monomodal particle size distribution is that, due to their largely similar or identical physicochemical properties, the metal microflakes behave largely similarly or identically in the impregnating agents described below and the polymer and / or adhesive matrices produced from them. Therefore, the particle size distribution can be particularly well adapted to the requirements of each individual application.

[0079] In the polymer and / or adhesive matrix, the metal microflakes can be in electrically conductive contact with each other and / or form a micro-rough surface.

[0080] Preferably, the polymer matrix contains at least one plastic selected from the group consisting of linear and / or branched and / or blocky, comb-like and / or statistically structured polyaddition resins, polycondensation resins and / or (co)polymers of ethylene unsaturated monomers.

[0081] Preferably selected are the (co)polymers from the group consisting of (meth)acrylate (co)polymers and / or polystyrene, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinylamides, polyacrylonitriles, polyethylenes, polypropylenes, polybutylenes, polyisoprenes and / or their copolymers.

[0082] Preferably selected are polyaddition resins or polycondensation resins from the group consisting of polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin amine adducts, polyurethanes, alkyd resins, polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, celluloses, polysulfides, polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides and / or polyureas.

[0083] Further examples of suitable plastics are listed below in the section on reticulated foams used as carrier materials.

[0084] Preferably, the adhesive matrix comprises at least one adhesive selected from the group consisting of biopolymers, polysaccharides, chemically curing adhesives, polymerization adhesives, cyanoacrylate adhesives (superglue), methyl methacrylate adhesives, anaerobically curing adhesives, unsaturated polyesters (UP resins), radiation-curing adhesives, polycondensation adhesives, phenol-formaldehyde resin adhesives, silicone-silane crosslinked polymer adhesives, lignin adhesives, polyimide adhesives, polysulfide adhesives, polyaddition adhesives, epoxy resin adhesives, polyurethane adhesives, silicone polyisocyanate adhesives, physically setting adhesives, solvent-based adhesives, contact adhesives, dispersion adhesives, cement, cement-based adhesives, foam concrete, gypsum-based adhesives, plastisols, adhesives without a hardening mechanism, and slaked lime and adhesives based thereon. adhesives, producible.

[0085] The device according to the invention contains at least one species of an adsorber material according to the invention based on at least one native adsorber material for the reversible adsorption and desorption of carbon dioxide from combustion exhaust gases.

[0086] According to the invention, all common and known basic and / or nanoporous, microporous, mesoporous and / or macroporous adsorber materials as described in the prior art are suitable as native adsorber materials. Examples of suitable adsorbent materials are - common and well-known, commercially available, weakly basic anion exchangers based on cross-linked polystyrenes or poly(meth)acrylates, which contain in particular primary ammonium groups in the hydroxide form, - common and well-known, commercially available, strongly basic anion exchangers based on cross-linked polystyrenes or poly(meth)acrylates, which contain in particular quaternary ammonium groups in the hydroxide form, - the polyamine or polyamine-polyol adsorbent materials described in column 8, line 60, to column 11, line 16, of American patent US 7,795,175 B2, which are supported on nanoparticles such as nanosilicates, - the fibrillated celluloses described in international patent application WO 2017 / 009241 on page 4, line 15, to page 25, line 18, which are functionalized with amino groups using aminosilanes, - the polyamine aldehyde adducts described in American patent US 9,968,880 B2 in column 4, line 19, to column 12, line 67, which are supported on pyrogenic silica, - the activated carbons described in European patent EP 3 706 898 B1 on page 5, paragraph

[0019] , to page 18, paragraph

[0118] , which are impregnated with sodium and / or potassium carbonate, - the inorganic or organic, non-polymeric and polymeric carrier materials with a specific BET surface area of ​​1 to 20 m² described in the international patent application WO 2021 / 259760 A1 on page 3, line 23, to page 22, end 2 / g, which are functionalized on their surface with amino-functional groups, - the support materials described in international patent application WO 2022 / 013107 A1 on page 4, line 13, to page 21, end, which contain immobilized primary and / or secondary amino groups substituted at the alpha-carbon atom with oxygen or a residue R; the residues R can be, for example, alkyl, alkenyl, and arylalkyl residues with 1 to 12 carbon atoms. A typical example of such adsorbent materials are polystyrene beads with alpha-methylbenzylamine, - the zeolites, metal-organic frameworks (MOFs), silicas or aluminium oxides described in the international patent application WO 2022 / 109746 A1 on page 6, paragraph

[0017] , to page 25, paragraph

[0088] , - the cycloaliphatic amines described in international patent application WO 2022 / 128431 A1 on page 3, line 22, to page 23, end, such as aziridine, diaziridine, azetidines, 1,2- and 1,3-diazetidine, pyrrolidine, diazolidine, triazolidine, piperidine, 1,2- and 1,3-diazinane, piperazine, triazinanes, tetrazinanes, azepanes, azocanes and mixtures thereof, in particular piperazine; the amines are used in mixtures with lithium, sodium and / or potassium carbonate and are supported on activated carbon or fibers such as cellulose fibers, - the zinc ion-containing zeolites described in the international patent application WO 2022 / 183058 A1 on page 8, paragraph

[0020] , to page 55, paragraph

[00226] , - the sodium bicarbonate described in international patent application WO 2022 / 235664 A2, on page 3, paragraph

[0013] , to page 29, paragraph

[00138] , which is suitable as an adsorbent material for the adsorption of carbon dioxide from water vapor-containing gas mixtures; the carbon dioxide is stored in the form of sodium sesquicarbonate, - the amino-functionalized polyacrylonitrile fibers described in the international patent application WO 2023 / 001810 A1 on page 5, line 10, to page 23, line 23, - the regenerated amino-functional adsorber materials A described in international patent application WO 2023 / 088812 A1 on page 4, line 35, to page 18, end; benzylamino groups are converted into amide groups over time and thereby lose their absorbing properties; however, the amide groups can be converted back into amino groups by reducing the carbonyl group with hydrogen or lithium aluminum nitride, - the adsorbent materials with primary and / or secondary amino groups containing less than 1400 ppm of metallic impurities as described in international patent application WO 2023 / 094386 A1 on page 4, line 16, to page 21, end. - the cross-linked polystyrene produced by reductive amination and modified by alpha-methylbenzylamino groups as described in the international patent application WO 2023 / 104656 A1 on page 4, line 5, to page 16, end.

[0087] Examples of other suitable native adsorbent materials can be found in the following publications: - Hao Lyu, Haozhe Li, Nikita Hanikel, Kaiyu Wang and Omar M. Yaghi, “Covalent Organic Frameworks for Carbon Dioxide Capture,” J. Am. Chem. Soc., 2022, 144, 28, 12989 to 12995, - Priyanka Sarkar, Ipsita Hazra Chowdhury, Surya Das und Sk. Manirul Islam, „Recent trends in covalent organic frameworks (COFs) for carbon dioxide reduction“, Material Advances, 2022, 3, 8063-8080, - Jannis Hack, Nobutaka Maeda und Daniel M. Meier, „Review on CO2 Capture Using Amine-Functionalized Materials“ ACS Omega 2022, 7, 44, 39520 bis 39530, - Qingdian Shu et al., „Direct Air Capture Using Electrochemically Regenerated Anion Exchange Resins“, Environmental Science & Technology, 2022, 56, 16, 11559-11566, und - M. Parvazinia et al., CO2 capture by ion exchange resins as amin functionalized adsorbents", Chemical Engineering Journal, 331, 2018, 335-342.

[0088] The adsorbent materials used according to the invention for the reversible adsorption of carbon dioxide exhibit a wide variety of forms. They are supported on and in carrier materials such as porous particles or fibers, or they themselves constitute porous particles and fibers. The porous adsorbent particles can form an adsorbent bed. The adsorbent fibers can form nonwovens, woven fabrics, felts, fleeces, spunbond materials, or meltblown materials made of micro- and nanofibers.

[0089] Preferred materials include weakly basic anion exchange resins containing primary amino groups in the hydroxide form, such as Lewatit® VP OC 1065 from Lanxess or Purolite® A109 from Purolite in the hydroxide form; strongly basic anion exchange resins containing quaternary amino groups in the hydroxide form, such as Amberlyst® A26 from Merck; and supported alkali carbonates, particularly those supported on activated carbon, such as sodium carbonate, sodium bicarbonate, sodium sesquicarbonate and / or potassium carbonate.

[0090] Preferably, organic, organometallic, inorganic, non-porous, nanoporous, microporous and / or macroporous materials are used as support materials.

[0091] Air filters, such as those installed in common and well-known filter systems, can be used as carrier materials. These air filters can be classified according to their separation efficiency. - High-performance particle filter (EPA = Efficient Particulate Air filter), smallest filterable particle size: 100 nm, - HEPA filter (High Efficiency Particulate Air filter), smallest filterable particle size: 100 nm, - High-performance particulate filter (ULPA = Ultra Low Penetration Air filter), smallest filterable particle size: 50 nm, - Medium filter, smallest filterable particle size: 300 nm, - Pre-filter, smallest filterable particle size: 1000 nm, and - Automotive cabin air filter, smallest filterable particle size: 500 nm can be subdivided.

[0092] Depending on the particle size of the particles to be filtered, their filtering effect is based on the following effects: - Diffusion effect: Very small particles (particle size: 50 nm to 100 nm) do not follow the gas flow, but due to their collisions with the gas molecules, have a trajectory similar to Brownian motion and thus collide with the filter fibers, to which they adhere. This effect is also referred to as the diffusion characteristic (diffusion regime). - Interception effect: Smaller particles (particle size: 100 nm to 500 nm) that follow the gas flow around the fiber adhere to it when they get too close to the filter phase. This effect is also known as the interception regime. - Inertial effect: Larger particles (particle size: 500 nm to >1 µm) do not follow the gas flow around the fiber, but instead collide with it due to their inertia and adhere to it. This effect is also known as the inertial impaction regime.

[0093] In the particle size range of 100 nm to 500 nm, the diffusion effect and the barrier effect occur together. In the particle size range of 500 nm to >1 µm, the inertial effect and the barrier effect also occur together.

[0094] According to filter effects, particles with a size of 200 nm to 400 nm are the most difficult to separate. They are also referred to as MPPS (most penetrating particle size). Filter efficiency drops to 50% in this size range. Larger and smaller particles are separated more effectively due to their physical properties.

[0095] EPA, HEPA, and UPLA filters are classified according to their effectiveness for these particle sizes using a test aerosol of di-2-ethylhexyl sebacate (DEHS). In their article "On the Minimum Efficiency and the Most Penetrating Particle Size for Fibrous Filters" in the Journal of the Air Pollution Control Association, Vol. 30, No. 4, April 1980, pages 377 to 381, K.W. Lee and B.Y.H. Liu provide formulas that allow the calculation of the minimum efficiency and MPPS for fiber filters based on the diffusion and inertial effects. The results show that MPPS decreases with increasing filtration rate and increasing fiber volume fraction, and increases with increasing fiber size.

[0096] Air filters D are also classified according to particle size according to DIN EN 779:2012: coarse dust classes G1 to G4 and fine dust classes M5 and M6 as well as F7 to F9. Further classification standards can be found in the Wikipedia article "Particle filter classes". Particle filter classes - Wikipedia (downloaded on 9.11.2022).

[0097] Common and well-known types of air filters include candle filters, flat membrane filters, bag filters, hollow fiber modules, hose filters and electret filters.

[0098] It should be emphasized that, within the scope of the present invention, these air filters do not serve for the filtration of suspended particles, but rather as prefabricated, commercially available carriers for the adsorbent materials.

[0099] Furthermore, - flexible materials such as woven fabrics, knitted fabrics, textiles, papers, nonwovens, fiber-oriented nonwovens, felts, random fiber nonwovens and spunbond nonwovens made of metal fibers, ceramic fibers, glass fibers, natural fibers and synthetic fibers such as synthetic fibers made of polyester, polyphenylene sulfide or polytetrafluoroethylene (PTFE, Teflon), - rigid materials such as porous solids and filter cartridges made of plastic, metal or ceramic and granular ceramic filter elements with expanded clay or silicon carbide as the base material and - Loose layers of granular materials, especially oxide materials, are used as carrier materials.

[0100] Reticulated foams made of plastics, such as those used for cleaning water for aquariums and ponds, can also be used as carrier materials.

[0101] Suitable plastics include common and well-known linear and / or branched and / or blocky, comb-like and / or statistically structured polyaddition resins, polycondensation resins and / or (co)polymers of ethylene unsaturated monomers.

[0102] Examples of suitable (co)polymers are (meth)acrylate (co)polymers and / or polystyrene, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinylamides, polyacrylonitriles, polyethylenes, polypropylenes, polybutylenes, polyisoprenes and / or their copolymers.

[0103] Examples of suitable polyaddition or polycondensation resins include polyesters, alkyds, polylactones, polycarbonates, polyethers, proteins, epoxy resin amine adducts, polyurethanes, alkyd resins, polysiloxanes, phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, cellulose, polysulfides, polyacetals, polyethylene oxides, polycaprolactams, polylactones, polylactides, polyimides, and / or polyureas.

[0104] As is well known, thermosets are produced from multifunctional, low molecular weight and / or oligomeric compounds by thermally and / or actinic radiation-initiated (co)polymerization.

[0105] Reticulation, i.e., the destruction of the cell walls of plastic foams, is typically carried out using so-called water reticulation. In this process, a mixture of gaseous, flammable substances, such as oxyhydrogen gas, is simultaneously mixed with pressurized steam at approximately 185 °C, triggered by an ignition impulse. This initiates an exothermic reaction, and the heat released by the explosive reaction perforates the cell walls, causing them to sinter in a controlled manner to the desired thickness of the foam's core material.

[0106] Reticulated foams can have a wide variety of three-dimensional shapes. They can be round, oval, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal, or octagonal plates or discs, cubes, cuboids, columns, truncated cones, spheres, or tubes with varying cross-sections and wall thicknesses. They may also feature depressions, protrusions, or perforations. Furthermore, they can have special three-dimensional shapes adapted to specific applications and devices.

[0107] Furthermore, the reticulated plastic foams can have dimensions ranging from square centimeters to square meters, the dimensions being determined by the devices according to the invention into which the reticulated plastic foams are fitted.

[0108] According to the invention, the reticulated plastic foams are preferably in round, rectangular, and square sheet form. They particularly preferably have a thickness of 0.5 cm to 30 cm, very preferably 1 cm to 20 cm, and particularly preferably 2 cm to 10 cm. They most preferably cover an area of ​​10 cm². 2 up to 10 m 2 , especially preferred 100 cm 2 up to 5 m 2 and especially 150 cm 2 up to 3 m 2 The square plates preferably have an area of ​​30 cm x 30 cm, 50 cm x 50 cm and 100 cm x 100 cm and thicknesses of 2 cm, 3 cm and 4 cm.

[0109] Reticulated foam filter mats made of the aforementioned plastics, in particular polyester urethane, polyether urethane, polyester ether urethane, polyester, polypropylene, and polyethylene, are especially preferred. Foam filter mats made of permanently hydrophilic polyester urethane, polyether urethane, and polyester ether urethane are particularly used. Foam filter mats of this type are generally used as aquarium and pond filters and are commercially available. They are available in pores ranging from 10 PPI (pores per inch) to 100 PPI. Preferably, reticulated foam filter mats of 10 PPI, 20 PPI, 30 PPI, and 40 PPI are used.

[0110] Depending on their intended use, reticulated plastic foams can be rigid or flexible.

[0111] Reticulated plastic foams are commercially available products. Sources of supply can be found in Filter technology - Industrial solutions | EMW.de Reticulated Foams - Koepp Schaumstoffe GmbH (koepp-schaum.de) Reticulated Filter Foam | Master Sponge & Foam Products Manufacturer (sponaesupplier.com) Filter foam | PPI foam - PANA Foamtec GmbH 10ppi-60ppi reticulated open-cell polyether-based polyurethane foam | Master Sponge & Foam Products Manufacturer (sponaesupplier.com) Black polyethylene PE foam | PE foam sheets | Foam sheets | Saar foam

[0112] Furthermore, open-cell foams made from natural materials such as sponges and wood, as well as from glass, ceramics and metals, which are produced using common and well-known foaming techniques, are suitable as substrate materials.

[0113] Furthermore, inert fibers in the form of nonwovens, woven fabrics, felts, fleeces, spunbond materials or melt-blown materials are suitable as carrier materials.

[0114] Examples of suitable fibers are: Seed fibers: such as cotton (CO), kapok (KP), poplar down, akon, bamboo fiber, nettle fiber, hemp fiber (HA), jute (JU), kenaf, flax (LI), hops, ramie (RA), hemp, Hard fibers: such as pineapple, caroá, curauá, henequen, New Zealand flax, sisal (SI), coconut (CC), Wool and fine animal hair: such as sheep wool (WO), alpaca, llama, vicuña, guanaco, angora (WA), rabbit, camel hair (WK), cashmere (WS), mohair (WM), coarse animal hair: such as cow hair, horsehair, goat hair, Silks: such as mulberry silk (SE), tussah silk (ST), mussel silk, Fibers made from natural polymers: such as cellulosic fibers, for example viscose (CV), modal (CMD), lyocell (CLY), cupro (CUP), acetate (CA), triacetate (CTA), Rubber fibers: such as rubber, Plant protein fibers: such as soy protein fiber, zein and other prolamins, Protein fibers: Fibers based on casein, albumins, collagen, glycoproteins, globulins, elastin, nucleoproteins, histones, keratin, chromoproteins, protamines, fibrinogen, phosphoproteins, prolamins, myosin, lipoproteins and hydrophobin. Fibers based on starch or glucose: such as alginate fibers (ALG) or chitosan fibers and Fibers made from synthetic biodegradable polymers: such as polylactide fibers (PLA) and polyesters (see Biodegradable Polyesters - New Paths with Bismuth Catalysts, DISSERTATION submitted to obtain the degree of Doctor of Natural Sciences of the Department of Chemistry of the University of Hamburg, by Gesa Behnken, from Hamburg, Hamburg 2008). Other suitable fibers that can be considered as carrier materials D are synthetic fibers, polymer fibers, and mineral fibers. An overview can be found in the Wikipedia article "Fibers": https: / / de.wikipedia.org / wiki / Faser#Mineralfasern [Downloaded on January 4, 2024].

[0115] The fabrics, woven fabrics, felts, nonwovens, spunbond materials or melt-blown materials can also consist of two or more different fiber species.

[0116] Particulate, inert, inorganic carrier materials are also suitable. Preferably, these have a mean particle size of 0.5 µm to 10 cm, determined by sieve analysis. Preferably, the mean particle size is between 1 mm and 9 cm. In particular, particles with a Sauter diameter of 6 mm to 8 mm are used.

[0117] Preferred are the particulate, inert, inorganic support materials from the group consisting of (i) packings for columns and Raschig rings, and from the group consisting of (ii) layered silicates, foam glasses, foam glass gravel, pumice, zeolites, expanded clays, expanded glasses, expanded micas, expanded perlite, foamed cements, ceramic foams, activated carbons and mixtures of at least two of these materials in the form of spheres, hollow spheres, shards, granules, ground chunks, pellets, rings, spheres with core-shell structures, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedra, truncated dodecahedra, icosahedra, truncated icosahedra, dumbbells, tori, plates, needles with circular, oval, elliptical, square, triangular, quadrilateral, pentagonal, hexagonal, heptagonal, octagonal or star-shaped cross-sections, as well as shards, rings, dumbbells, tori curved in at least one direction of space,Needles and plates, selected.

[0118] The fixed metal microflakes are applied (i) to and / or into the native adsorbent materials and / or (ii) to and / or into the support materials using liquid impregnating agents. These liquid impregnating agents are water-based or based on organic solvents. The impregnating agents contain the metal microflakes used according to the invention as a dispersed phase. They may also contain molecularly dispersed substances and / or other dispersed substances.

[0119] Preferably, water-based liquid impregnating agents are used.

[0120] The liquid impregnating agents are applied using conventional and well-known coating methods such as dipping, spraying (especially compressed air spraying, airless spraying, air-mix spraying and hot spraying), curtain coating, brushing, doctor blade application, two-component coating, roller application, wiping, pouring, troweling, strip coating, centrifuging and drum coating. Spraying methods are particularly common.

[0121] After application, the liquid impregnating agents are cured and / or dried, so that a solid polymer and / or adhesive matrix is ​​formed which fixes the metal microflakes to and / or the adsorbents and / or the carrier materials.

[0122] Depending on the reactive functional groups present in the liquid impregnating agents, they are cured thermally or by radical polymerization, which is initiated by actinic radiation such as UV radiation or by radical initiators. Both mechanisms can also be combined in a single impregnating agent. This is then referred to as "dual cure." Table 1 provides an overview of suitable functional groups for the crosslinking reactions. Table 1: Examples of complementary reactive functional groups for thermal curing and radiation curing of impregnating agents binder and Networking tools or Networking tools and binder -SH -C(O)-OH -OH -C(O)-OC(O)- -NH-C(O)-OR 5 -CH2-OH -CH2-O-CH3 -NH-C(O)-CH(-C(O)OR 5 )2 -NH-C(O)-CH(-C(O)OR 5 )(-C(O)-R 5 ) >Si(OR 5 )2 -C(O)-OH O -CH-CH2 -O-C(O)-CR 5 =CH2 -OH -O-CR 5 =CH2 -C(O)-CH2-C(O)-R 5 -O-CR 5 =CH2 -CH=CH2 -CR=CH2 -CH=CH2 R 5 = Organic residue such as alkyl, cycloalkyl and / or aryl.

[0123] Impregnating agents can be classified into groups based on their binders. Oil-based impregnating agents

[0124] These impregnating agents contain natural drying oils that undergo auto-oxidative polymerization in the presence of catalysts and atmospheric oxygen. Chemically modified oxidative drying oils such as polyurethane oils or low-molecular-weight polybutadiene oils can also be used. Impregnating agent based on cellulose

[0125] Nitrocellulose lacquers typically contain additional resins and solvents to improve their application properties. Other cellulose-based impregnating agents contain organic cellulose esters such as cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate. Rubber-based impregnating agent

[0126] These impregnating agents based on chlorinated rubber, chlorinated rubber-alkyd resin combinations and chlorinated rubber-acrylate resin combinations are resistant to water, which may be advantageous for the present invention in specific applications. Impregnating agent based on vinyl resins

[0127] These impregnating agents contain polyolefins and polyolefin derivatives such as polyethylene and polyisobutene. Ethylene copolymers such as ethylene-vinyl acetate copolymers or ethylene-maleic anhydride copolymers are water-soluble and can form salts. Chlorosulfonated polyethylenes have very high chemical resistance, especially to oxidizing agents. Impregnating agents based on polyvinyl halides and vinyl halide copolymers

[0128] Impregnating agents containing PVC and chlorinated polyvinyl chloride have advantageous mechanical properties and high abrasion resistance. Impregnating agents with vinylidene chloride copolymers have numerous technical applications. Important examples of copolymers without additional functional groups are vinyl acetate, dibutyl maleate, or isobutyl vinyl ether copolymers. Terpolymers with carboxyl groups are produced using dibutyl maleate or vinyl acetate and a dicarboxylic acid. Copolymers and terpolymers with hydroxyl groups are obtained using hydroxyacrylates or vinyl acetate and vinyl alcohol. Vinylidene chloride copolymers with acrylonitrile or acrylic resins have excellent chemical resistance and are primarily used as films for food packaging. Examples of fluoropolymers include cyclic perfluorinated polymers.Crosslinkable perfluorinated polymers contain epoxy groups, ether groups, hydroxyl groups or carboxyl groups as crosslinking functional groups. Impregnating agents based on vinyl ester polymers and copolymers

[0129] Impregnating agents based on vinyl acetate polymers and vinyl acetate copolymers with vinyl laurate, dibutyl maleate, or crotonic acid exhibit particularly high lightfastness and strong adhesion to metals. Polyvinyl alcohol is typically produced by the hydrolysis of polyvinyl acetate. It has high water solubility and is resistant to oils and greases, lubricants, and waxes. Polyvinyl acetals such as polyvinyl formal and polyvinyl butyral are produced by the reaction of polyvinyl acetate with aldehydes. They can be considered terpolymers of vinyl acetate, vinyl alcohol, and vinyl acetal. They can be physically crosslinked but can also be chemically crosslinked by hydroxyl groups. Impregnating agents based on vinyl ether polymers

[0130] Vinyl ether polymers are made from methyl vinyl ether or isobutyl vinyl ether and are often used as plasticizing resins in impregnating agents. Impregnating agents based on acrylates

[0131] Polyacrylates are only minimally attacked by chemicals and therefore impart high resistance to impregnating agents. They are colorless, transparent, and do not yellow even after prolonged thermal exposure. They do not absorb radiation above 300 nm and are therefore not degraded by UV radiation, provided they do not contain styrene or similar aromatic compounds. They have no unstable double bonds, but possess a high, stable luster and are hydrolysis-stable. Depending on their lateral functional groups, they can be crosslinked in a variety of ways (see Table 3). Alkyd impregnating agent

[0132] Alkyd resin binders contain oils / fatty acids, dicarboxylic acids (mainly phthalic acid or phthalic anhydride), and polyalcohols. They are classified as short-oil, medium-oil, or long-oil resins. They are modified with natural fatty acids or oils. For specific technical applications, alkyd resins are further modified with resin acids, benzoic acid, styrene, vinyltoluene, isocyanates, acrylates, epoxies, and silicone compounds. Waterproofing agent based on saturated polyesters

[0133] Saturated polyesters are produced by the polycondensation of polycarboxylic acids such as terephthalic acid and polyalcohols such as ethylene glycol. Polyesters containing hydroxyl groups can be crosslinked with melamine resins, benzoguanamine resins, and blocked isocyanates. Saturated polyesters containing carboxyl groups can be crosslinked with triglycidyl isocyanurate or epoxy resins. Saturated polyesters containing lateral acrylate groups can be cured by UV radiation and electron beam curing. Waterproofing agent based on unsaturated polyester

[0134] Unsaturated polyester resins, or UP resins, are soluble linear polycondensation products produced by the reaction of typically unsaturated polyhydric carboxylic acids such as malic acid or fumaric acid and dihydric alcohols such as ethylene glycol. Curing is initiated by peroxide or CC radical initiators. However, they can also be cured by UV radiation in the presence of photoinitiators. Polyurethane-based impregnating agents

[0135] Polyurethanes are binders with urethane, urea, biuret, or allophanate groups as crosslinking elements. These impregnating agents contain low-molecular-weight, oligomeric, or polymeric components that can be crosslinked by blocked polyisocyanates in one-component systems and by free polyisocyanates in two-component systems. The cured coatings exhibit high chemical resistance and excellent lightfastness and weather resistance. Impregnating agents based on epoxy resins

[0136] There are various types of epoxy resins, such as bisphenol A resins, bisphenol F resins, epoxy novolacs, aliphatic epoxy resins, cycloaliphatic epoxy resins, glycidyl esters, and heterocyclic epoxy compounds. They can be crosslinked by amines, polyesters, phenolic resins, amino resins, or polyisocyanates. Furthermore, they can be chemically modified, resulting in epoxy resin esters and epoxy resin (meth)acrylic acid esters. Impregnating agents based on urea, benzoguanamine and melamine resins

[0137] Alkylated urea, benzoguanamine, glycoluril, toluenesulfonamide, and melamine formaldehyde resins are a versatile group of crosslinking agents for polymers containing hydroxyl, amide, and carboxyl groups. They are used in both water-based and solvent-based impregnating agents. Impregnating agents based on phenolic resins

[0138] Phenolic resins are polycondensation products of phenols and formaldehyde and are self-crosslinking in the presence of bases or basic salts. Phenolic resins are pale yellow to dark brown in color and are therefore unsuitable for color applications. Because they form hard and brittle films, they must be mixed with other resins such as epoxy resins, polyvinyl butyral resins, or polyester resins. Impregnating agents based on silicone resins and organic-inorganic hybrid resins

[0139] Polysiloxane or silicone resins for coating purposes are produced from mixtures of di- or trifunctional organosilane monomers such as phenyl and methyl triethoxysilane, methylphenyldichlorosilane, and dimethyldichlorosilane through controlled hydrolysis and condensation. Pure silicone resins, however, are often too soft and too thermoplastic for coating applications. Therefore, they are blended with common and well-known resins such as alkyd resins, acrylic resins, epoxy resins, and phenolic resins. A particularly suitable group of silicone resins are hybrids of siloxane-polyurethane and siloxane-epoxy or siloxane-acrylate and sol-gel polymers. The sol-gel hybrid polymers are produced by the polycondensation of siloxanes containing hydrolyzable groups. Impregnating agents based on protective colloids

[0140] Protective colloids are formed particularly by water-soluble polymers such as - partially saponified polyvinyl acetate, polyvinyl alcohol and polyvinylpyrrolidone, - Nanocellulose, microcellulose and macrocellulose as well as starches, - Cellulose ethers (tylose) such as ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and Polyether acrylates, proteins, alginates, peptins, and gelatin are formed. Methylcellulose is particularly preferred. Impregnating agents based on physically hardening polymers

[0141] These impregnating agents contain common and well-known, water-dilutable, physically curing, high-molecular-weight polymers that do not require crosslinking agents for chemical crosslinking. Preferably, the water-dilutable, physically curing, high-molecular-weight polymers have a mass-average molecular weight M wThese polymers have a hardness exceeding 100,000 Daltons and exist in the form of finely divided dispersions with particle sizes from 1 nm to 1,000 nm, and particularly from 10 nm to 1,000 nm. They are typically produced by mini- or microemulsion polymerization. Butadiene, styrene, vinyl acetate, and (meth)acrylates are particularly preferred as monomers. The polymer matrix C is formed when the water, acting as a coalescing agent, evaporates after application, causing the previously dispersed polymer particles to coalesce and the polymer molecules to crosslink at room temperature or slightly elevated temperature through loop formation. The concentrations of the dispersed polymer particles in the impregnating agents can vary widely and depend on the specific requirements. Preferably, the concentrations are in the range of 0.1 wt% to 30 wt%, more preferably 0.1 wt% to 25 wt%, and particularly 0.1 wt% to 20 wt%.-%, each based on the total amount of an aqueous impregnating agent present. Impregnating agents based on adhesives

[0142] The adhesive matrix is ​​constructed using at least one adhesive selected from the group consisting of biopolymers, polysaccharides, chemically curing adhesives, polymerization adhesives, cyanoacrylate adhesives (superglue), methyl methacrylate adhesives, anaerobically curing adhesives, unsaturated polyesters (UP resins), radiation-curing adhesives, polycondensation adhesives, phenol-formaldehyde resin adhesives, silicone-silane crosslinked polymer adhesives, lignin adhesives, polyimide adhesives, polysulfide adhesives, polyaddition adhesives, epoxy resin adhesives, polyurethane adhesives, silicone polyisocyanate adhesives, physically setting adhesives, solvent-based adhesives, contact adhesives, dispersion adhesives, cement, cement-based adhesives, foam concrete, gypsum-based adhesives, plastisols, adhesives without a hardening mechanism, and slaked lime and adhesives based thereon. adhesives, producible.

[0143] Aqueous impregnating agents based on epoxy resins are particularly preferred for the production of the polymer matrices. These impregnating agents or dispersions are particularly often found in them. - Water, - at least one species of metal microflakes of a medium particle size d 50 from 0.6 µm to <1,000 µm, - at least one epoxy-reactive wetting agent, in particular a reaction product of polyoxypropylene monoamine (Jeffamine®) with a molar excess of bisphenol-A diglycidyl ether, - at least one crosslinking agent based on amines, in particular Waterpoxy® 751 (amine adduct, hydrogen equivalent (HEW) = 224, 60 wt% in water), - at least one hardening catalyst.

[0144] Furthermore, aqueous impregnating agents or dispersions based on physically hardening polymers are particularly preferred for the production of the fixed metal microflakes. Particularly preferred aqueous dispersions contain - Water, - at least one species of metal microflakes B of a medium particle size d 50 from 0.6 µm to <1,000 µm and - at least one mini- or microemulsion polymer in the form of dispersed polymer particles of an average particle size d 50 from 10 nm to <1,000 µm as a physically curable film former. Furthermore, they preferably contain at least one additive. Preferred additives are: - at least one progressive additive or spreading agent, - at least one stabilizing agent, - at least one amphoteric surfactant and / or niotenoid and / or - at least one essential oil.

[0145] The film formers are common and well-known, water-dilutable, physically hardening, high-molecular-weight polymers that do not require crosslinking agents for chemical crosslinking.

[0146] Preferably, the water-dilutable, physically curing, high-molecular-weight polymers have a mass-average molecular weight M w They have a density of over 100,000 Daltons and exist in the form of finely divided dispersions with particle sizes from 1 nm to 1,000 nm, and especially from 10 nm to 1,000 nm. They are usually produced by mini- or microemulsion polymerization.

[0147] Butadiene, styrene, vinyl acetate and (meth)acrylates are particularly preferred as monomers.

[0148] The film formation occurs when the water, acting as a coalescing agent, evaporates after application, causing the previously dispersed polymer particles to coalesce and the polymer molecules to crosslink at room temperature or slightly elevated temperature through loop formation.

[0149] The concentrations of the dispersed polymer particles in the aqueous dispersions can vary widely and depend on the requirements of the individual case. Preferably, the concentrations are in the range of 0.1 wt.% to 30 wt.%, more preferably 0.1 wt.% to 25 wt.%, and particularly 0.1 wt.% to 20 wt.%, in each case based on the total amount of an aqueous dispersion present.

[0150] Preferably, the at least one spreading additive or spreading agent is selected from the group consisting of modified and unmodified silicones, in particular poly(dimethylsiloxane), polyacrylates of a molecular weight of about 10,000 Daltons, and cellulose acetobutyrate.

[0151] Preferably, the concentrations of the flow additives in the aqueous dispersions according to the invention are 0.1 wt.% to 2.0 wt.%, preferably 0.1 wt.% to 1.0 wt.% and in particular 0.1 wt.% to 0.5 wt.%, in each case based on the amount of film formers in an existing aqueous dispersion.

[0152] Preferably, stabilizing agents such as fatty acid salts like sodium oleate, hydroxycarboxylic acid salts such as malates, i.e. salts or esters of malic acid, and citrates, ascorbic acid and polyelectrolyte complexes, as described in German patent application DE 10 2010 001 891 A1, are used.

[0153] Examples of suitable non-ionic surfactants or niotenes are sorbitan esters, fatty alcohol polyglycol ethers and alkylphenol polyglycol ethers.

[0154] Examples of suitable amphoteric surfactants or amphoteric surfactants are those approved under food law for cleaning food and beverage equipment, such as those known from German patent DE 100 38 377 C2. These have the general formula I. RR 1 R 2 N + -(CR 3 R 4 ) n -COO - (I),

[0155] In the general formula |, the group R represents an aliphatic or cycloaliphatic group with 8 to 25 carbon atoms. Preferably, the group R represents an aliphatic group. The aliphatic group R can be linear or branched; preferably, it is linear. Examples of suitable aliphatic groups are octyl, nonyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl (cetyl), heptadecyl, octadecyl, nonadecyl, eicosanyl, or ceryl. Of these, the groups with 8 to 16 carbon atoms, especially the lauryl group, are particularly advantageous and are therefore especially preferred. The groups R 2 and R 1 are identical or different aliphatic residues with 1 to 4 carbon atoms. Examples of suitable residues R 1 and R 2 These are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, of which methyl groups are advantageous and therefore particularly preferred. The R groups3 and R 4 are the same or different from each other and represent aliphatic residues with 1 to 4 carbon atoms or hydrogen atoms. Examples of suitable residues R 3 and R 4 are the residues described above R 1 and R 2 Preferably, the residues are R 3 and R 4 around hydrogen atoms. The index n stands for an integer from 1 to 4, preferably from 1 to 3, and particularly for 1. Accordingly, lauryldimethylcarboxymethylammonium betaine is particularly preferred.

[0156] In particular, the aqueous dispersions according to the invention contain at least one essential oil.

[0157] Examples of essential constituents of essential oils are ocimene, myrcene, linalool, geraniol, neral, citronellal, geranyl acetate, linalyl acetate, carveol, carvacrol, thymol, apiol, cinnamaldehyde, anethole, dillapiol, estragole, coriandrin, limonene, alpha-terpinene, phellandrene, menthol, carvone, menthone, menthofuran, cineole, anethofuran, alpha-bisabolol, alpha-carophyllene, alpha-pinene, camphene, sabinol, sabinene, borneol, camphor, fenchone, bornyl acetate, isobornyl acetate, chamazulene, and beta-carophyllene.

[0158] The essential oils are produced from the following plants, plant parts and animal products: African Bluegrass, Aglaia, Ajowan, Elecampane, Elecampane Root, Algae Absolute, Ammi visnage, Amyris, Angelica Seed, Angelica Root, Anise, Star Anise, Artemisia afra, Artemisia arborescens, Artemisia ludoviciana, Valerian, Basil, Basil sanctum, Sweet Basil, Bay St. Thomas Oil, Benzoin Siam Resinoid, Bergamot, Birch, Savory, Cabreuva, Cadewood, Cadeberries, Cajeput, Calmus, Cananga, Cassia, Red Champaca, White Champaca, Rockrose, Citronella Ceylon Type, Citronella Java Type, Clementine, Combava, Copaiba Balsam, Cypriol Nargamotha, Damania, Davana, Dill Seed, Dill Herb, Southernwood, Oakmoss, Vervain, Elemi, Tarragon, Epilobium augustifolium, Eucalyptus globulus Eucalyptus citriodoa, Eucalyptus radiata, Eucalyptus polybractea, Eucalyptus dives, Eucalyptus smithii, Fennel, Sitka spruce, Norway spruce, Norway spruce, Fokienia, Fragonia, Frangipani, Galbanum, Galangal root, Geranium, Rock cranesbill, Rose geranium, Bourbon geranium, Gingerlily, Goldenrod, GrapefruitPink grapefruit, hemp, santolina, hinoki, howood, honey, hops, immortelle, Balkan immortelle, immortelle bracteiferum, ginger, iris, Indian jasmine, Arabian jasmine, Egyptian jasmine, blackcurrant, blue chamomile, Roman chamomile, camphor, kanuka, cardamom, carrot seeds, kewra, Scots pine, Scots pine, mountain pine, star pine, Swiss stone pine, coriander, coriander leaves, caraway, cumin, black cumin, turmeric, yellow root, larch needles, larch resin, bitter lavender, lavandin grosso, lavandin abrial, spike lavender, mailette, highland lavender, Kashmir lavender, French lavender, ledum, lemongrass, Leptospermum citratum, lovage, lime, linaloe berries, litsea, bay laurel, manolia blossoms, magnolia leaves Wild marjoram, sweet marjoram, dead mandarin, green mandarin, manuka, lemon balm, mimosa, peppermint, mint, spearmint, spearmint, medicinal mint, lemon mint, wild bergamot, bee balm, nutmeg, myrrh, myrtle, lemon myrtle, honey myrtle, spikenard, clove leaves, clove flowerBeroli, Niaouli, Oponax, Orange, Blood Orange, Bitter Orange, Spanish Oregano, Oregano vulgare, Wild Marjoram, Palmarosa, Palo Santo, Patchouli, Peruvian Balsam, Parsley, Petitgrain Bigarade, Petitgrain Lemon, Petitgrain Bergamot, Petitgrain Mandarin, Green Pepper, Black Pepper, Allspice Berries, Pistachio, Rainforest, Ravintsara, Ravensara anisata, Ravensara aromatica, Rhododendron, Rose petals (Turkish, Bulgarian, white Bulgarian and Persian), Rosemary, Spanish Highland Rosemary, French Highland Rosemary, Rosemary Borneon, Rosemary Verbenone, Sage, Lavender Sage, Clary Sage, Sandalwood, Blue Yarrow, Schinus, California Pepper, Schinus terebinthifolius, Brazilian Pepper, Celery, Styrax, Balsam Fir, Douglas Fir Hemlock, Giant Fir, Siberian Fir, Silver Fir, Tea Tree, White Cloud Tree, Thuja, Thyme, Wild Thyme, Tolu Balsam, Tonka Bean, Tuberose, Vanilla, Violet Leaves, Vetiver, Bourbon Vetifer, Vitex Berries, Chaste Tree, LantanaJuniper berry, juniper, mountain juniper, African and Indian frankincense, frankincense carterii, wormwood, wintergreen, long ylang, hyssop, yuzu, Zanthoxylum alatum, Szechuan pepper, Atlas cedarwood, cedar needles, Himalayan cedar, cinnamon bark, cinnamon leaves, cinnamon, Swiss pine, yellow and green lemon, false cypress, Lawson cypress, Spanish, French, Moroccan and Mexican cypress, and blue cypress.

[0159] Many of these essential oils have biocidal properties and a refreshing, calming, or stimulating and pleasant fragrance. All evaporate without leaving any residue.

[0160] The composition of aqueous dispersions can vary widely and thus be excellently adapted to the requirements of the individual case.

[0161] A particularly advantageous aqueous dispersion contains, in each case based on the total amount of the aqueous dispersion according to the invention, - 0.001 wt.% (10 ppm) to 30.0 wt.% (300,000 ppm), preferably 0.01 wt.% (100 ppm) to 25.0 wt.% (250,000 ppm), particularly preferably 0.1 wt.% (1,000 ppm) to 20.0 wt.% (200,000 ppm) and most preferably 1 wt.% (10,000 ppm) to 15.0 wt.% (150,000 ppm) of biocidal metal microparticles, - 1.0 wt.% to 20 wt.%, preferably 1.0 wt.% to 15 wt.% and in particular 1.0 wt.% to 10 wt.% of at least one emulsion polymer in the form of dispersed polymer particles as a film former, - 0.1 wt.% to 2.0 wt.%, preferably 0.1 wt.% to 1.0 wt.% and particularly 0.1 wt.% to 0.5 wt.% of at least one gradient additive, - 0.1 wt.% to 3.0 wt.%, preferably 0.1 wt.% to 2.0 wt.% and particularly 0.1 wt.% to 1.0 wt.% of at least one stabilizing agent, - 0.1 wt.% to 4.0 wt.%, preferably 0.1 wt.% to 3.0 wt.% and particularly 0.1 wt.% to 2.0 wt.% of at least one amphoteric surfactant and / or niotenoid and - 0.01 wt.% to 3.0 wt.%, preferably 0.01 wt.% to 2.0 wt.% and particularly 0.01 wt.% to 1.0 wt.% of at least one essential oil.

[0162] In particular, it consists of water and the components specified above in the specified quantities.

[0163] During application and physical curing of these preferred aqueous dispersions, no volatile organic compounds (VOCs) are released other than essential oils and water, which is a significant advantage of these aqueous dispersions.

[0164] In general, it is particularly advantageous if the impregnating agents described above are free of most-penetrating particle-size metal microparticles (MPPS) of a medium particle size d. 50from 0.2 µm to 0.4 µm.

[0165] The production of impregnating agents or dispersions is carried out by mixing and homogenizing the components described above in water. The emulsion polymers are preferably used in the form of powders obtained by spray drying. The production of the impregnating agents does not require any special methodological features, but is carried out according to the usual and known methods for the production of aqueous dispersions by mixing the components described above in suitable mixing equipment such as stirred tanks, ultrasonic dispersers, dissolvers, Ultraturrax, inline dissolvers, stirred mills, bead mills, static mixers, toothed dispersers, countercurrent mixers, or extruders.

[0166] The aqueous dispersions can be applied using common and well-known application methods such as immersion, spraying (especially compressed air spraying, airless spraying, air-mix spraying and hot spraying), curtain coating, brushing, doctor blade application, two-component coating, roller application, calender coating, wiping, pouring, troweling, strip coating, centrifuging and drum coating.

[0167] In a preferred method for impregnating the adsorbent materials and / or the particulate, inert carrier materials described above, a system is used that includes an automatic feed of the adsorbent materials and / or the particulate carrier materials onto an endless belt guided by at least two transport rollers and featuring a vibrating section. The fed adsorbent materials and / or particulate carrier materials are vibrated and, in a first station, sprayed with at least one of the liquid impregnating agents described below. The vibration ensures that the adsorbent materials and / or particulate carrier materials are coated as uniformly as possible.In a second station, the impregnating agents are thermally cured – also under vibration – in a continuous oven, with IR emitters and / or UV radiation, so that the biocidal coating forms on the adsorbent materials and / or particulate carrier materials, consisting of the polymer and / or adhesive matrix and the metal microflakes. The vibration prevents the particles or fibers from sticking together and the cured impregnating agents from forming firmly adhering films on the continuous belt. If this does occur to some extent, the impregnated adsorbent materials and / or particulate carrier materials are separated in a third station and then discharged into a storage container. After the continuous belt is redirected, any remaining cured impregnating agents are scraped off with doctor blades.

[0168] The device described above according to the invention serves for the reversible adsorption and desorption of carbon dioxide from combustion exhaust gases according to the method according to the invention.

[0169] In the process according to the invention, the at least one device according to the invention is closed at the inlet and outlet after the adsorption phase at 20°C to 50°C. The closing device in the extraction line to a compressor is then opened, and the remaining combustion gases are extracted from the closed device according to the invention and discharged via the open outlet line with the pressure vessel valve closed. After the remaining combustion gases have been removed, the outlet line is closed. In the desorption phase, the carbon dioxide-saturated adsorbent material is heated to a temperature between 80°C and 150°C, and the desorbed carbon dioxide is forced into the pressure vessel by means of the compressor.After the desorption phase is completed, the suction line and the pressure vessel are closed, and the adsorption materials in the device according to the invention are cooled to 20°C to 50°C, after which a further adsorption phase is initiated.

[0170] In an advantageous embodiment of the method according to the invention, at least two devices according to the invention are connected in parallel, wherein at least one device according to the invention is in the adsorption phase and at least one device according to the invention is in the desorption phase. This allows the temperature swing process to be carried out continuously.

[0171] Advantageous embodiments of the device according to the invention are described with reference to the Fig. 1 to 6 explained in more detail. Fig.Figures 1 to 6 are schematic representations intended to illustrate the principle and function of the device according to the invention. Since a person skilled in the art can consider further embodiments within the scope of the present invention based on this teaching, without having to inventively invent, the following do not limit the scope of the invention. Fig. 1 to 6 do not include the invention.

[0172] They show Fig. 1 the top view of the longitudinal section through a first embodiment of the device 1 according to the invention with a cooling and heating device 2, a device 3 for pumping out and compressing the carbon dioxide and a gas cylinder 4; Fig. 2 the top view of the cross-section through the first embodiment of the device 1 according to the invention. Fig. 1 with chambers for the absorber material 1.3 and the heating and cooling device 2 with the liquid circuit 2.2, in which the halogen-free liquid 2.1 is carried in countercurrent flow; Fig. 3 the top view of the inlet-side gas-permeable cover 1.11 of the first embodiment of the device 1 according to the invention. Fig. 1 with the gas inlets 1.11.1, the wall 2.2.1 of the liquid circuit 2.2 and the cross-section through the outlet 2.2.2 of the halogen-free liquid 2.1; Fig. 4 the top view of the longitudinal section through a second embodiment of the device 1 according to the invention, wherein the combustion gases 1.2 are deflected several times when flowing through the adsorber materials 1.3, wherein the halogen-free liquid 2.1 is guided through the liquid circuit 2.2 in countercurrent flow against the combustion gases 1.2 and is also deflected several times; Fig.5 the top view of the longitudinal section through a third embodiment of the device 1 according to the invention with a cooling device 2.3 with a cooling circuit 2.3.1 with an annular distribution line (cooling) 2.2.3 and an annular collecting line (cooling) 2.3.2 as well as a heating device 2.4 and a heating circuit 2.4.1 with an annular distribution line (heating) 2.4.2 and an annular collecting line 2.4.3 and Fig. 6 the top view of the longitudinal section through a section of a packed bed of an adsorbent material with metal microflakes 1.4, which are fixed on and in the particles of a support 1.5 or a native adsorbent material 1.3.1 using a polymer and / or adhesive matrix 1.6.

[0173] In the Fig. Reference symbols 1 to 6 have the following meaning: 1 Device for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases 1.1 1.1 Combustion exhaust gases 1.2 Cooled and water-depleted combustion exhaust gases 1.3 Adsorbent material with fixed metal microflakes 1.4; 1.6 or 1.4; 1.5; 1.6 1.3.1 Native adsorbent material free of fixed metal microflakes 1.4; 1.6 or 1.4; 1.5; 1.6 1.4 Platelet-shaped metal microparticles or metal microflakes 1.5 Carrier material 1.6 Polymer and / or adhesive matrix 1.7 Carbon dioxide-depleted or carbon dioxide-free combustion exhaust gases 1.8 Shut-off device, gate valve 1.9 Carbon dioxide sensor 1.10 Wall of the device 1 1.11 Gas-permeable cover 1.11.1 Gas inlet 2 Heating and cooling device 2.1 Halogen-free liquid, heat exchanger 2.2 Fluid Cycle 2.2.1 Wall of the liquid circuit 2.2 2.2.2 Outlet of the halogen-free liquid 2.1 in cross-section 2.3 Cooling device 2.3.1 Cooling circuit 2.3.2 Manifold (cooling) 2.3.3 Distribution line (cooling) 2.4 Heating device 2.4.1 Heating circuit 2.4.2 Distribution line (heating) 2.4.3 Collective pipe (heating) 3 Device for pumping out and compressing the desorbed carbon dioxide 3.1 Extraction line 3.1.1 Shut-off and through-flow valve in the suction line 3.1 3.2 Compressor, compressor 3.3 Output line 3.3.1 Shut-off and through-flow valve in the outlet line 3.3 4 Removable pressure vessel or removable gas cylinder 4.1 Pressure line 4.2 Shut-off and bypass valve of the removable pressure vessel or removable gas cylinder A. Discharge for the carbon dioxide-depleted or carbon dioxide-free combustion exhaust gases 1.7 Z Inlet for the cooled and water-depleted combustion exhaust gases 1.2 ▲ Flow direction of the cooled and water-depleted combustion gases 1.2 and the carbon dioxide-depleted or carbon dioxide-free combustion gases 1.7 Δ Flow direction of the at least one halogen-free liquid 2.1 in the device 2 Detailed description of the characters. Preliminary remarks.

[0174] Before the production of the adsorbent materials 1.3 with the fixed silver microflakes 1.4; 1.6, the respective quantity of impregnating agent that may be applied to the respective native adsorbent materials 1.3.1 at most is determined by comparative test series so that the absorption capacity of the adsorbent materials 1.3 to be used according to the invention for carbon dioxide is reduced by the metal microflakes 1.4; 1.6 fixed to the native adsorbent materials 1.3.1 to 15% of the absorption capacity of the native adsorbent materials 1.3.1 free of fixed silver microflakes 1.4; 1.6.

[0175] The device according to the invention includes mountings for its components and functional peripherals for its operation, consisting of conventional and known mechanical, pneumatic, hydraulic, optical, electrical, and electronic computing, switching, measuring, and control devices, electric motors, pneumatically operated motors, energy storage devices, actuators, electrical, hydraulic, and pneumatic lines, data transfer lines, gas flow meters, temperature measuring devices, pressure measuring devices such as manometers, alarm devices, timers, and optical displays. Several devices according to the invention are connected to a central electronic control and monitoring system via radio or WLAN.

[0176] The electrical, mechanical and / or thermal energy for operation of the device according to the invention 1 is obtained, for example, from batteries, alternators, power generators, rotating shafts and / or the combustion gases, which can form an energy network as part of the functional periphery.

[0177] The brackets and functional peripherals are located in the Fig. Items 1 to 6 are not shown for the sake of clarity. Production Example 1: The production of an epoxy resin-silver microflake dispersion as an impregnating agent

[0178] 2 parts by weight of commercially available silver microflakes with a mean particle size d determined by light microscopy 50Silver microflakes measuring 2.4 µm are dispersed in 100 parts by weight of an 80% aqueous solution of an epoxy-reactive wetting agent. The wetting agent is the reaction product of a polyoxypropylene monoamine (Jeffamine®) with a molar excess of bisphenol A diglycidyl ether. This resulted in 102 parts by weight of a dispersion containing 1.96 wt% silver microflakes, based on the solids content.

[0179] The 102 parts by weight of the silver microflake dispersion are mixed with 398 parts by weight of a 56 wt% aqueous dispersion of Waterpoxy® 1455 from BASF SE. The 500 parts by weight of the resulting epoxy resin-silver flake dispersion are mixed with 70 parts by weight of Waterpoxy® 751 (amine adduct, hydrogen equivalent (HEW) = 224, 60 wt% in water) from BASF SE as a curing catalyst. The resulting 550 parts by weight of the dispersion are homogenized. The ready-to-spray dispersion has a solids content of 36 wt% based on its total weight. Before application to the absorber materials 1.3, it is stirred for 10 minutes to optimize the spray viscosity. Production Example 2: The production of a native sodium carbonate adsorbent material supported on activated carbon pellet 1.5 1.3.1

[0180] Activated carbon pellets 1.5 with a Sauter diameter of 6 mm to 8 mm are stored in a pressure vessel in a saturated aqueous sodium carbonate solution for 24 hours at room temperature. To accelerate the impregnation, a vacuum is applied over the sodium carbonate solution and the activated carbon pellets 1.5, causing the adsorbed air to escape more quickly from the pores of the activated carbon pellets 1.5. The resulting native adsorbent material 1.3.1 is then filtered off and dried in a convection oven at 150°C. Production Example 3: The production of an adsorbent material 1.3 based on the native sodium carbonate adsorbent material 1.3.1

[0181] The native sodium carbonate adsorbent material 1.3.1 of production example 2 is impregnated with the epoxy resin-silver microflake dispersion of production example 1 in a coating system. The coating system comprises an automatic feed of the native sodium carbonate adsorbent material 1.3.1 onto a continuous belt guided by three transport rollers and featuring a vibrating section. The fed native sodium carbonate adsorbent material 1.3.1 is vibrated and, in a first station, sprayed with the epoxy resin-silver microflake dispersion of production example 1. The vibration ensures that the native sodium carbonate adsorbent material 1.3.1 is coated as uniformly as possible. In a second station, the impregnating agent is thermally cured – also under vibration – in a continuous oven with IR emitters, so that the adsorbent material 1.3.1 is bonded with the fixed silver microflakes 1.4. 1.5; 1.6 forms.Vibration prevents the particles of adsorbent material 1.3 from clumping together and the cured impregnating agent from forming firmly adhering coatings or films on the continuous belt. If this does occur to some extent, the impregnated adsorbent material 1.3 is separated in a third station and then discharged into a storage container and stored under nitrogen until use. After the continuous belt is redirected, any remaining cured impregnating agent is scraped off with doctor blades.

[0182] Preferably, the impregnation is carried out under an inert gas such as nitrogen or carbon dioxide-free or carbon dioxide-depleted air.

[0183] The Fig. Figure 6 shows the section through a cutaway of a packed bed made of the adsorbent materials 1.3 of production example 3 with the fixed silver microflakes 1.4; 1.5; 1.6. Production Example 4: The production of an adsorbent material 1.3 based on a weakly basic anion exchange resin 1.3.1 in the hydroxide form

[0184] Lewatit® VP OC 1065 from Lanxess (native adsorbent material 1.3.1) is impregnated with the epoxy resin silver microflake dispersion from production example 1 in the corresponding coating system, as described in production example 3. The resulting adsorbent material 1.3 with the fixed silver microflakes 1.4, 1.5, and 1.6 is transferred to a storage container and stored under nitrogen until use. Production Example 5: The production of an adsorbent material 1.3 based on a strongly basic anion exchange resin 1.3.1 in hydroxide form

[0185] Amberlyst® A26 from Merck (native adsorbent material 1.3.1), a strongly basic anion exchange resin containing quaternary amino groups in the hydroxide form, is impregnated with the epoxy resin-silver microflake dispersion from Production Example 1 in the corresponding coating system, as described in Production Example 4. The resulting adsorbent material 1.3 with the fixed silver microflakes 1.4, 1.5, and 1.6 is discharged into a storage vessel and stored under nitrogen until use. Examples 1 to 9 and comparative experiments V1 to V9: Performance of adsorption / desorption cycles (temperature swing process) in the devices according to the invention 1 of Figures 1 to 5. General experimental procedure for Examples 1 to 9 and comparative experiments V1 to V9.

[0186] The combustion exhaust gases 1.1 from a running diesel engine are purified using a conventional and well-known catalyst for the selective reduction of NOx (SCR) and a conventional and well-known catalyst for the selective oxidation of CO2 (SCO). The purified combustion exhaust gases 1.1 are cooled to 30°C in a cooling device with water separation. The cooled, water-depleted combustion exhaust gases 1.2 are fed through the inlet Z to the adsorber materials 1.3, which are gas-tightly enclosed by the wall 1.10 and held at both the inlet and outlet by a gas-permeable cover 1.11. The adsorber materials adsorb the carbon dioxide at 30°C. The carbon dioxide-depleted or carbon dioxide-free combustion exhaust gases 1.7 are discharged through the outlet A. As soon as the carbon dioxide sensor 1.9 in outlet A indicates the presence of the greenhouse gas, the diesel engine is switched off and the adsorption phase is complete.

[0187] Before the desorption phase, the device 1 is closed at the inlet and outlet by means of the shut-off valves 1.8. Then, the valve 3.1.1 of the suction line 3.1 of the device 3 to the compressor 3.2 is opened. The remaining combustion gases 1.2; 1.7 are extracted from the closed device 1 and, with valve 4.1 of the gas cylinder 4 closed, discharged via the outlet line 3.3 and the open valve 3.3.1.

[0188] At the beginning of the desorption phase, valve 3.3.1 is closed, and valve 4.1 is opened towards gas cylinder 4. Then, the carbon dioxide-saturated adsorption material 1.3 in the closed apparatus 1 is heated to a temperature of 140°C using device 2 in Examples 1 to 3, and to a temperature of 80°C in Examples 4 to 9, 11, and 12. The desorbed carbon dioxide is extracted using compressor 3.2 and forced through a pressure line 4.1 into gas cylinder 4.

[0189] The end of desorption is indicated by a rapid pressure drop in device 1. After the desorption phase is complete, valves 3.1.1 and 4.1 are closed. Device 1 is then cooled back down to 30°C using device 2 and ethylene glycol 2.1 as a heat transfer medium in liquid circuit 2.2, following the countercurrent principle. A further adsorption phase is then initiated.

[0190] The Temperature Swing Process can be carried out in different embodiments of the device 1 according to the invention.

[0191] In the device 1 according to the invention, Fig.On the inlet side, the cooled, water-depleted combustion gases 1.2 flow through the gas inlets 1.11.1 of a gas-permeable cover 1.11 into the adsorber materials 1.3. The carbon dioxide-depleted or carbon dioxide-free combustion gases 1.7 flow out through another gas-permeable cover on the outlet side. The special feature of the heating and cooling device 2 is that the tubular wall 2.2.1 of the liquid circuit 2.2 containing the halogen-free liquid 2.1 is expanded in the area of ​​the adsorber materials 1.3 in such a way that it forms a star-shaped configuration in cross-section. This divides the space containing the adsorber materials into several chambers, thereby achieving intensive heat exchange. The halogen-free liquid 2.1 flows in the liquid circuit in the opposite direction to the flow direction of the combustion gases 1.2. The device 1 is tubular with a circular, oval or square cross-section.

[0192] The special feature of the device 1 according to the invention is that Fig. 4 is that the combustion gases 1.2 are deflected several times as they flow through the adsorber materials 1.3, whereby the halogen-free liquid 2.1 is carried in countercurrent flow to the combustion gases 1.2 through the liquid circuit 2.2 and is also deflected several times.

[0193] The special feature of the device 1 according to the invention is that Fig.Section 5 states that it comprises a cooling device 2.3 and a cooling circuit 2.3.1. The cooling circuit 2.3.1 includes an annular distribution line (cooling) 2.2.3 in the area of ​​the adsorbent materials, which distributes the halogen-free liquid 2.1 to several parallel cooling tubes. The annular collection line (cooling) 2.3.2 collects the halogen-free liquid 2.1, which is then returned to the cooling device 2.3 in the cooling circuit 2.3.1. Similarly, the halogen-free liquid 2.1 is heated by the heating device 2.4 and, in the heating circuit 2.4.1, is directed to the annular distribution line (heating) 2.4.2, through the heating tubes to the annular collection line 2.4.3, and from there back to the heating device 2.4. Examples 1 to 9 in detail

[0194] For example 1, the adsorber material 1.3 of manufacturing example 3 and the device 1 according to the invention are used. Fig. 1 to 3 used.

[0195] For example 2, the adsorber material 1.3 of manufacturing example 3 and the device 1 according to the invention are used. Fig. 4 used.

[0196] For example 3, the adsorber material 1.3 of manufacturing example 3 and the device 1 according to the invention are used. Fig. 5 used.

[0197] For example 4, the adsorber material 1.3 of manufacturing example 4 and the device 1 according to the invention are used. Fig. 1 to 3 used.

[0198] For example 5, the adsorber material 1.3 of manufacturing example 4 and the device 1 according to the invention are used. Fig. 4 used.

[0199] For example 6, the adsorber material 1.3 of manufacturing example 4 and the device 1 according to the invention are used. Fig. 5 used.

[0200] For example 7, the adsorber material 1.3 of manufacturing example 5 and the device 1 according to the invention are used. Fig. 1 to 3 used.

[0201] For example 8, the adsorber material 1.3 of manufacturing example 5 and the device 1 according to the invention are used. Fig. 4 used.

[0202] For example 9, the adsorber material 1.3 of manufacturing example 5 and the device 1 according to the invention are used. Fig. 5 used. Comparison trials V1 to V9

[0203] For the comparison experiments V1 to V9, examples 1 to 9 are repeated except that instead of the adsorber materials 1.3 from production examples 3 to 5, the corresponding native adsorber materials 1.3.1 are used. Conclusion

[0204] Using the devices according to the invention, the Fig.Materials 1 to 3, 5 and 6, in combination with the adsorber materials 1.3 from production examples 3 to 5, can undergo at least 50 adsorption / desorption cycles. Due to the increased thermal conductivity of the adsorber materials 1.3, the temperature swings occur faster and more energy-efficiently than with the native adsorber materials 1.3.1 of the prior art in comparative tests V1 to V9. Example 10: Carrying out adsorption / desorption cycles (temperature swing process) in two parallel-connected devices according to the invention 1 of Figure 5

[0205] For example 10, two devices 1 according to the invention are described in the Fig. 5 devices are connected in parallel, with one device 1 being in the adsorption phase and another device 1 being in the desorption phase. The adsorbent material 1.3 from production example 3 is used.

[0206] The combustion exhaust gases 1.1 from a running diesel engine are cleaned using a conventional and well-known catalyst for the selective reduction of NOx (SCR) and a conventional and well-known catalyst for the selective oxidation of NOx (SCO). The cleaned combustion exhaust gases 1.1 are cooled to 30°C in a cooling device with water separation.

[0207] The cooled, water-depleted combustion gases 1.2 are directed to a Y-shaped branch of the combustion gas pipe (not shown). A first branch is open to feed the cooled, water-depleted combustion gases 1.2 through the inlet Z to the adsorber materials 1.3 of the first device 1, which are gas-tightly enclosed by the wall 1.10. The adsorber materials 1.3 adsorb the carbon dioxide at 30°C. The carbon dioxide-depleted or carbon dioxide-free combustion gases 1.7 are discharged from outlet A. As soon as the carbon dioxide sensor 1.9 in outlet A indicates the presence of the greenhouse gas, the first branch is closed, and the adsorption phase of the first device 1 is complete.

[0208] During the adsorption phase of the first device 1, the second device is in the desorption phase. Device 1 is closed at both the inlet and outlet by means of the shut-off valves 1.8. Subsequently, the valve 3.1.1 of the extraction line 3.1 of device 3 to the compressor 3.2 is opened. The remaining combustion gases 1.2; 1.7 are extracted from the closed device 1 and, with valve 4.1 of the gas cylinder 4 closed, are discharged via the outlet line 3.3 and the open valve 3.3.1.

[0209] At the beginning of the desorption phase, valve 3.3.1 is closed, and valve 4.1 is opened towards gas cylinder 4. The carbon dioxide-saturated adsorption material 1.3 is then heated to a temperature of 140°C in the closed device 1 using device 2. The desorbed carbon dioxide is extracted using compressor 3.2 and forced through a pressure line 4.1 into gas cylinder 4.

[0210] The end of desorption is indicated by a rapid pressure drop in device 1. After the desorption phase is complete, valves 3.1.1 and 4.1 are closed. Device 1 is then cooled back down to 30°C using device 2 and ethylene glycol 2.1 as a heat transfer medium in the liquid circuit 2.2, operating on the countercurrent principle. A further adsorption phase is then initiated in the second device 1 by opening the shut-off valves 1.8 and closing the first branch, thus directing the cooled, water-depleted combustion gases 1.2 to the second device 1.

[0211] During the adsorption phase of the second device 1, the first device 1 goes through the desorption phase.

[0212] The major advantage of this method is that the temperature swing process does not have to be interrupted, but can be carried out with the diesel engine running. Examples 11 and 12: Carrying out adsorption / desorption cycles (temperature swing process) in the devices 1 according to the invention as shown in Figure 4. Production example 6: The production of an aqueous dispersion of silver microflakes. 1.4

[0213] For Examples 11 and 12, an aqueous dispersion of silver microflakes 1.4 is prepared by mixing and homogenizing its components. The aqueous dispersion consists of distilled water and, based on the total amount of the dispersion, - 4.0 wt% of commercially available silver flakes B with a mean particle size d determined by light microscopy 50 of 2.4 µm, - 6.0 wt% of a miniemulsion copolymer of styrene, butadiene and butyl methacrylate in the form of dispersed polymer particles of a medium particle size d 50 of 50 nm as a physically curable film former, - 1.0 wt% modified poly(dimethylsiloxane) as a leveling additive or spreading agent, - 1.5 wt% sodium citrate as a stabilizing agent, - 2.0 wt% lauryldimethyl-carboxymethyl-ammonium betaine as an amphoteric surfactant and - 1.0 wt% of an essential oil obtained from the Swiss pine. Production Example 7: The production of an adsorbent material 1.3 based on a weakly basic anion exchange resin 1.3.1 in the hydroxide form

[0214] Lewatit® VP OC 1065 from Lanxess (native adsorbent material 1.3.1) is impregnated with the aqueous dispersion from production example 6 in the corresponding coating system, as described in production example 3. The resulting adsorbent material 1.3 with the fixed silver microflakes 1.4, 1.5, and 1.6 is transferred to a storage container and stored under nitrogen until use. Production Example 8: The production of an adsorbent material 1.3 based on a strongly basic anion exchange resin 1.3.1 in hydroxide form

[0215] Amberlyst® A26 from Merck (native adsorbent material 1.3.1) is impregnated with the aqueous dispersion from production example 6 in the corresponding coating system, as described in production example 3. The resulting adsorbent material 1.3 with the fixed silver microflakes 1.4, 1.5, and 1.6 is transferred to a storage container and stored under nitrogen until use. The implementation of the Temperature Swing Process

[0216] For Example 11, the adsorbent material 1.3 from Production Example 7 is used. For Example 12, the adsorbent material from Production Example 8 is used. In both examples, the temperature swing process is carried out according to the general experimental procedure for Examples 1 to 9 and the comparative experiments V1 to V9. In both cases, at least 50 adsorption / desorption cycles can be performed. Due to the increased thermal conductivity of the adsorbent materials 1.3, the temperature changes (temperature swings) occur advantageously rapidly.

Claims

[1] Device (1) for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1) from internal combustion engines, incinerators and power plants, which, viewed in the flow direction of the combustion exhaust gases (1.1), - at least one device for cooling the combustion exhaust gases (1.1) to 10°C to 50°C for condensing the water contained in the combustion exhaust gases (1.1) or - at least one device for cooling the combustion exhaust gases (1.1) to 10°C to 50°C for condensing the water contained in the combustion exhaust gases (1.1) and (i) at least one catalyst for the selective reduction (SCR) of NOx or (ii) at least one catalyst for the selective reduction (SCR) and at least one catalyst for the selective oxidation (SCO) of ammonia, and - at least one supply line (Z) of the cooled and water-depleted combustion exhaust gases (1.2) is connected downstream of the device (1), characterized bythat the device (1) can be closed off from the at least one supply line (Z) for the cooled and water-depleted combustion exhaust gases (1.2) and at least one outlet line (A) for the carbon dioxide-depleted or carbon dioxide-free combustion exhaust gases (1.7) and (I) at least one device (2) which serves alternately for both cooling and heating at least one species of adsorbent material (1.3) for the reversible adsorption and desorption of carbon dioxide by means of at least one halogen-free liquid (2.1) as a heat exchanger, (II) at least one device (3) for pumping out and compressing the carbon dioxide released during desorption and (III) comprises at least one removable pressure vessel (4) for storing the desorbed carbon dioxide, wherein - the at least one adsorbent material (1.3) comprises at least one species of platelet-shaped metal microparticles (1.4) or metal microflakes (1.4) with an average particle size d 50 from 0.6 µm to <1,000 µm, which is (i) fixed on and / or in at least one native adsorbent material (1.3.1) and / or (ii) fixed on and / or in at least one species of a carrier material (1.5) for the native adsorbent material (1.3.1) by means of at least one species of a polymer and / or adhesive matrix (1.6), - the fixed metal microflakes (1.4) are present in such a quantity that the absorption capacity of the adsorbent material (1.3) for carbon dioxide at 30°C (303.15 K) is reduced to 1% to 50% of the absorption capacity of the native adsorbent material (1.3.1) free of fixed metal microflakes (1.4; 1.6), and wherein - the at least one halogen-free liquid (2.1) has a melting point <20°C and a boiling point >150°C and is selected from the group consisting of ethylene glycol, polypropylene glycol, butylene glycol, glycerol, glycol ethers, silicone oils and ionic liquids. [2] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to claim 1, characterized by that the flow direction of the at least one halogen-free liquid (2.1) in the device (2) is opposite to the flow direction of the combustion exhaust gases (1.2; 1.7). [3] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to claim 1 or 2, characterized by that the device (2) comprises the following components: - at least one closed liquid circuit (2.2) with a cooling device (2.3) and a heating device (2.4) for the alternating cooling and heating of the at least one halogen-free liquid (2.1) and the adsorber material (1.3) or - at least two separate closed liquid circuits (2.2), of which at least one is equipped with a cooling device (2.3) for cooling the at least one halogen-free liquid (2.1) and the adsorber material (1.3) and of which at least one is equipped with a heating device (2.4) for heating the at least one halogen-free liquid (2.1) and the adsorber material (1.3). [4] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 3, characterized bythat the at least one native adsorbent material (1.3.1) is selected from the group consisting of basic and / or nanoporous, microporous and / or macroporous materials. [5] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 4, characterized by that the at least one native adsorbent material (1.3.1) is selected from the group consisting of primary amino group-containing, weakly basic anion exchangers in the hydroxide form, strongly basic anion exchangers in the hydroxide form and supported alkali carbonates such as sodium carbonate, sodium bicarbonate, sodium sesquicarbonate and / or potassium carbonate. [6] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 5, characterized bythat the platelet-shaped metal microparticles (1.4) or metal microflakes (B) are selected from the group consisting of metal microflakes of gold, osmium, silver, copper, copper-silver alloys, zinc, tin, copper bronzes, brass bronzes and brass. [7] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 6, characterized by that the platelet-shaped metal microparticles (1.4) are silver microflakes. [8] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 7, characterized bythat the polymer matrix (1.6) contains at least one plastic from the group consisting of linear and / or branched and / or block-like, comb-like and / or randomly structured polyaddition resins, polycondensation resins and / or (co)polymers of ethylenically unsaturated monomers. [9] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 8, characterized bythat the adhesive matrix (1.6) consists of at least one adhesive selected from the group consisting of biopolymers, polysaccharides, chemically curing adhesives, polymerization adhesives, cyanoacrylate adhesives (superglues), methyl methacrylate adhesives, anaerobic curing adhesives, unsaturated polyesters (UP resins), radiation-curing adhesives, polycondensation adhesives, phenol-formaldehyde resin adhesives, silicone-silane cross-linked polymer adhesives, lignin adhesives, polyimide adhesives, polysulfide adhesives, polyaddition adhesives, epoxy resin adhesives, polyurethane adhesives, silicone-polyisocyanate adhesives, physically setting adhesives, solvent-based adhesives, contact adhesives, dispersion adhesives, cement, cement-based adhesives, foam concrete, gypsum-based adhesives, plastisols, adhesives without a setting mechanism and slaked lime and adhesives based thereon. [10] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to one of claims 1 to 9, characterized by that the at least one carrier material (1.5) is selected from the group consisting of organic, organometallic and inorganic, non-porous, nanoporous, microporous and / or macroporous materials. [11] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) of internal combustion engines, combustion furnaces and power plants according to claim 10, characterized bythat the organic, organometallic and inorganic, non-porous, nanoporous, microporous and / or macroporous carrier materials (1.5) from the group consisting of prefabricated air filters, organometallic frameworks, MOF, organic frameworks, COF, reticulated foams made of plastics, open-cell foams made of natural materials, sponges, glass, ceramics, metals, natural fibers, chemical fibers, polymer fibers and mineral fibers with an average fiber length of 500 nm to 50 mm in the form of scrims, woven fabrics, felts, nonwovens, spunbonded materials and melt-blown materials as well as particulate, inert, inorganic carrier materials with an average particle size d 50 from 0.5 µm to 10 cm. [12] Device (1) for the reversible adsorption of carbon dioxide in combustion exhaust gases (1.1) from internal combustion engines, incinerators and power plants according to 10 or 11, characterized bythat the inorganic carrier materials (1.5) from the group consisting of (i) packings for columns and Raschig rings, and from the group consisting of (ii) layered silicates, foam glasses, foam glass gravel, pumice stones, zeolites, expanded clays, expanded glasses, expanded mica, expanded perlite, foam cements, ceramic foams, activated carbons and mixtures of at least two of these materials in the form of spheres, hollow spheres, shards, granules, ground chunks, pellets, rings, spheres with core-shell structures, ellipsoids, cubes, cuboids, pyramids, cones, cylinders, rhombuses, dodecahedrons, truncated dodecahedrons, icosahedrons, truncated icosahedrons, dumbbells, tori, platelets, needles with a circular, oval, elliptical, square, triangular, quadrangular, pentagonal, hexagonal, heptagonal, octagonal or star-shaped cross-sections as well as shards, rings, dumbbells, tori, needles and plates bent in at least one direction of space. [13] A process for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1) from internal combustion engines, incinerators and power plants, in which carbon dioxide is adsorbed on at least one adsorbent material (1.3) in the adsorption phase at 10°C to 50°C and, after saturation of the adsorbent material (1.3), is desorbed, pumped out, compressed and collected in the desorption phase at temperatures of 80°C to 150°C, after which a new adsorption / desorption cycle is initiated, characterized by that at least one device (1) according to one of claims 1 to 12 is used. [14] Process for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1) from internal combustion engines, combustion furnaces and power plants according to claim 13, characterized by that one - which closes at least one device (1) on the inlet and outlet sides after the adsorption phase at 10°C to 50°C, - the valve (3.1.1) of a suction line (3.1) of the device (3) is opened to a compressor (3.2), the remaining combustion gases (1.1; 1.2) are sucked out of the closed device (1) and, with the valve (4.1) of the pressure vessel (4) closed, are discharged via the outlet line (3.3) and the open valve (3.3.1), after which - in the desorption phase, the valve (3.3.1) is closed, the valve (4.1) is opened, the closed device (1) is heated to a temperature between 80°C and 150°C by means of the at least one device (2) and the desorbing carbon dioxide is pressed into the pressure vessel (4) through a pressure line (4.1) by means of the compressor (3.2), - after completion of the desorption phase, the valves (3.1.1; 4.1) are closed and the device (1) is cooled to 10°C to 50°C using the at least one device (2), after which - initiates another adsorption phase. [15] Process for the reversible adsorption and desorption of carbon dioxide in combustion exhaust gases (1.1) from internal combustion engines, combustion furnaces and power plants according to claim 13 or, characterized by that at least two devices (1) are connected in parallel, wherein at least one device (1) is in the adsorption phase and at least one device (1) is in the desorption phase.

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