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    • 专利摘要:
    Process for carrying out gas scrubbing by means of an electrolytic solution as scrubbing liquid which is brought into contact with a gas (1) to be cleaned in at least one gas scrubber (2) and discharged from the gas scrubber (2) after scrubbing with gas, the scrubbed electrolyte solution successively following b) Electrochemical conversion of the electrolytic solution in a conversion device (5), so that in the course of gas scrubbing absorbed by the electrolyte solution organic compounds degraded at least with the formation of carbon dioxide, water vapor and hydrogen and the c) recovering a regenerated electrolyte solution in a device (8) for deionization and desorption of ions, wherein the supplied electrolyte solution is passed through a cell with several pairs of DC or DC Direct current source connected to three-dimensional electrodes, wherein the cations of the electrolytic solution are adsorbed on the electrodes serving as cathodes, wherein by reversing the cation-loaded three-dimensional electrodes, each with an auxiliary electrode, the cations subsequently desorbed from the or the electrode (s) and with hydroxide Ions are converted to the regenerated electrolyte solution, d) recycling the regenerated electrolyte solution to the gas scrubber (2).
    公开号:AT519109A4
    申请号:T51163/2016
    申请日:2016-12-20
    公开日:2018-04-15
    发明作者:
    申请人:Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg；
    IPC主号:
    专利说明:

    per aqua diamond electrodes production GmbH & Co KG Description
    Process for carrying out gas scrubbing by means of an electrolyte solution
    The invention relates to a method for carrying out gas scrubbing by means of an electrolyte solution as a scrubbing liquid.
    It is known and customary to use gas scrubbers for the purification of gases or gas mixtures, in particular for the purification of exhaust gases. In gas scrubbers, the gas or gas mixture is brought into contact with an electrolyte solution in order to absorb such solid, liquid or gaseous constituents of the gas or gas mixture into the scrubbing liquid. For example, by means of gas scrubber suspended in smoke solid particles or suspended in gases liquid particles are separated. For example, the use of scrubbers for absorbing sulfur dioxide contained in the flue gas is also known.
    From EP 2 407 230 A1 a process for sorption drying is known. The material to be dried is subjected to a heat treatment by heat conduction and / or by a gaseous heat transfer medium and / or by thermal radiation. The water-saturated air is passed through a sorbent of an aqueous alkali salt solution which is a potassium hydroxide solution and / or potassium carbonate solution. By spraying or misting the interface between the water vapor and the alkali salt solution is kept large in area. The process is used for drying and / or mass separation. The water vapor pressure lowering effect of a potassium salt solution as well as the selective chemisorption for the coupled material and energy transport is used.
    So far, it has not been possible to recover the after the washing process with impurities, pollutants and the like loaded electrolyte solution in a suitable manner for a new washing process in the gas scrubber. The electrolyte solutions containing chemicals must therefore be disposed of properly after the washing process and thus usually consuming.
    The invention is therefore based on the object to enable a continuous regeneration of the electrolyte solution in a method of the type mentioned, so that the regenerated electrolyte solution can be used for gas scrubbing.
    According to the invention, this object is achieved in that the loaded electrolyte solution is continuously regenerated according to the following successive regeneration steps: a) hydrolyzing the loaded electrolyte solution, b) electrochemical conversion of the electrolyte solution in a conversion device so that at least organic compounds taken up by the electrolyte solution during gas scrubbing c) recovering a regenerated electrolyte solution in an ion deionization and desorption apparatus, wherein the supplied electrolyte solution is passed through a cell having a plurality of pairs of DC or DC Direct current source connected to three-dimensional electrodes is passed, wherein the cations of the electrolytic solution are adsorbed on the electrodes serving as cathodes, wherein by reversing the polarity with K ions are subsequently desorbed from the electrodes and reacted with hydroxide ions to form the regenerated electrolyte solution, d) recycling the regenerated electrolyte solution to the gas scrubber.
    The erfmdungsgemäße method is advantageously suitable both for aqueous basic electrolyte solutions and for aqueous acidic electrolyte solutions and aims in particular on the removal of organic contaminants and on the removal of carbon dioxide from gases or gas mixtures from. Due to the special and continuous regeneration of the electrolyte solution, the consumption of
    Chemicals are particularly low. Waste materials are almost non-existent. In particular, the method according to the invention makes it possible to recover valuable substances from the electrolyte solution in the course of regeneration, in particular from the organic impurities removed from the gases in the course of gas scrubbing.
    In order to minimize the growth of germs, it is advantageous if the electrolytic solution used for gas scrubbing is a basic electrolyte solution which preferably has a pH of at least 12.0, preferably> 13. The high pH also prevents carbon dioxide taken up by the electrolyte solution from reacting with the electrolyte solution to form a sparingly soluble bicarbonate which could precipitate in the electrolyte solution and interfere with regeneration.
    According to a preferred embodiment, the electrolytic solution used for gas scrubbing is a potassium carbonate solution or a potassium hydroxide solution. These advantageously have a particularly high adsorption capacity for carbon dioxide, so that carbon dioxide is removed in the course of gas scrubbing particularly effectively from the gas to be purified. In particular, the electrolytic solution used for gas scrubbing contains potassium carbonate and potassium hydroxide.
    In a preferred embodiment, the electrolyte solution is electrostatically charged when introduced into the gas scrubber, in particular by Leitungsionisation- or Koraonaionisation and deposited on arranged in the gas scrubber deposition electrodes and then derived for subsequent regeneration. As a result, in particular Raumlauft is particularly effective, in particular substantially completely separated from the Elektrolylösung. This is particularly advantageous in combination with another preferred embodiment according to which the gas is exposed to UV radiation, in particular UV radiation having a wavelength <200 nm, preferably a wavelength of 185 nm, before or after the gas scrubbing in the gas scrubber , As a result of the high-energy UV radiation, poorly adsorbable organic compounds are split by photolysis into environmentally compatible constituents, in particular in the electrolytic solution. The deposition of the electrolyte solution on separation electrodes ensures optimal and trouble-free treatment of the gas, in particular of air, with UV-steel. Due to the UV irradiation, OH radicals, singlet oxygen and ozone are formed from water and oxygen contained in the gas, which react with the molecules of the organic compounds present in the ambient air or in the gas and oxidize these completely or partially. In particular, any hydrocarbons still present in the gas or other gases or vapors which are not removable in the basic wash and which are usually only slightly absorbable by the electrolyte solution during gas scrubbing can be degraded to water and carbon dioxide or to compounds which can be separated off by basic scrubbing. These can be removed from the gas in a particularly effective manner by a second basic wash.
    According to a preferred embodiment, the gas, in particular Raumlauft, is cooled or heated during the gas scrubbing by means of the electrolyte solution. It is advantageous if the regenerated electrolyte solution is cooled or heated before the gas scrubbing via heating / cooling devices and / or via at least one heat exchanger. Preferably, the regenerated electrolyte solution is cooled before gas scrubbing via a Peltier element cascade, by means of a refrigerator or by adiabatic cooling, in particular by evaporation of water of the electrolyte solution. For heating, the electrolytic solution is preferably heated by burning fuel oil or natural gas or by means of a heat pump, a heat accumulator, photovoltaic or Peltier elements. Therefore, as needed, the regenerated electrolytic solution can be supplied with heat from an external source, or heat can be dissipated from the regenerated electrolytic solution via a heat exchanger.
    According to a further preferred embodiment, the humidity of the gas to be purified, especially if this is room air, adjusted by changing the ion concentration of the electrolyte solution. During gas scrubbing, a certain equilibrium arises between the electrolyte solution sprayed into the gas scrubber and the room air introduced into the gas scrubber, since liquids, here the electrolyte solution, depending on the ion concentration, always in equilibrium with the moisture (gas moisture) of the room air are located. This equilibrium causes a defined in the electrolyte solution
    Ion concentration and in the room air sets a defined humidity. The higher the ion concentration of the sprayed electrolyte solution, the lower the humidity of the purified air leaving the scrubber. The lower the ion concentration of the sprayed electrolyte solution, the higher the humidity of the purified air leaving the scrubber. The adjustment of the ion concentration takes place after the regeneration of the electrolyte solution.
    In order that all of the impurities absorbed by the electrolytic solution in the gas scrubbing dissolve completely in the electrolytic solution, it is advantageous if the electrolytic solution for hydrolyzing is heated in accordance with regeneration step a). This ensures that all impurities derived from impurities of the subsequent treatment in accordance with the regeneration steps b) and c) are accessible.
    In order to prevent any interference by solid particles in the regeneration steps b) and c), it is provided according to a preferred embodiment that from the electrolyte solution after hydrolyzing according to regeneration step a) by means of a mechanical separation device in the electrolyte solution undissolved inorganic substances, which from the Electrolyte solution were added to the gas scrubber, are deposited.
    According to a preferred embodiment, the electrolytic solution in the electrochemical conversion according to regeneration step b) in particular in at least one einkammrigen designed as a flow cell electrolytic cell having an electrode package of at least two connected to a voltage source contact electrodes, continuously in and discharged, wherein it flows through the electrode package.
    According to a further preferred embodiment, the electrochemical conversion according to regeneration step b) the residence time of the electrolyte solution in the electrolytic cell, the temperature of the electrolyte solution, the pH of the electrolyte solution, the ion concentration of the electrolyte solution and the current and the voltage of the
    Voltage source set as process parameter. The electrochemical conversion can therefore be controlled or adjusted as desired by simply adapting the mentioned process parameters.
    According to a further preferred embodiment, the electrolyte solution is passed immediately after the electrochemical conversion according to regeneration step b) in an electrochemical cell, in which from the electrolyte solution originating water is split into hydrogen and oxygen, wherein the oxygen, as needed, the regenerated electrolyte solution or directly the gas purified by the gas scrubber and the hydrogen being discharged. Thus, the oxygen content of the purified air can be easily adjusted.
    According to a further preferred embodiment, the electrolyte solution is passed immediately before recovery according to regeneration step c) in a degasser, in which the electrolyte solution is supplied to phosphoric acid until the pH of the electrolyte solution is <5. As a result, the carbonates and bicarbonates formed during gas scrubbing or electrochemical oxidation are converted into corresponding phosphates ("displacement reaction"), carbon dioxide and water also being formed. The position of the equilibrium of the individual species of the phosphates is dependent on the pH value - according to a Haegg diagram known to those skilled in the art. Phosphoric acid is added in an amount such that the pH of the electrolyte solution is reduced to less than or equal to 5, with carbonates and bicarbonates present substantially completely decomposing to form carbon dioxide. The carbon dioxide is discharged from the room into the environment or prepared according to a correspondingly intended further utilization.
    Advantageously, according to a further preferred embodiment variant, the phosphoric acid is recovered in the regeneration step c) and returned to the degasser. In particular, the phosphate anions are adsorbed in the regeneration step c) to the three-dimensional electrodes serving as anodes, wherein the phosphate anions are subsequently desorbed from the electrodes by Umpolung the loaded with phosphate anions three-dimensional electrodes each with an auxiliary electrode and reacted with oxonium ions to phosphoric acid , which is drained and returned to the degasser.
    It is also advantageous if, in the regeneration step c), the deionized solution is discharged after the capacitive deionization. It is preferable to add wash solution (electrolyte solution) before desorption in order to increase the enrichment effect. Water is added especially when the solubility limit is exceeded or when the capacitively enriched anions are to be discarded.
    Preferably, the drained deionized solution is stored in a surge tank. If necessary, the regenerated electrolyte solution can be diluted with this.
    According to a preferred embodiment, in the regeneration step c) the auxiliary electrodes are three-dimensional electrodes and the desorption of the ions is carried out at a DC voltage below the decomposition voltage of the solution in the cell.
    Furthermore, it is advantageous that in Regeneratonsschritt c) the hydroxide ions during the desorption of the anions, in particular the phosphate anions, are enriched in the auxiliary electrodes.
    To reduce the ion concentration of the regenerated electrolyte solution, it is advantageous if water is added to the regenerated electrolyte solution before gas scrubbing.
    Contains the gas to be unified both acidic and basic impurities, such as is the case with stall air, it is advantageous for purifying the air, if this in a first gas scrubber with a basic electrolyte solution and then in a second gas scrubber with an acidic electrolyte solution is brought into contact, wherein the loaded electrolyte solutions are regenerated continuously in each case according to the consecutive regeneration steps a) to c). Contains the gas to be purified large amounts of organic acids, as is the case in particular with biogas, it is advantageous if regeneration step b) is carried out in two stages in a two-part conversion device. In this context, it is also advantageous if, in the second stage, the electrolyte solution is subjected to total oxidation in an electrolytic cell which contains diamond particles.
    The invention further relates to a device for carrying out gas scrubbing by means of an electrolyte solution as scrubbing liquid with a gas scrubber, a conversion device for decomposing absorbed by the electrolyte solution in the gas scrubber organic compounds, wherein the conversion device has a flow cell designed as an electrolysis cell, a device for deionization and desorption for forming a regenerated electrolytic solution, said apparatus being arranged downstream of the converting device and having a plurality of pairs of three-dimensional electrodes connected to a DC or DC source for adsorbing ions from the electrolytic solution and for each pair of three-dimensional electrodes each having an auxiliary electrode for separately reversing with the three-dimensional electrodes and a recycle for returning the regenerated electrolyte solution to the scrubber.
    This device allowed gas scrubbing with a continuous regeneration of the scrubbing liquid (electrolyte solution) including recycling of the regenerated electrolyte solution. The need for chemicals is therefore particularly low. From the adsorbed substances advantageous recyclables can be obtained.
    For heating or cooling of the gas to be washed, it is advantageous if the device has a heat exchanger, via which the electrolyte solution derived from the gas scrubber is feasible in countercurrent to the regenerated electrolyte solution. Further, the apparatus may include a heating / cooling device for heating or cooling the regenerated electrolyte solution.
    Particularly preferably, the device according to the invention is an air conditioner. In contrast to conventional air conditioning systems with heat exchangers, on whose solid surfaces the water vapor contained in the room air condenses out, so that these surfaces are kept constantly moist, the water adsorbed from the room air in the electrolytic solution is rapidly removed during cooling by means of gas scrubbers.
    If solids-containing gases are cleaned, it is advantageous if a mechanical separation device is provided between the scrubber and the conversion device for separating inorganic contaminants which are not soluble in the electrolyte solution.
    According to a preferred embodiment, an electrochemical cell for generating oxygen and hydrogen is provided immediately after the conversion device. The generated oxygen may be supplied to the regenerated electrolyte solution to increase the oxygen content of the gas scrubbed therewith, for example, room air.
    According to a further preferred embodiment, the device for deionization and desorption is preceded by a degasser. By means of this carbon dioxide can be expelled from carbonate-containing electrolyte solutions, which is for a proper execution of the deionization and the desorption of advantage.
    Further features, advantages and details of the invention will now be described in more detail by means of embodiments of the invention and with reference to the single figure, Fig.l, which shows a highly simplified schematic flow diagram.
    Example 1 - Dehumidify. Tempering and cleaning room air
    Room air is continuously subject to a certain input of impurities and / or pollutants. These include, for example, exhaled by humans carbon dioxide (about 800g per person per day) or any derived from furniture or floors volatile organic compounds - so-called "VOCs", (volatile organic compounds) - such as solvent vapors. Especially in the
    Room air accumulating carbon dioxide significantly affects the quality of the indoor air. Increasing the carbon dioxide concentrations over a longer period of time over 1500 ppm, this has the known physiological effects such as respiratory depression, headache or dizziness. Each person loses about 1kg of water per day in the form of sweat, which is entered as "polluted" water vapor in the room air. In the room air also dust collects, consisting of different particles, such as soot particles, plastic particles, dead skin, bacteria, mold spores, fine hair or lint from garments. Especially in industrial production buildings, the room air is subject to a particularly high level of entry of such impurities, so that it is expedient in such buildings to purify the room air continuously.
    Fig. 1 shows a schematic flow diagram of an inventive air conditioning, whose operation will be explained below. 1st step - gas scrubbing
    As indicated in Fig. 1, the room air to be treated 1 is introduced into a scrubber 2, in particular sucked by this. The scrubber 2 is supplied continuously with a basic electrolyte solution serving as a scrubbing liquid, which, as also indicated in FIG. 1, is sprayed into the scrubber 2 and thus forms droplets in this finely distributed manner. In particular, the electrolytic solution is a potassium carbonate or a potassium hydroxide solution ("potassium hydroxide") having a pH of at least 12, preferably a pH> 13. However, the electrolytic solution may also contain potassium carbonate (K 2 CO 3) together with potassium hydroxide (KOH). The high pH of the electrolyte solution is advantageous because it suppresses the growth of germs in the air conditioner. During the gas scrubbing, any impurities present in the room air 1 are adsorbed on the surface of the sprayed electrolytic solution (chemisorption), so that the room air 1 is cleaned. For example, dust particles contained in the room air 1, gaseous organic compounds, in particular VOCs or acid gases, such as, for example, hydrogen sulfide, are adsorbed by the electrolyte solution. In particular, carbon dioxide contained in the room air 1 is chemically bound to potassium hydroxide of the electrolytic solution. Carbon dioxide first reacts to form potassium carbonate (Equation I) and then further to potassium hydrogen carbonate (Equation II):
    KOH + CO2 -> K2CO3 + H2O Equation I
    K2CO3 + CO2 5 = * KHCO3 Equation II
    If potassium hydrogen carbonate is formed during gas scrubbing, this could in principle undesirably precipitate when its saturation concentration is exceeded. Due to the high pH of the electrolyte solution, the equilibrium of equation II is advantageously on the side of the potassium carbonate. This, as well as any existing potassium bicarbonate is, as will be explained, removed at a later date from the electrolyte solution.
    Preferably, the electrolyte solution is electrostatically charged during the spraying, for example by means of a high voltage source via a line ionization or by corona ionization. The finely distributed electrolyzed electrolyte solution loaded with impurities is deposited on the scrubber 2, in particular lamellar Ab separating electrodes (not shown in FIG. 1) and subsequently discharged. The distance between the lamellar Ab separating electrodes is in the millimeter range and is in particular up to 10.0 mm. By electrostatic charging and subsequent deposition of the electrolyte solution to Ab separating electrodes, the electrolyte solution is substantially completely separated from the purified room air 1, which is for the below optionally provided UV irradiation of the room air 1 is advantageous.
    According to this optional embodiment, room air discharged from the scrubber 2 is exposed to UV steels with a wavelength <200 nm, in particular with a wavelength of approximately 185 nm. Due to the high-energy UV radiation, especially in the electrolyte solution poorly sorbable organic compounds are completely or partially oxidized by photolysis. In conjunction with the in the
    Room air 1 contained molecular oxygen (O2) and water vapor generate UV rays highly reactive OH radicals and singlet oxygen and ozone. The formed oxidizing agents, especially the radicals, react with and oxidize the molecules of the organic compounds (e.g., methane) contained in the room air 1. For example, methane breaks down into water and carbon dioxide. Any larger organic molecules contained in the room air 1 are partially oxidized, in particular carboxyl or hydroxyl groups being incorporated into the molecules or molecular fragments, and thus in particular carboxylic acids, aldehydes, ketones and alcohols being formed. For example, formaldehyde derived from paints, adhesives or glue (wood furniture) could be oxidized to the corresponding carboxylic acid. In particular, CH-acidic organic compounds are formed by the partial oxidation, for example carboxylic acids, aldehydes, ketones or alcohols. These are accessible to chemisorption, so that in this case a UV oxidation downstream basic gas scrubbing is particularly advantageous. UV irradiation of the room air 1 is therefore a particularly advantageous supplement to gas scrubbing. The UV irradiation can be carried out between two or more basic gas scrubbing.
    The room air 1 is cooled or heated during the gas scrubbing. For this purpose, a suitably tempered electrolyte solution is sprayed into the scrubber 1, for cooling a cooled electrolyte solution, for heating a heated electrolyte solution. The heating or cooling of the electrolyte solution takes place during its return to the scrubber 2 after regeneration, preferably via heating / cooling devices 10, 11, in particular via at least one heat exchanger 3. Cooling of the electrolyte solution takes place in particular via a Peltier element cascade. Alternatively, the cooling of the electrolyte solution takes place, for example, by means of a chiller or an adiabatic cooling, in particular by an evaporation of water from the electrolyte solution. The energy required to heat the electrolyte solution is provided, for example, by combustion of fuel oil or natural gas, by means of a heat pump, a heat storage, photovoltaic or Peltier elements.
    The moisture of the cleaned room air 1 emerging from the scrubber 2 can be adjusted via the ion concentration of the electrolyte solution. During gas scrubbing, a certain equilibrium arises between the electrolyte solution sprayed into the gas scrubber and the room air 1 introduced into scrubber 2, since liquids, here the electrolyte solution, always in equilibrium with the moisture (gas moisture), depending on the ion concentration the room air 1 are located. This equilibrium leads in the concrete application example to the fact that in the electrolyte solution a defined ion concentration and in the room air 1 a defined humidity, so a certain proportion of water vapor adjusts. The higher the ion concentration of the sprayed electrolytic solution, the lower the humidity of the purified air leaving the scrubber 2 room air 1. The lower the ion concentration of the sprayed electrolyte solution is, the higher is the humidity of the cleaned from the scrubber 2 exiting room air 1. The setting The ion concentration occurs after the regeneration of the electrolyte solution, as will be described below.
    In contrast to conventional air conditioning systems with heat exchangers, on whose solid surfaces the water vapor contained in the room air condenses out, so that these surfaces are kept constantly moist, during dehumidifying by means of gas scrubber 1, the water vapor adsorbed from the room air in the electrolyte solution is rapidly transported away. As already mentioned, the high pH value of the electrolyte solution advantageously suppresses the growth of germs. At the mentioned pH value of at least 12, the washing solution is essentially sterile, so that the inventive air conditioning system is kept essentially germ-free.
    The electrolyte solution containing the impurities and derived from the gas scrubber 2 is, as will be described below, regenerated over several regeneration steps and then reintroduced into the scrubber 2 as scrubbing liquid. 2nd step - regeneration of the loaded electrolyte solution
    The electrolyte solution derived from the scrubber 2 is passed over the heat exchanger 3 and cools or heats, as mentioned above, the already regenerated scrubbing solution (electrolyte solution) in its return to scrubber 1. In the derived electrolyte solution sorbed organic compounds, optionally with supply of Heat, completely or substantially completely dissolved in the electrolyte solution. When organic acids have been adsorbed by the electrolyte solution, they dissociate, neutralizing the acids or the ions formed by the dissociation of the acids to form water-soluble salts which are dissolved directly in the electrolyte solution.
    For regeneration, the electrolyte solution is passed in an optional first regeneration step in a mechanical separator 4, in which any adsorbed from the indoor air 1 insoluble inorganic impurities, such as sand are separated from the electrolyte solution. The mechanical separation takes place for example by means of filtration, sedimentation, flotation or centrifugation.
    The electrolyte solution derived from the gas scrubber 2 is passed, if appropriate after carrying out the mentioned mechanical separation process, into a conversion device 5, in which the second regeneration step takes place. The conversion device 5 is constructed, for example, according to the not yet published Austrian patent application A50387 / 2016 and works according to the method described there for electrochemical conversion. In this second regeneration step, the electrolyte solution, in particular in at least one single-cell electrolysis cell designed as a flow cell, which has an electrode package comprising at least two contact electrodes connected to a voltage source, is continuously fed in and out, through which the electrode packet flows. The process parameters (residence time of the electrolytic solution in the electrolytic cell, the temperature of the electrolytic solution, the pH of the electrolytic solution, the ion concentration of the electrolytic solution, the current and voltage of the voltage source) are adjusted so that organic compounds are decomposed in the electrolytic solution, wherein the anode carbon dioxide and water and hydrogen are formed at the cathode. These resulting gases, which are formed only in small quantities, can be safely diverted from the building into the environment. A substantial portion of the carbon dioxide formed is sorbed by the electrolyte solution. In the
    Electrolyte solution remain in particular potassium hydroxide, potassium carbonate and Kaliumhy drogencarb onat.
    In the course of the third regeneration step, which is also optional, the electrolyte solution thus obtained is passed into an electrochemical cell 6, in which water is split and thus hydrogen (Eh) and oxygen (O2) is generated. The hydrogen is discharged into the environment (to the outside), the oxygen is introduced, as needed, in the already regenerated wash solution, so as to increase the oxygen content of the air to be cleaned 1 in the course of gas scrubbing. Alternatively, the oxygen can be fed directly to the room air via a separate line. The electrolytic solution emerging from the electrochemical cell 6 further contains, in particular, potassium hydroxide, potassium carbonate and potassium bicarbonate.
    In the course of the fourth regeneration step, the electrolyte solution is passed into a degasser 7, in which the electrolyte solution is brought into contact with a phosphoric acid (H3PO4) introduced into the degasser 7. As a result, the carbonates and bicarbonates formed during gas scrubbing are converted into corresponding phosphates ("displacement reaction"), carbon dioxide and water also being formed. The position of the equilibrium of the individual species of the phosphates is dependent on the pH value - according to a Haegg diagram known to those skilled in the art. So much phosphoric acid is added that the pH of the electrolytic solution is lowered to less than or equal to 5, with carbonates and bicarbonates present decaying substantially completely under the formation of carbon dioxide. The carbon dioxide is discharged from the room into the environment or prepared according to a further intended further utilization.
    Phosphoric acid and pure potassium hydroxide solution are recovered separately from each other in the next regeneration step (fifth regeneration step) from the thus obtained electrolyte solution by means of capacitive deionization and subsequent desorption in a cell 8. The previously described conversion of the carbonates and bicarbonates into the corresponding phosphates in the course of the fourth
    Regeneration step is advantageous because otherwise occur in the capacitive deionization large amounts of carbon dioxide, which would disturb them.
    This fifth regeneration step is carried out in particular according to one of the methods described in the not yet published Austrian patent application A51103 / 2016. For example, according to the following method disclosed in this patent application, the pure KOH solution and the phosphoric acid are produced. The electrolyte solution is passed in a closed circuit through a cell having an inlet and an outlet, which contains at least one pair, in particular several pairs, of three-dimensional electrodes respectively connected to a DC or DC source, until the solution is capacitively deionized, Therefore, until the potassium cations (K + ions) are adsorbed on the electrodes serving as cathodes and phosphate anions are adsorbed on the electrodes serving as anodes. The remaining aqueous solution is drained and may optionally be stored in a surge tank 9. The cell is then filled with clean deionized water. The K + -enriched three-dimensional electrodes are separated from the voltage source. The second, enriched with phosphate anions three-dimensional electrodes are reversed, each with an auxiliary electrode, all auxiliary electrodes are also three-dimensional electrodes. Inlet and outlet are closed. At a DC voltage below the decomposition voltage of water, the phosphate anions desorb from the three-dimensional electrodes, OH ions are enriched in the auxiliary electrodes. H30 + ions formed in the solution react with the phosphate anions to form phosphoric acid. The phosphoric acid is discharged and returned to the degasser 7.
    The emptied cell is now filled with clean deionized water or with "fresh" wash solution (electrolyte solution). The three-dimensional electrodes enriched with the K + ions are respectively connected to the positive pole and the three-dimensional auxiliary electrodes enriched with OH'-ions are connected to the negative pole of the DC voltage source. Therefore, at a voltage below the decomposition voltage, the K + ions desorb from the electrodes, the OH 'ions from the auxiliary electrodes. In the cell potassium hydroxide (KOH) is formed. The potassium hydroxide solution is discharged from the cell. By supplying water from the Ausgleichsgemäß 9, the potassium hydroxide solution can be diluted if necessary. The potassium hydroxide solution is passed over the at least one heat exchanger 3 and optionally via heating / cooling devices 10, 11 and heated or cooled in this way - depending on whether the room air 1 is to be cooled or heated.
    Example 2 - Cleaning of house air and carbon dioxide utilization
    Stable air from poultry houses is heavily contaminated with ammonia, amines, carbon dioxide and organic dusts originating from feed and feathers.
    To clean the stall air, it is introduced in a manner analogous to Example 1 in a scrubber and "washed" there with a basic electrolyte solution, in particular a potassium hydroxide solution. The basic electrolyte solution absorbs organic acids, thiols, carbon dioxide and any germs from the stable air. The regeneration of the basic electrolyte solution in the first regeneration step, the hydrolysis, requires the supply of heat in order to dissolve any solid particles suspended in it, for example from feed residues, feathers, hay, etc., so that the organic compounds contained in the solid particles become accessible for treatment , The further regeneration is carried out analogously to Example 1 in the form of the regeneration steps described therein (electrochemical conversion in a conversion device 5, introduction into a degasser 7 and contact and conversion of the carbonates and bicarbonates into phosphates, with phosphoric acid, capacitive deionization with subsequent desorption and recovery of the wash solution ). Optionally, the optional regeneration steps described in Example 1 (separation of inorganic constituents in a mechanical separation device 4, water splitting in an electrochemical cell 6) can also be carried out.
    By way of derogation from Example 1, the air already washed with the basic electrolyte solution, in the application example, the stable air, for further treatment in a second gas scrubber, in which a gas scrubbing with an acidic electrolyte solution, for example with sulfuric acid, is performed, whereby existing in the stable air basic Contaminants, such as ammonia and amines are removed. The regeneration of this electrolyte solution can be carried out in a manner analogous to that of the electrolytic solution according to Example 1.
    The electrochemical conversion, the capacitive deionization and the desorption can be recovered in the specific example sulfuric acid and ammonia solution can be obtained. Furthermore, carbon dioxide is formed in the degasifier 7 as a by-product.
    Example 3 - Treatment of biogas and carbon dioxide utilization
    Biogas produced by direct fermentation from biomass contains large amounts of carbon dioxide, in particular biogas consists of up to about 50% carbon dioxide. For feeding the biogas into a natural gas network and the subsequent thermal utilization, it is necessary to increase the calorific value of the biogas by removing the carbon dioxide.
    The biogas to be treated is introduced in a manner analogous to Example 1 in a gas scrubber and "washed" there with a basic electrolyte solution, in particular a potassium hydroxide solution. Any organic acids present in the biogas are adsorbed by the electrolyte solution. The regeneration is carried out analogously to Example 1 in the form of the regeneration steps described therein (electrochemical conversion in a conversion apparatus 5, introduction into a degasser 7 and contact and conversion of the carbonates and bicarbonates into phosphates, with phosphoric acid, capacitive deionization with subsequent desorption and recovery of the washing solution) , Optionally, the optional regeneration steps described in Example 1 (separation of inorganic constituents in a mechanical separation device 4, water splitting in an electrochemical cell 6) can also be carried out.
    Since biogas often contains large amounts of organic acids, the electrochemical conversion is preferably carried out in two stages in a two-part conversion device. In the first stage, a Kolbe electrolysis is carried out in which carboxylic acids or salts of the carboxylic acids are converted to alkanes and carbon dioxide. In particular, alkenes are also formed. The Kolbe electrolysis is preferably carried out on platinum, glass graphite or graphite electrodes. The remaining after the Kolbe electrolysis in the electrolyte solution organic compounds are in a second stage in electrochemical cells, in particular using Di amantel ektroden, el ektrolysi ert.
    Reference number 1 ................. Room air 2 ................. Gas scrubber 3 .......... ....... Heat exchanger 4 ................. Separator 5 ................. Conversion device 6 ... .............. electrochemical cell 7 ................. degasser 8 .............. ... cell 9 ................. Compensating vessel 10, 11 ......... heating / cooling device
    权利要求:
    Claims (38)
    [1]
    claims
    1. A method for carrying out gas scrubbing by means of an electrolyte solution as a scrubbing liquid, which in at least one gas scrubber (2) with a gas to be cleaned (1) is brought into contact and after the gas scrubbing from the gas scrubber (2), wherein the loaded electrolyte solution according to b) Electrochemical conversion of the electrolytic solution in a conversion device (5), so that in the course of gas scrubbing absorbed by the electrolyte solution organic compounds degraded at least with the formation of carbon dioxide, water vapor and hydrogen and recovering the resulting gases; c) recovering a regenerated electrolytic solution in an ion deionization and desorption apparatus (8), wherein the supplied electrolytic solution is passed through a cell having a plurality of pairs of DC voltage the cations of the electrolytic solution are adsorbed to the electrodes serving as cathodes, wherein the cation subsequently desorbed from the electrodes by reversing the cation-loaded three-dimensional electrodes, each with an auxiliary electrode desorbed with hydroxide ions to the regenerated electrolyte solution d) recycling the regenerated electrolyte solution to the scrubber (2).
    [2]
    2. The method according to claim 1, characterized in that the electrolyte solution used for gas scrubbing is a basic electrolyte solution, which preferably has a pH of at least 12.0, preferably of> 13.
    [3]
    3. The method according to claim 1 or 2, characterized in that the electrolyte solution used for gas scrubbing is a potassium carbonate solution.
    [4]
    4. The method according to claim 1 or 2, characterized in that the electrolyte solution used for gas washing is a potassium hydroxide solution.
    [5]
    5. The method according to claim 1 or 2, characterized in that the electrolytic solution used for gas scrubbing contains potassium carbonate and potassium hydroxide.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the electrolyte solution during introduction into the gas scrubber (2), in particular by Leitungsionisation- or Koraonaionisation, electrostatically charged and deposited in the scrubber (2) arranged deposition electrodes and then for subsequent regeneration is derived.
    [7]
    7. The method according to claim 6, characterized in that the gas (1) immediately before or immediately after the gas scrubbing ETV radiation, in particular UV radiation having a wavelength <200 nm, preferably a wavelength of 185 nm exposed.
    [8]
    8. The method of any one of claims 1 to 7, characterized in that the gas (1) is cooled or heated during the gas scrubbing by means of the electrolyte solution.
    [9]
    9. The method according to claim 8, characterized in that the gas (1), which, while the gas scrubber is cooled or heated, is room air.
    [10]
    10. The method according to claim 8 or 9, characterized in that the regenerated electrolyte solution before the gas scrubber via heating / cooling devices (10, 11) and / or via at least one heat exchanger (3) is cooled or heated.
    [11]
    11. The method according to any one of claims 8 to 10, characterized in that the regenerated electrolyte solution is cooled before the gas scrubber via a Peltier element cascade.
    [12]
    12. The method according to any one of claims 8 to 10, characterized in that the electrolyte solution is cooled by means of a refrigerator.
    [13]
    13. The method according to any one of claims 8 to 10, characterized in that the electrolyte solution is cooled by means of adiabatic cooling, in particular by an evaporation of water of the electrolyte solution.
    [14]
    14. The method according to any one of claims 8 to 10, characterized in that the electrolyte solution is heated by burning fuel oil or natural gas or by means of a heat pump, a heat accumulator, photovoltaic or Peltier elements.
    [15]
    15. The method according to any one of claims 1 to 14, characterized in that the moisture of the gas to be cleaned (1) is adjusted by changing the ion concentration of the electrolyte solution.
    [16]
    16. The method according to any one of claims 1 to 15, characterized in that the electrolytic solution for hydrolyzing according to regeneration step a) is heated.
    [17]
    17. The method according to any one of claims 1 to 16, characterized in that from the electrolyte solution after hydrolyzing according to regeneration step a) by means of a mechanical separation device (4) in the electrolyte solution undissolved inorganic substances which have been absorbed by the electrolyte solution in the gas scrubbing, be deposited.
    [18]
    18. The method according to any one of claims 1 to 17, characterized in that the electrolytic solution in the electrochemical conversion according to regeneration step b) in particular in at least one einkammrigen designed as flow cell electrolytic cell having an electrode package of at least two connected to a voltage source contact electrodes, continuously and discharged, while flowing through the electrode package.
    [19]
    19. The method according to any one of claims 1 to 18, characterized in that in the electrochemical conversion according to regeneration step b) the residence time of the electrolyte solution in the electrolysis cell, the temperature of the electrolyte solution, the pH of the electrolyte solution, the ion concentration of the electrolyte solution and the current and the voltage of the voltage source are process parameters which are adjusted.
    [20]
    20. The method according to any one of claims 1 to 19, characterized in that the electrolyte solution is passed immediately after the electrochemical conversion according to regeneration step b) in an electrochemical cell (6), in which from the electrolyte solution originating water is split into hydrogen and oxygen, wherein the oxygen is supplied as needed to the regenerated electrolyte solution or directly to the gas purified by the gas scrubbing and wherein the hydrogen is discharged.
    [21]
    21. The method according to any one of claims 1 to 20, characterized in that the electrolyte solution is passed immediately before recovery according to regeneration step c) in a degasser (7), in which the electrolyte solution is supplied to phosphoric acid until the pH of the electrolyte solution <5 is.
    [22]
    22. The method according to claim 21, characterized in that the phosphoric acid is recovered in regeneration step c) and returned to the degasser (7).
    [23]
    23. The method according to claim 21 or 22, characterized in that the phosphate anions are adsorbed in the regeneration step c) to the anode serving as three-dimensional electrodes, wherein by reversal of the phosphate anions loaded three-dimensional electrodes, each with an auxiliary electrode, the phosphate anions subsequently desorb from the electrodes and reacted with oxonium ions to phosphoric acid, which is discharged and recycled to the degasser (7).
    [24]
    24. The method according to any one of claims 1 to 23, characterized in that in the regeneration step c) after the capacitive deionization, the deionized solution is discharged and in particular by Elekrolytlösung (washing solution) is replaced.
    [25]
    25. The method according to claim 24, characterized in that the drained deionized solution is stored in a surge tank (9).
    [26]
    26. The method according to any one of claims 1 to 25, characterized in that in regeneration step c) the auxiliary electrodes are three-dimensional electrodes and the desorption of the ions is carried out at a DC voltage below the decomposition voltage of the solution located in the cell.
    [27]
    27. The method according to any one of claims 1 to 26, characterized in that in Regeneratonsschritt c) the hydroxide ions during the desorption of the anions, in particular the phosphate anions, are enriched in the auxiliary electrodes.
    [28]
    28. The method according to any one of claims 1 to 27, characterized in that the regenerated electrolyte solution is fed to the gas scrubbing to change their ion concentration water.
    [29]
    29. The method according to any one of claims 1 to 28, characterized in that the gas to be cleaned (1) is brought in a first gas scrubber with a basic electrolyte solution and subsequently in a second scrubber with an acidic electrolyte solution in contact, wherein the charged electrolyte solutions respectively be regenerated continuously in accordance with the consecutive regeneration steps a) to c).
    [30]
    30. The method according to any one of claims 1 to 29, characterized in that regeneration step b) is carried out in two stages in a two-part conversion device.
    [31]
    31. The method according to claim 30, characterized in that in the second stage, the electrolyte solution is subjected to a total oxidation in an electrolytic cell containing diamond particle electrodes.
    [32]
    32. Apparatus for carrying out gas scrubbing by means of an electrolyte solution as a scrubbing liquid with a gas scrubber (2), a conversion device (5) for decomposing organic compounds absorbed by the electrolyte solution in the scrubber (2), wherein the conversion device (5) comprises an electrolytic cell designed as a flow cell a device for deionization and desorption (8) for forming a regenerated electrolyte solution, said device (8) of the conversion device (5) is connected downstream and a plurality of pairs of connected to a DC or DC power source three-dimensional electrodes for adsorption of ions from the Electrolyte solution and per pair of three-dimensional electrodes depending on an auxiliary electrode for separate polarity reversal with the three-dimensional electrodes and a return for returning the regenerated electrolyte solution in the gas scrubber (2).
    [33]
    33. Apparatus according to claim 32, characterized in that it comprises a heat exchanger (3), via which the from the gas scrubber (1) derived electrolyte solution in countercurrent to the regenerated electrolyte solution is feasible.
    [34]
    34. Apparatus according to claim 32 or 33, characterized in that it comprises a heating / cooling device (10, 11) for heating or cooling of the regenerated electrolyte solution.
    [35]
    35. An apparatus which is an air conditioner according to one or more of claims 32 to 34.
    [36]
    36. Device according to one of claims 32 to 35, characterized in that between the gas scrubber (2) and the conversion device (5) is provided a mechanical separation device (4) for separating non-soluble in the electrolyte solution inorganic impurities.
    [37]
    37. Device according to one of claims 32 to 36, characterized in that immediately after the conversion device (5) an electrochemical cell (6) for generating oxygen and hydrogen is provided.
    [38]
    38. Device according to one of claims 32 to 37, characterized in that the device for deionization and desorption (8) a degasser (7) is arranged upstream.
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    同族专利:
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    AT519109B1|2018-04-15|
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    引用文献:
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    KR101590728B1|2014-10-28|2016-02-03|한양대학교 에리카산학협력단|System and method for removing harmful substance|AT521381B1|2018-07-19|2020-01-15|Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg|Method and device for carrying out gas scrubbing using an electrolyte solution|
    CN109224105A|2018-08-20|2019-01-18|四川建元天地环保科技有限公司|Purposes of the organic electrolyte in environment deodorization|
    FR3113671A3|2020-08-31|2022-03-04|Libero MAZZONE|Process and installation for treating collected urine|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA51163/2016A|AT519109B1|2016-12-20|2016-12-20|Process for carrying out gas scrubbing by means of an electrolyte solution|ATA51163/2016A| AT519109B1|2016-12-20|2016-12-20|Process for carrying out gas scrubbing by means of an electrolyte solution|
    PCT/EP2017/083261| WO2018114768A1|2016-12-20|2017-12-18|Method for carrying out gas scrubbing by means of an electrolyte solution|
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