High capacity co 2 absorber, calipatron

Abstract

The invention relates to a CO2 absorber (calipatron) capable of absorbing CO2 gas in the ambient air in certain and defined volumes without the use of certain amines, such as sodium hydroxide, which are irritating or toxic to the trachea.

Description

[0001] HIGH CAPACITY CO2 ABSORBER, CALIPATRON

[0002] Field of the Invention

[0003] The invention relates to a new generation product to be used as a respiratory aid in case of elevated CO2 concentration in completely enclosed environments such as submarines, flight cabins, escape capsules where ventilation is not possible for long periods of time.

[0004] In particular, the invention relates to a calipatron capable of absorbing CO2 gas in ambient air in certain and defined volumes without the use of certain amines which are toxic or irritating to the trachea, such as sodium hydroxide.

[0005] State of the Art

[0006] Today, increased carbon dioxide (CO2) concentration is the most important factor deteriorating air quality in submarines, flight cabins, escape pods or search and rescue vehicles that are completely submerged under water, or in space operations. Increased CO2 concentration indoors can restrict the movement of personnel, resulting in headaches, dizziness, reduced ability to think and eventually asphyxiation due to insufficient oxygen intake. The CO2 concentration in open air conditions is around 380 ppm on average and can rise up to 500 ppm in outdoor and city air due to exhaust and domestic industrial use. Inside buildings, this value can reach up to several thousand ppm. When the CO2 concentration reaches around 20.000 ppm (2%), deep breathing becomes necessary, at 40.000 ppm respiration is significantly affected, 100.000 ppm causes visual disturbances, tremors and unconsciousness, and 250.000 ppm is lethal. Personnel working on submarines are routinely exposed to high levels of ambient carbon dioxide (CO2) concentrations (i.e. 2,000 - 5,000 ppm) (Rodeheffer et al., 2018).

[0007] In the state of the art, the chemicals used to purify the ambient airare sodalime (sodium hydroxide and calcium hydroxide) and are based on combining the acidic character of CO2 with these alkaline formulations and performing a neutralization reaction. Reactions are carried out in devices called 'scrubbers'. However, these chemicals have low vapor pressures and leak into the respiratory air. In low concentrations, they are irritating to the lungs, and in high concentrations, they have a suffocating effect by causing pulmonary oedema. Since air is a gas mixture, the CO2 content can also be separated by synthetic membranes made of polymers or ceramic materials such as polyamide or cellulose acetate (Jang et al., 2011 ; Kerry, 2007).

[0008] Again today, since the driving force in gas separation with membrane technology is the pressure difference between the inlet and the clean air outlet, the performance of the membrane used in this process depends on permeability and selectivity. Permeability is affected by the size of the gas molecule. The selectivity of a membrane is a measure of the permeability rate of the gases involved. It can be calculated as the permeability ratio of two gases in binary separation (Chong et al. 2016). Gas separation equipment based on membrane technology typically pumps gas into the membrane module, and the targeted gases are separated based on differences in diffusion and solubility. For example, in the case of a nitrogen (N2) I oxygen (02) mixture, if oxygen is to be separated from the ambient air, it will be collected on the upstream side, and nitrogen will be collected on the downstream side. As of 2016, it has been reported that 25% to 40% oxygen can be produced between 10 and 25 tons per day using membrane technology (Chong et al., 2016).

[0009] In the state of the art, the material of the membrane plays an important role in providing the desired performance characteristics. It is important to choose a membrane with high permeability and sufficient selectivity, as well as matching the membrane properties with the system operating conditions (pressure, temperature, gas composition). Synthetic membranes used for this purpose are made from a variety of polymers, including polyethylene, polyamides, polyimides, cellulose acetate, polysulfone, and polydimethylsiloxane (Isalski, 1989). Nanoporous membranes also exist whose dynamics differ from polymeric membranes. Silica membranes, on the other hand, are mesoporous and can be made to be highly homogeneous. The pore size of these membranes gives them very high permeability. Synthesized membranes have smooth surfaces and modifications can be made to the surface to greatly increase selectivity. Functionalization of silica membrane surfaces with amine-containing molecules (on surface silanol groups) enables the membranes to absorb CO2 more effectively (Jang et al., 2011 ). Surface functionalization (and hence chemistry) can be designed to be more effective for dry and wet gas flows (Chew et al., 2010). Also, ordered mesoporous silica membranes in the current technique are suitable for surface modification that facilitates CO2 separation. Surface functionalization with amines has been reported to significantly increase CO2 selectivity by leading to reversible carbamate formation (during CO2 flux) (Kim et al., 2015). Another option is CO2 capture using zeolite membranes and metal-organic frameworks. Zeolites are crystalline aluminosilicates with a regularly repeated structure of pores at the molecular level. Zeolite membranes selectively separate molecules based on pore size and polarity and can therefore be used in specific gas separation processes. The thin layers of the zeolite structure can act as selective permeators because they can adsorb CO2 within the pores. Due to their separation capacity based on both molecular size and adsorption affinity, zeolite membranes have been used to separate CO2 from N2, methane (CH4), and H2. At low temperatures, the adsorption capacity of zeolite is large, and the high concentration of adsorbed CO2 molecules blocks the flow of other gases. Therefore, at lower temperatures, CO2 selectively passes through the zeolite pores. Several recent research efforts have focused on developing novel zeolite membranes that maximize CO2 selectivity by exploiting the low-temperature inhibition phenomenon. Researchers have managed to separate CO2 / N2 and CO2 / CH4 mixtures at room temperature by reaching factors of 100 and 21 , respectively. Y-type (Si:AI>3) zeolite membranes, DDR type and SAPO-34 membranes have also shown promise in separating CO2 and CH4 at various pressures and feed compositions (Himeno et al., 2007; Kusakabe et al., 1997; Li et al. ., 2006).

[0010] In the state of the art, carbon dioxide separation from the gas mixture in zeolitic- imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs), has been achieved and extensive modelling studies have been conducted (Gurdal and Keskin, 2012; Keskin and Sholl, 2009). On the other hand, in many designs for CO2 removal, adsorbents containing monoethanolamine (MEA) are used and CO2-rich air is passed through a porous plate containing MEA. In this process, conditions for close contact are achieved and a foam is formed. The CO2-rich MEA is then extracted and reused after regeneration. This process is carried out in a reactor where MEA is heated under pressure and CO2 is released. MEA is currently used on nuclear submarines and ships. However, this process, which also includes heat treatment, is a very energyconsuming process (Dams et al., 1991 ; Wally Mazurek, 1998). Still in the present art, another design for cleaning CO2 from the interior of nuclear submarines includes a four-layer amine-containing resin bed, a process air fan, a steam generator for amine regeneration, a condensing heat exchanger and a CO2 compressor (Boynton and Colling Jr, 1983). This equipment has disadvantages such as taking up a lot of space and high energy consumption. Another solid phase amine plant based on zeolite material has been tested on one of the Swedish Navy's AlPs, showing promising results. Successful experiments were also conducted at the Defense and Civilian Institute of Environmental Medicine in Toronto (Seminar et al., 2012). However, the disadvantage of this design, which can also be considered as a molecular sieve for CO2, is that it requires intense energy during the regeneration phase (Chen et al., 2014; Waldemar Mazurek, 2005).

[0011] Apart from all these, methanolamine is a toxic chemical and the permissible exposure limit is 0.5 ppm. In addition, it has been reported to produce fugitive emissions. Macroporous ion exchange resins (Macroporous Ion Exchange Resin (Puralite MN500)) have been used to cope with problems based on MEA emission, but their high cost is perceived as a problem (W. Mazurek, 2015). Closed-loop designs using amine solutions for CO2 removal have been proposed by Martin Jensen. However, although this design does not emit MEA, it consumes high levels of pure water (W. Mazurek, 2015).

[0012] In the state of the art, the use of amine-immobilized hollow fiber membranes was envisaged in other designs by Hedley and Earwicker and later by Toft et al. Similarly, in these structures, which also contain mesoporous silica / polyethyleneimine-based CO2 absorbers, flow rates were found to be low and sufficient selectivity could not be achieved (W. Mazurek, 2015).

[0013] Disadvantages such as low CO2 retention, leakage and high cost have been reported in regenerative forms of ion exchange resins where nano and / or micro-porous structures are used (W. Mazurek, 2015). In the cryogenic CO2 removal system that works at -170 degrees suggested by French researchers, CO2 levels <0.5% (5.000 ppm) can be achieved by using molecular sieves for CO2. Cryogenic systems reduce dependence on consumables, manpower, and maintenance and are particularly important in nuclear-powered submarines with long missions (W. Mazurek, 2015). A recent study revealed that solubility is strongly related to one of three different liquid properties, and calculations were made with anion electrostatic potential (ESP) measurements (Liu and Turner, 2022). Kang et al. used the extreme learning machine (ELM) algorithm to calculate the solubility of H2S and CO2 in different liquids (Kang, Liu, et al., 2018; Kang, Qian, et al., 2018). In this case, formulations that chemically interact with CO2 through the cation or anion of the liquid gas holder should be preferred. These can be amino acid-bearing liquids (AAlLs), or modified liquids carrying one or more amine groups ( Sheshkovas et al., 2022 ). Both, experiments and simulation studies have shown that the solubility of CO2 is higher in liquids carrying imidazolium cation (Anthony et al., 2002; Cadena et al., 2004; Camper et al., 2008). There is a lot of diversity here and it is known that the length of the alkyl-side chain of the cation is effective on the solubility of CO2 in liquid. On the other hand, fluorine- containing side chains greatly increase CO2 retention but also cause an increase in viscosity. Some studies show that anion has a stronger effect on gas solubility than cation. The CO2 absorption properties of liquids prepared by modifying them with amino functional groups are not inferior to the traditional MEA solution. Bates et al. proposed to prepare targeted compounds starting from liquid containing an organic cation and a primary amine group (Bates et al., 2002). The designed functionalized compounds were exposed to CO2 for 3 h and a CO2 capture level of 0.5 mol CO2 / mol IL was achieved, which is equal to the MEA capture performance. By taking advantage of CO2 capture through interaction with amine groups, compounds containing multiple amine sites have been developed. Among them, amino acids are widely used in the preparation of gas absorbing liquids ( Sistla and Khanna, 2015 ).

[0014] Again, in the state of the art, ionic liquids prepared by introducing amine groups into the structure of anion and cation or by including superbases have shown higher performance in CO2 capture (Xu, 2017). There are also approaches to hybridize gas absorbers to porous materials such as molecular sieves, zeolites, and graphene oxide to increase CO2 capture performance. Additionally, metal-organic frameworks (MOFs) are also an option for CO2 capture.

[0015] Today, some researchers have reported that they brought the CO2 / N2 selectivity ratio to 129.03 with the composites they prepared by using gas absorbing liquids in polymers. In this study, smart membranes consisting of piezoelectric Polyvinylidene fluoride (PVDF) polymer and graphene with liquid phase were used. Butyl modified imidazolium -hexafluorophosphate (C8H15F6N2P) and -tetrafluoroborate structures were preferred (Widakdo et al., 2022). On the other hand, as smart silica-based CO2 adsorbents; There are also studies using the aminopropyl triethoxysilane derivatives, 3-aminopropyl triethoxysilane, (2-aminoethyl)-3-aminopropyl triethoxysilane, (3- trimethoxysilylpropyl)-diethylenetriamine, N-methylaminopropyl-trimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane and mesoporous multilayers, -lamellar silica structures, polyethyleneimine functionalized Core-shell 5A@mesoporous silica and silica-tetraethylenepentamine forms (lijima et al., 2018).

[0016] Here, according to the following reaction, 1 mole of amine can bind 1 mole of CO2 stoichiometrically in the presence of moisture. At the end of the reaction, bicarbonate anion is formed.

[0017] In a recent study by Lijima et al. it was explained that CO2 is captured by gas absorbing liquids and reduced by electrochemical reduction method, whereby CO2 is effectively captured and bonded through hydrogen bonding as it changes the charge distribution on the surface. By replacing the conventional gold (Au) electrode with gas absorbing liquids, Lijima et al. modified the electron transfer in the reduction reaction, reducing the overpotential and providing a new way to reduce the energy consumption of the reaction. In this design, the conversion of CC to formic acid increases the solubility of CO2 in solution, but also prevents the formation of competitive hydrogen (lijima et al., 2018).

[0018] There is a patent document no. EP4273130, which uses organic bases in the zwitterion structure, and a patent no. US11745147B2, which uses modified ionic liquids that are liquid at room temperature. In the aforementioned EP4273130, a zwitterion compound with a ring structure was used as a CO2 absorber, while in US11745147B2, polymerized 1 -ethyl 3-methyl imidazolium was attached to zeolite and used together with unpolymerized ionic liquid. The second patent covers compositions and methods for promoting the separation of gas mixtures, such as a mixture of carbon dioxide and methane. The composition of the invention is based on a curable polymerized ionic liquid that is liquid at room temperature. In the patent in question, the groups at the R1 and R4 positions in the imidazolium ring are selected from groups such as alkyl with an independent and optionally substituted carbon number ranging between C1 -C6, alkenyl with an optionally substituted carbon number ranging between C2-C6, alkynyl optionally between C2-C6, alkoxy optionally between C1 -C6, aminoalkyl optionally between C1 -C6, haloalkoxy optionally between C1-C6. Similarly haloalkyl with carbon number ranging from C1 -C6, preferably substituted aryl and preferably substituted heteroaryl; each occurrence of R2 and R3 was independently selected from groups consisting of hydrogen (H), preferably substituted alkyl with carbon number ranging from C1 -C6, preferably substituted C2-C6 alkenyl, preferably substituted C2-C6 alkynyl, preferably alkoxy with carbon number ranging from C1 -C6, preferably aminoalkyl with carbon number ranging from C1 -C6, preferably C1. Haloalkoxy with carbon numbers ranging from C1-C6 and optionally haloalkyl with carbon numbers ranging from C1 -C6, as the Y variable (anion), anions selected from one or more of Tf2 N-, BF4 - , N(CN)2 - , PF6- , C(CN)3 - , B(CN)4 were used. In some embodiments, the methods and systems utilize an ionic liquid incorporated into one or more electrochemical cells (US11298649B2).

[0019] Another present invention related to this subject generally relates to methods and systems for capturing a Lewis acid gas (e.g. CO2, SO2, borane compounds, etc.). In some embodiments, the methods and systems utilize an ionic liquid incorporated into one or more electrochemical cells (US11298649B2). In this patent, ionic liquid functionalized with ethylenediamine was used. Non-limiting examples of anions of functional ionic liquid include halide, sulfate, sulfonate, carbonate, bicarbonate, phosphate, nitrate, acetate, triflate, nonaflate, bis(triphlyl)am ide, trifluoroacetate, heptafluorobutanoate, haloalum inate. Or an anionic site of a cation exchange resin may comprise, triazolide, amino acid derivatives (e.g. proline deprotonated on nitrogen), tetrafluoride, phosphorus tetrafluoride, phosphorus hexafluoride, alkylsulfonate, fluoroalkylsulfonate, arylsulfonate, bis(alkylsulfonyl)amide, bis(fluoroalkylsulfonyl)amide, bis(arylsulfonyl)amide, (fluoroalkylsulfonyl) (fluoroalkylcarbonyl)amide, hydrogensulfate, alkyl sulfate, aryl sulfate, carboxylate, hydrogenphosphate, dihydrogen phosphate, hypochlorite.

[0020] Object of the Invention

[0021] In order to eliminate the disadvantages of the known state of the art, an object of the invention is to provide the preparation of air filters in which new generation gas absorbing chemicals with high carbon dioxide retention are used by attaching them to the solid phase containing nanotechnology as an alternative to both non-regenerative alkaline solutions such as NaOH, Ca(OH) and amines that can be used regeneratively.

[0022] Another object of the invention is to use the gas absorbing liquid or liquids containing functional groups or without functional groups but modified in terms of CO2 absorbing for a very different purpose than the quantitative analysis of CO2 and for the first time in the design of a regenerative and efficient CO2 absorbing device.

[0023] A further object of the invention is that the absorbers are capable of long-term (90 days) and repeatable purification of air with a volume of approximately (61 *6*6m3) and a CO2 concentration of up to 10,000 ppm in environments where the air flow rate is similar to submarine conditions.

[0024] Another object of the invention is that these liquids, also known for their gas-retaining properties, are structurally very diverse and have remarkable properties such as low vapor pressures, excellent chemical and thermal stability, potential recovery and reuse.

[0025] Another object of the invention is that gas absorbers can be described as salts, which are structurally formed by the binding of large volumes of organic cations with organic and / or inorganic anions by electrostatic interactions and which are liquid even at room temperature.

[0026] Another object of the invention is that gas absorbing liquids with adjustable physicochemical properties such as cation / anion pairing, viscosity and vapor pressure can easily replace conventional amine solvents in absorption.

[0027] Another object of the invention is not to prolong survival time, as would be expected in other strategic missions requiring prolonged underwater stays, in mines, escape capsules, space landers and emergency situations. It can also be used for life support in shelters that require long-term underground missions and in closed systems such as air or spacecraft.

[0028] Another object of the invention is to develop a system that can increase the time submarines can stay underwater without snorkeling up to ninety (90) days and is more advantageous to use than a system that generates power using carbon dioxide gas in the supercritical fluid phase. This proposed solution is only intended to support fuel cells and extend charging time and does not support indoor air quality. Extending the time under water provides a great operational advantage to the air-independently driven diesel-electric submarine in defensive missions. Because it becomes easier to detect a submarine that surfaces or snorkels above the water to get air.

[0029] Another object of the invention is to extend the invisibility period in submarines to ninety days or more with replaceable gas holder cartridges. It is necessary for submarines to come to the surface by snorkeling at certain intervals for two reasons, these are the need for diesel engines to charge the batteries and the need for ventilation for the interior. While standard diesel-electric submarines can stay underwater for 5-7 days without contact with air, air-independent diesel-electric submarines can stay underwater for approximately 21 days without contact with air. Because it becomes easier to detect a submarine that surfaces or snorkels above the water to get air. Extending the time under water provides a great operational advantage to the air- independently driven diesel-electric submarine in defensive missions.

[0030] Another object of the invention is to increase CO2 solubility and retention capacity by selectively using a gas-retaining liquid, liquid mixtures or chemicals having a high level of CO2 dissolving capacity modified by a synthetic approach.

[0031] Another object of the invention is to take the CO2 collected in the gas holder liquidbased material for regeneration as HCOs’ ion dissolved in water and convert it into carbonate after a second neutralization process.

[0032] In the light of the above explanations, this invention is related to the preparation of a new CO2 scavenging calipatron with higher CO2 retention than the existing technology.

[0033] Description of the Figures

[0034] Table 1 . Schematic structures of gas absorbing liquids according to cations and anions Table 2. Names and open structures of some gas absorbing chemicals in ion pair form

[0035] Figure 1 is the general view of the column envisaged for the CO2 capture and conversion process, which is the subject of the invention,

[0036] Figure 2 is the view of the ventilation system components in which the filter of the invention can operate efficiently. Description of the Reference Numbers

[0037] Detailed Description of the Invention

[0038] The invention relates to a design comprising filters (2) arranged in a column (1 ) in which the chemicals that can selectively absorb CO2 gas at maximum level and at the same time will not leak into the indoor air are supported by suitable porous forms and / or supportive polymeric membranes with expanded surface area (figure 1 ).

[0039] Figure 1 shows the general view of the column (1 ) foreseen for the CO2 capture and conversion process subject to the invention. According to the figure, the column (1 ) subject to the invention includes an inlet (13), an outlet (14), a 1 st section (11 ) and a 2nd section (12). CO2 absorbing filter (2) is positioned in the said sections (11 , 12).

[0040] Figure 2 shows the view of the ventilation system components where the filter (2) of the invention can operate efficiently. According to the figure, the column (1 ) with filters (2) in it is connected to a vacuum generator (3). The generator (3) in question is, on the other hand, connected to a compressor (4). Ambient air (A) is drawn through the compressor (4) and transferred to the vacuum generator (3). At the same time, air (B) containing CO2 is drawn into the column (1 ) with the vacuum created by the vacuum generator (3). The air (C) filtered in the column comes out of the vacuum generator (3). Without limitation, binary mixtures or ternary mixtures of at least one or two of the gas absorbing cation anion pairs shown in Table 1 have also been prepared by suitably combining a low molecular weight amino acid form.

[0041] In Table 1 , the schematic structures of gas absorbing chemicals that can be used for this purpose are shown according to their cations and anions. Hydrophilic or lipophilic properties also differ depending on the alkyl groups carried by the cation. Table 1. Schematic structures of gas absorbing liquids according to cations and anions

[0042] Although it is known that liquids with gas absorbing properties provide high levels of solubility for CO2, different levels of gas solubility (O2, NH3, CH4, H2S, SO2, Ar, H2, N2, CO2) have also been detected in different liquids. This situation requires careful screening regarding selective solubility in CO2 studies with gas absorbing liquids.

[0043] As a result of continuous monitoring and reducing the amount of CO2 gas in the submarine atmosphere, it is vital for the defence industry to deploy submarines for long periods without surfacing. Competitive efforts are continuing to extend the surfacing time in all classes except nuclear submarines and to ensure that the mental abilities and mobility of the personnel are at a high level in this process. Considering all these developments, the absorption rate and capacity of the design in question for carbon dioxide absorption should be high, vapor pressure should be low and regeneration should be easy. Other factors should be taken into consideration: the stability or degradation rate of the solvent used, whether it has a corrosive character, and the production cost.

[0044]

[0045] Table 2. Names and open structures of some gas absorbing chemicals in ion pair form

[0046] At least one of the structures shown in Table 2, without limitation, ethyl modified tetrafluoroborate salt and / or other alkyl modified hexafluorophosphate salts bearing an imidazolium ring with a second alkyl group bonded to it, or structures formed by mixing such gas absorbing liquids with tetrafluoroborate salts of alkali metals (LiBF4, NaBF4 and KBF4) at temperatures ranging from 20-50 °C were used in this design as CO2 absorbers.

[0047] In addition to these structures, it comprises an ion pair consisting of quaternary ammonium cation (R1 -R4, C=1 -16) and tertafluoroborate anion, which does not contain imidazolium ring but carries alkyl groups with different carbon number and / or an ion pair prepared with one of the anions shown in Table 1 without limitations against quaternary ammonium.

[0048] In this way, in strategic missions requiring longer underwater stays, escape pods, space backs and emergencies, the expected survival time will be extended or the visibility of the submarine will be reduced, while at the same time it will be possible for the personnel to make sound decisions. It can also be used for life support in shelters that require other long-term underground missions and in closed systems such as air or spacecraft.

[0049] On the other hand, the functional liquid or liquids in the present invention are physically or partially chemically attached to carbon derivatives such as micro- or nano-sized graphite, expanded-graphite and / or zeolitic structures or their forms prepared in certain proportions and arrangement, which exhibit a porous structure with a high surface area, and CO2 capture performance is improved.

[0050] The systems of the present invention comprise the placement of chemicals attached to a porous filter (2) medium in which CO2 gas made of different polymeric / metallic materials can easily diffuse, in layers of filter (2) in a column (1 ) made of Teflon and / or aluminum. The ultimate goal of the invention in question is to make the air rich in CO2 (20.000 ppm (2%)) contain CO2 below 2.000 ppm (<0.2% pCO2) by passing it through the air purifying filter (2), the outline of which is schematically shown in Figure 2.

[0051] The invention in question aims to provide sustainable clean air in a closed area (61 * 6 * 6 m3) where an average of 60 personnel work for 90 days, with the help of CO2 retaining filters (2). The invention in question requires that the filters (2) placed on the grids on the column (1 ) be regenerable, but since the regeneration process requires extra energy, this process must be done when the task is completed.

[0052] The invention in question envisages the intermittent usage period, which starts with the periodic activation of each column, to be 10 days (240 hours). The columns in question will be packaged in a way that they can be installed and removed, and when they become dirty, a new column (1 ) can be installed instead.

[0053] The invention relates, without limitation, to the use of certain cations based on imidazolium as shown in Table 1 and ion pairs consisting of anions as shown in Table 1 and some or all of the CO2-soluble gas absorbing liquids as shown in Table 2, either singly or in binary or ternary mixtures. Additionally, the ion pair prepared with a nitrogen in the quaternary ammonium form (R1-R4, C=1 -16), a halogen anion (F-, CI-, Br- or I- ) and / or one of the anions shown in Table 1 without limitation contains. The invention provides a cation, bearing an imidazolium ring with an alkyl modified (C4) and a second alkyl group attached (C1-C9) as a CO2 absorber liquid and, without limitation, one of tetrafluoroborate, sulfate, phosphate, hexafluorophosphate, nitrate, acetate or triflate salts. It involves the use of binary or ternary mixtures of one of the ion pairs shown in Table 2 with a liquid carrying an ethyl (C2) modified imidazolium ring and carrying one of the salts of tetrafluoroborate or sulfate, phosphate, hexafluorophosphate, nitrate, acetate or triflate with a second alkyl group attached.

[0054] The invention relates to structures formed by mixing a butyl-mod ified tetrafluoroborate salt bearing an imidazolium ring bonded to a second alkyl group and / or tetrafluoroborate salts of alkali metals (LiBF-4, NaBF4 and KBF4) at atmospheric pressure at temperatures ranging from 20-50 °C as a CO2 absorber liquid.

[0055] The invention relates to structures formed by mixing as CO2 absorber liquid an ethyl- modified tetrafluoroborate salt bearing an imidazolium ring bonded to a second alkyl group and / or other alkyl-modified (C1 -C10) hexafluorophosphate salts, or by mixing said gas absorber liquids with tetrafluoroborate salts of alkali metals (LiBF4, NaBF4 ve KBF4) at temperatures ranging from 20 to 50 °C.

[0056] The invention includes, in addition to other chemicals as CO2 absorbers, also small molecular weight double-ion (zwitterion) forms (C2H5NO2), at the level of 0.05 -5.0000 wt%. It also contains, in addition to these structures, a nitrogen in the form of quaternary ammonium (R1-R4, C=1 -16), which does not contain an imidazolium ring but carries four alkyl groups, and an ion pair prepared with tertafluoroborate, or without limitation, one of the anions shown in Table 1. Similarly, it contains nitrogen in quaternary ammonium form (R1 -R4, C=1 -16), a halogen anion (F, CI-, Br- or I-) and / or an ion pair prepared with one of the anions shown in Table 1 , without limitation.

[0057] The present invention relates to the coupling of single binary or ternary mixtures or chemically modified forms of the described gas absorbing liquids or amine modified gas absorbing liquids to nano-sized carbon derivatives and / or molecular sieves such as zeolite or similar molecular sieves by electrostatic interactions or hydrogen bonding.

[0058] The invention requires a pressure increase (2-3 bar) at the inlet (13) of the gas into the column, where the gases are confronted with chemically modified gas absorbing liquids in the reaction medium by the countercurrent principle. The present invention relates to the optimization of the design of the column (1 ) (column length, column diameter, column material selection) and the particle size of the filler, since the flow dynamics of the gases in the column (1 ) change when functional gas absorbing liquids are attached to the solid phase. It also requires flow rate with a pressure of 5-6 bar.

[0059] The invention relates to a vacuum generator (3) (pressure regulators and manometers) connected to the column outlet (14), operating at a flow rate of 175L / min (or 10 m3 / h), and further comprises engineering solutions for the purification of about 2,200 m3of air from CO2. If the clean air standard (approximately 60 people) x 30 m3air (1.800 m3) is considered, the air quality predicted here may even be above the clean air standard. In order to increase the retention rates of the material used in the column (1 ), the invention contemplates the attachment of functional groups of adsorbents and gasretaining liquid molecules to the support phase by adsorption, and / or covalent or ionic bonding or hydrogen bonding.

[0060] Regeneration strategies will be different if the invention uses gas absorbing liquids or super bases. This process may involve regeneration steps using physical and chemical methods such as heat treatment, chemical titration, neutralization, and sonification, and sometimes a combination of both.

[0061] References

[0062] Anthony, J. L., Maginn, E. J., Brennecke, J. F. 2002. "Solubilities and thermodynamic properties of gases in the ionic liquid 1 -n-butyl-3-methylimidazolium hexafluorophosphate". The Journal of Physical Chemistry B, 106(29), 7315-7320.

[0063] Atalay, S., Kili, A., Muhlis, A., Saridede, N., Kelimeler, A. 2015. "iyonik sivilarin hidrometalurjik uygulamalari", 30-36.

[0064] Aydogdu, S., Ertekin, K., Suslu, A., Ozdemir, M., Celik, E., Cocen, U. 2011. "Optical CO2 sensing with ionic liquid doped electrospun nanofibers". Journal of fluorescence, 21(2), 607-613.

[0065] Bates, E. D., Mayton, R. D., Ntai, I., Davis, J. H. 2002. "CO2 capture by a task-specific ionic liquid". Journal of the American Chemical Society, 124(6), 926-927.

[0066] Boynton, C. K., Colling Jr, A. K. 1983. "Solid Amine CO2Removal System for Submarine Application". SAE Transactions, 601-614.

[0067] Cadena, C., Anthony, J. L., Shah, J. K., Morrow, T. I., Brennecke, J. F., Maginn, E. J. 2004. "Why is CO2 so soluble in imidazolium-based ionic liquids?". Journal of the American Chemical Society, 126(16), 5300-5308.

[0068] Camper, D., Bara, J. E., Gin, D. L., Noble, R. D. 2008. "Room-temperature ionic liquid— amine solutions: tunable solvents for efficient and reversible capture of CO2". Industrial & Engineering Chemistry Research, 47(21 ), 8496-8498.

[0069] Celik, S., Ertekin, K., Gundogdu, C., Ergun, Y., Alp, S. 2012. "Dissolved carbon dioxide sensing with phenyl-linked carbazole oxazolones in ionic liquid and ethyl cellulose moieties". Spectroscopy Letters, 45(1 ), 74-83.

[0070] Chen, C., Kim, J., Ahn, W.-S. 2014. "CO2 capture by amine-functionalized nanoporous materials: A review". Korean Journal of Chemical Engineering, 37(11 ), 1919— 1934.

[0071] Chew, T.-L., Ahmad, A. L., Bhatia, S. 2010. "Ordered mesoporous silica (OMS) as an adsorbent and membrane for separation of carbon dioxide (CO2)". Advances in colloid and interface science, 153(1-2), 43-57. Chong, K. C., Lai, S. 0., Thiam, H. S., Teoh, H. C., Heng, S. L. 2016. "Recent progress of oxygen / nitrogen separation using membrane technology". J. Eng. Sci. Technol, 11 7), 1016-1030.

[0072] Coldur, M., Oguzlar, S., Ongun, M. Z., Oter, O., Yildirim, S. 2020. "Usage of thiocyanate-based ionic liquid as new optical sensor reagent: Absorption and emission based selective determination of Fe (III) ions". Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 224, 117385.

[0073] Dams, R. A. J., Leppard, C. J., Martin, T. W. 1991. "Air purification systems for submarines and their relevance to spacecraft". CJB Developments Limited, Airport Service Road, Portsmouth, UK.

[0074] Freeman, S. A., Dugas, R., Van Wagener, D. H., Nguyen, T., Rochelle, G. T. 2010. "Carbon dioxide capture with concentrated, aqueous piperazine". International Journal of Greenhouse Gas Control, 4(2), 119-124.

[0075] Gurdal, Y., Keskin, S. 2012. "Atomically detailed modeling of metal organic frameworks for adsorption, diffusion, and separation of noble gas mixtures". Industrial & engineering chemistry research, 57(21 ), 7373-7382.

[0076] "Denizaltilar Ve Tahrik Sistemleri-2: Havadan Bagimsiz Tahrikli Dizel-Elektrik Denizaltilar". https: / / mavivatan.net / denizaltilar-ve-tahrik-sistemleri-2-havadan- bagimsiz-tahrikli-dizel-elektrik-denizaltilar / sitesinden eri§im saglanmi§tir. Son eri§im tarihi: 29.08.2022

[0077] Himeno, S., Tomita, T., Suzuki, K., Nakayama, K., Yajima, K., Yoshida, S. 2007. "Synthesis and permeation properties of a DDR-type zeolite membrane for separation of CO2 / CH4 gaseous mixtures". Industrial & Engineering Chemistry Research, 46(21 ), 6989-6997.

[0078] Huang, X. 2022. "Experimental and simulation study on the capture and separation of CO2 / CH4 by alkali metal complex ionic liquid". Fuel, 329, 125444. lijima, G., Kitagawa, T., Katayama, A., Inomata, T., Yamaguchi, H., Suzuki, K., ... Masuda, H. 2018. "CO2 reduction promoted by imidazole supported on a phosphonium-type ionic-liquid-modified Au electrode at a low overpotential". ACS Catalysis, 8(3), 1990-2000. Isalski, W. H. 1989. "Separation of gases" (C. 5). Oxford University Press, USA.

[0079] Jang, K.-S., Kim, H.-J., Johnson, J. R., Kim, W., Koros, W. J., Jones, C. W., Nair, S. 2011. "Modified mesoporous silica gas separation membranes on polymeric hollow fibers". Chemistry of Materials, 23(12), 3025-3028.

[0080] Kang, X., Liu, C., Zeng, S., Zhao, Z., Qian, J., Zhao, Y. 2018. "Prediction of Henry’s law constant of CO2 in ionic liquids based on SEP and So-profile molecular descriptors". Journal of Molecular Liquids, 262, 139-147.

[0081] Kang, X., Qian, J., Deng, J., Latif, U., Zhao, Y. 2018. "Novel molecular descriptors for prediction of H2S solubility in ionic liquids". Journal of Molecular Liquids, 265, 756-764.

[0082] Kerry, F. G. 2007. "Industrial gas handbook: gas separation and purification". CRC press.

[0083] Keskin, S., Sholl, D. S. 2009. "Assessment of a metal- organic framework membrane for gas separations using atomically detailed calculations: CO2, CH4, N2, H2 mixtures in MOF-5". Industrial & Engineering Chemistry Research, 48(2), 914- 922.

[0084] Kim, H.-J., Chaikittisilp, W., Jang, K.-S., Didas, S. A., Johnson, J. R., Koros, W. J., ... Jones, C. W. 2015. "Aziridine-functionalized mesoporous silica membranes on polymeric hollow fibers: Synthesis and single-component CO2 and N2 permeation properties". Industrial & Engineering Chemistry Research, 54(16), 4407-4413.

[0085] Kumar, S., Srivastava, R., Koh, J. 2020. "Utilization of zeolites as CO2 capturing agents: Advances and future perspectives". Journal of CO2 Utilization, 41, 101251.

[0086] Kusakabe, K., Kuroda, T., Murata, A., Morooka, S. 1997. "Formation of a Y-type zeolite membrane on a porous a-alumina tube for gas separation". Industrial & engineering chemistry research, 36(3), 649-655.

[0087] Li, S., Falconer, J. L., Noble, R. D. 2006. "Improved SAPO-34 membranes for CO2 / CH4 separations". Advanced Materials, 78(19), 2601-2603. Liu, X., Turner, C. H. 2022. "Quantifying the anion effect of gas solubility within ionic liquids using the solvation affinity index". Chemical Engineering Science, 260, 117851.

[0088] Mazurek, W. 2015. "Key Developments in Submarine Air Monitoring and Air Purification". Submarine Air Monitoring and Air Purification, 1-37.

[0089] Mazurek, Waldemar. 2005. "Submarine atmospheres". Air quality in airplane cabins and similar enclosed spaces, 351-382.

[0090] Mazurek, Wally. 1998. "Current submarine atmosphere control technology". Life Support & Biosphere Science, 5(3), 279-285.

[0091] Ongun, M. Z., Oter, 0., Sabanci, G., Ertekin, K., Celik, E. 2013. "Enhanced stability of ruthenium complex in ionic liquid doped electrospun fibers". Sensors and Actuators B: Chemical, 183, 11-19.

[0092] OTER, O., AYDIN, M., Ertekin, K. 2016. "Suppression of interfering ions by using ionic liquid and micelle moieties in spectrofluorimetric analysis of manganese". Turkish Journal of Chemistry, 40(3), 373-384.

[0093] Oter, O., Aydogdu, S. 2011. "Determination of aluminum ion with morin in a medium comprised by ionic liquid-water mixtures". Journal of fluorescence, 27(1 ), 43-50.

[0094] Oter, O., Ertekin, K., Derinkuyu, S. 2009. "Photophysical and optical oxygen sensing properties of tris (bipyridine) ruthenium (II) in ionic liquid modified sol-gel matrix". Materials Chemistry and Physics, 113(1 ), 322-328.

[0095] Oter, 0., Ertekin, K., Topkaya, D., Alp, S. 2006a. "Emission-based optical carbon dioxide sensing with HPTS in green chemistry reagents: room-temperature ionic liquids". Analytical and bioanalytical chemistry, 386(5), 1225-1234.

[0096] Oter, 0., Ertekin, K., Topkaya, D., Alp, S. 2006b. "Room temperature ionic liquids as optical sensor matrix materials for gaseous and dissolved CO2". Sensors and Actuators B: Chemical, 117(1 ), 295-301.

[0097] Oter, 0., Sabanci, G., Ertekin, K. 2013. "Enhanced CO2 sensing with ionic liquid modified electrospun nanofibers: effect of ionic liquid type". Sensor Letters, 11(9), 1591-1599. Posner, S. 2004. "Survey and technical assessment of alternatives to decabromodiphenyl ether (decaBDE) in textile applications". Kern I PM, 5.

[0098] Rodeheffer, C. D., Chabal, S., Clarke, J. M., Fothergill, D. M. 2018. "Acute exposure to low-to-moderate carbon dioxide levels and submariner decision making". Aerospace Medicine and Human Performance, 89(6), 520-525.

[0099] Seminar, E., Air, I., Feb, Q., Architecture, E. 2012. "Indoor Air Quality in", (Ci), 8554.

[0100] Sheshkovas, A. Z., Veselovskaya, J. V, Rogov, V. A., Kozlov, D. V. 2022. "Thermochemical study of CO2 capture by mesoporous silica gel loaded with the amino acid ionic liquid 1 -ethyl-3-methylimidazolium glycinate". Microporous and Mesoporous Materials, 341, 112113.

[0101] Sistla, Y. S., Khanna, A. 2015. "CO2 absorption studies in amino acid-anion based ionic liquids". Chemical Engineering Journal, 273, 268-276.

[0102] Topal, Sevinc Z, Ertekin, K., Topkaya, D., Alp, S., Yenigul, B. 2008. "Emission based oxygen sensing approach with tris (2, 2'-bipyridyl) ruthenium (II) chloride in green chemistry reagents: room temperature ionic liquids". Microchimica Acta, 161(1 ), 209-216.

[0103] Topal, Sevinc Zehra, Ertekin, K., Gurek, A. G., Yenigul, B., Ahsen, V. 2011. "Tuning pH sensitivities of zinc phthalocyanines in ionic liquid modified matrices". Sensors and Actuators B: Chemical, 156(1 ), 236-244.

[0104] Widakdo, J., Huang, T.-J., Subrahmanya, T. M., Austria, H. F. M., Chou, H.-L., Hung, W.-S., ... Lai, J.-Y. 2022. "Bioinspired ionic liquid-graphene based smart membranes with electrical tunable channels for gas separation". Applied Materials Today, 27, 101441.

[0105] Xu, Y. 2017. "CO2 absorption behavior of azole-based protic ionic liquids: influence of the alkalinity and physicochemical properties". Journal of CO2 Utilization, 19, 1-8.

Claims

CLAIMS1. High-performance CO2 absorber calipatron, characterized as a CO2 absorber, as well as its ion pair formed by its tetrafluoroborate and or hexafluorophosphate with an imidazolium ring modified butyl and bonded to a second alkyl group, an imidazolium ring with an ethyl group and a second alkyl group attached and its tetrafluoroborate or hexafluorophosphate salt and / or other alkyl modified quaternary ammonium-hexafluorophosphate salts, or mixtures of two or three thereof.

2. CO2 absorber (calipatron) according to claim 1 , characterized in; said CO2 absorber comprises structures formed by mixing said chemicals with tetrafluoroborate salts of alkali metals (LiBF-4, NaBF4 and KBF4) at atmospheric pressure at temperatures ranging from 20-50 °C.

3. CO2 absorber according to claims 1 and 2, characterized in that; it comprises quaternary ammonium nitrogen (R1 -R4, C=1 -16) without imidazolium ring, and its ion pair prepared with tertafluoroborate, halide anions and / or one of the anions shown in Table 1 without limitation.

4. CO2 absorber according to claim 1 , characterized in that it comprises small molecular weight double-ion (zwitterion) forms ((C2H5NO2) as a CO2 absorber liquid.

5. CO2 absorber according to claim 1 , characterized in that; due to the layering of the components that make up the mixture, the design does not require limitations for the components by mass.

6. CO2 absorber according to claim 1 , characterized in that; the cations of some of the structures therein contain alkyl modified (C=1 -4) imidazolium derivatives.

7. CO2 absorber according to claim 1 , characterized in that; at least one of the gas absorbing liquids therein is water soluble.

8. CO2 absorber according to claim 1 , characterized in that; the water-soluble component or components therein range from 0.001 to 40.00% by mass.

9. CO2 absorber according to claim 1 , characterized in that it comprises, in addition to gas absorbing liquids, one of porous carbon derivatives such as graphene, carbon nanotubes, expanded graphite and / or at least one of a molecular sieve structure comprising at least one of [SiO4]4- and [AIO4]5- tetrahedrons in which aluminum central atoms are surrounded by oxygen atoms and at least one ofinterconnected tetrahedrons and reticulated structures containing voids and channels.

10. CO2 absorber according to claim 1 , characterized in that it does not contain any toxic CO2 absorber chemicals.11 . CO2 absorber according to claim 1 , characterized in that; it does not contain any CO2 absorber chemical in its structure which is irritating to the lungs and trachea.

12. CO2 absorber according to claim 1 , characterized in that; it has the potential to be regenerated.

13. CO2 absorber according to claim 1 , characterized in that; it can be used in submarine vehicles, as well as in other strategic missions requiring prolonged underwater immersion, in mines, in escape capsules, in emergency situations, in spacecraft and in all situations where breathing needs to be improved and air quality needs to be improved.

14. High-performance CO2 absorber according to claims 1 -13, characterized in that; it comprises an inlet (13), an outlet (14) and a column (1 ) for a CO2 capture and conversion process comprising sections (11 , 12), a CO2 absorbing filter (2) positioned in the chambers (11 , 12).

15. CO2 absorber according to claim 14, characterized in that; it comprises a 1 st section (11 ) and a 2nd section (12).

16. Ventilation system comprising a CO2 absorber as claimed in claim 1 -15, characterized by comprising the following; column (1 ) with filters (2) positioned inside, a vacuum generator (3) connected to said column (1 ) and providing vacuum to the column (1 ) to draw in air (B) containing CO2, from which filtered air (C) is removed, a compressor (4) for drawing ambient air (A), connected on the other side to the said generator (3).

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