EP3292232B1 - Reduktionsverfahren zur elektrochemischen kohlenstoffdioxid-verwertung, alkalicarbonat- und alkalihydrogencarbonaterzeugung - Google Patents

Reduktionsverfahren zur elektrochemischen kohlenstoffdioxid-verwertung, alkalicarbonat- und alkalihydrogencarbonaterzeugung Download PDF

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EP3292232B1
EP3292232B1 EP16733951.4A EP16733951A EP3292232B1 EP 3292232 B1 EP3292232 B1 EP 3292232B1 EP 16733951 A EP16733951 A EP 16733951A EP 3292232 B1 EP3292232 B1 EP 3292232B1
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carbon dioxide
catholyte
cathode
hydrogen carbonate
alkali metal
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French (fr)
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EP3292232A1 (de
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Günter Schmid
Maximilian Fleischer
Philippe Jeanty
Ralf Krause
Erhard Magori
Anna Maltenberger
Sebastian Neubauer
Christian Reller
Bernhard Schmid
Elena Volkova
Kerstin WIESNER-FLEISCHNER
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Siemens Energy Global GmbH and Co KG
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Siemens Energy Global GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/23—Carbon monoxide or syngas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/083—Separating products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide

Definitions

  • the present invention relates to a reduction process for the electrochemical utilization of carbon dioxide. Carbon dioxide is fed into an electrolysis cell and reduced at a cathode.
  • a natural breakdown of carbon dioxide takes place, for example, through photosynthesis.
  • carbon dioxide is converted into carbohydrates in a process that is broken down into many sub-steps in terms of time and space. This process cannot easily be adapted on a large scale.
  • a copy of the natural photosynthesis process with large-scale photocatalysis has so far not been sufficiently efficient.
  • US 2012/228147 A1 discloses methods and systems for the electrochemical production of formic acid from carbon dioxide.
  • the cathode is selected from the group consisting of indium, lead, tin, cadmium and bismuth.
  • U.S. 3,959,094 A discloses a method and system for synthesizing methanol from the CO 2 in air using electrical energy. The CO 2 is absorbed into a solution of KOH to form K 2 CO 3 , which is electrolyzed to produce methanol, a liquid hydrocarbon fuel.
  • US 2008/223727 A1 discloses electrochemical processes for the reduction of carbon dioxide, for example the conversion of carbon dioxide into formate salts or formic acid.
  • the table shows Faraday efficiencies [%] of products that are produced during the reduction of carbon dioxide on various metal electrodes.
  • the specified values apply to a 0.1 M potassium hydrogen carbonate solution as the electrolyte and current densities below 10 mA / cm 2 .
  • a silver cathode would produce predominantly carbon monoxide and only a little hydrogen.
  • the reactions at the anode and cathode can be represented with the following reaction equations: Cathode: 2 CO 2 + 4 e - + 4 H + ⁇ 2 CO + 2 H 2 O Anode: 2 H 2 O ⁇ O 2 + 4 H + + 4 e -
  • An electrolysis system not according to the invention for carbon dioxide utilization comprises at least one electrolyzer with an anode in an anode compartment and a cathode in a cathode compartment, the cathode compartment having at least one access for carbon dioxide and the cathode compartment being designed to bring the incoming carbon dioxide into contact with the cathode .
  • the cathode compartment comprises a catholyte or is designed to be able to accommodate a catholyte, wherein the catholyte can access the cathode compartment via the same access as the carbon dioxide or via a separate second access.
  • at least the anode compartment, when the cell is in operation, anode compartment and cathode compartment have alkaline cations.
  • a catholyte is an electrolyte that is directly influenced by the cathode during electrolysis.
  • anolyte is also used in the following when an electrolyte is referred to that is directly influenced by the anode during electrolysis.
  • Alkaline cations refer to positively charged ions which have at least one element of the first main group of the periodic table.
  • the anode compartment of the electrolyser has at least one access for an anolyte and comprises an anolyte or is at least designed to receive an anolyte via this access, this anolyte having chlorine anions.
  • the anode compartment and the cathode compartment are separated from one another by a membrane.
  • the membrane is at least one mechanically separating layer, for example a diaphragm, which separates at least the electrolysis products produced in the anode compartment and cathode compartment from one another. Then you could too speak of a separator membrane or separating layer. Since the electrolysis products are in particular gaseous substances, a membrane with a high bubble point of 10 mbar or greater is preferably used. The so-called bubble point is a defining variable for the membrane used, which describes the pressure difference ⁇ P between the two sides of the membrane from which a gas flow through the membrane would start.
  • the membrane can also be a proton- or cation-conducting or permeable membrane. While molecules, liquids or gases are separated, a flow of protons or cations is guaranteed from the anode compartment to the cathode compartment.
  • a membrane is preferably used which has sulfonated polytetrafluoroethylene, for example Nafion.
  • the electrolysis system further comprises at least one separation basin for crystallizing an alkali hydrogen carbonate and / or alkali carbonate from the catholyte.
  • this separation basin has a product outlet.
  • a second separation basin can also be provided for the most advantageous possible crystallization process. This is then typically arranged in the catholyte circulation direction after the first separation basin.
  • the reduction of carbon dioxide produces different products: For example, carbon monoxide, ethylene, methane, ethanol or monoethylene glycol are produced. In all these cases, hydroxide ions are also formed, which are neutralized to hydrogen carbonate by excess carbon dioxide.
  • the source of the alkaline cations lies in the anode compartment. A cation current through the membrane compensates for the electrical current caused by the applied voltage. For example, the alkali cations and the chloride anions are metered into the anolyte in the form of a chloride salt.
  • the alkali cations migrate through the membrane into the catholyte circuit, where they react in the cathode compartment with the carbonate or hydrogen carbonate formed there to form an alkali metal carbonate or alkali hydrogen carbonate and in particular leave the catholyte circuit via the separate product outlet of the separation basin.
  • the electrolysis system not according to the invention has the advantage that, in addition to chlorine, at least one alkali metal carbonate and / or alkali metal hydrogen carbonate is generated as a valuable chemical substance. Whether alkali carbonate or alkali hydrogen carbonate is produced depends, for example, on the alkali metal and the recycling process. In aqueous solution, for example, the solubility is crucial. The less soluble carbonate or hydrogen carbonate crystallizes out. In the case of sodium and potassium, it is the hydrogen carbonate that is more sparingly soluble than the carbonate and then has to be calcined in a subsequent step. The combustion of sodium in carbon dioxide is an example that produces carbon monoxide and directly sodium carbonate Na 2 CO 3.
  • the electrolysis system described serves to utilize carbon dioxide and it can typically also be used to provide at least one third valuable substance, such as carbon monoxide, ethylene, methane, ethanol or monoethylene glycol.
  • a third valuable substance such as carbon monoxide, ethylene, methane, ethanol or monoethylene glycol.
  • the actual cathode reaction in which the carbon dioxide is reduced, is followed by a subsequent reaction, namely the neutralization of the hydroxide ions (OH-). These are neutralized in particular by excess carbon dioxide to form hydrogen carbonate (HCO 3 - ).
  • HCO 3 - hydrogen carbonate
  • the pH value in the cathode compartment is buffered in a pH value range of 6 to 8 will. It also has the effect that the electrolyte concentration increases continuously.
  • the catholyte is fed into a catholyte circuit, that is to say is pumped into the cathode compartment and also discharged from it again, the hydrogen carbonate formed in the cathode compartment can be removed from the catholyte.
  • the catholyte circuit in particular in the catholyte circuit, but for example also in the anolyte circuit, there is in each case at least one pump which provides for an electrolyte circuit.
  • alkali metal cations that are present in the cathode compartment originate from the anode compartment, into which they were initially introduced, in particular as alkali metal chloride as an oxidation reactant or in the form of another alkali metal salt, for example to increase conductivity.
  • the alkali ions are preferably fed into the anode compartment as alkali chloride.
  • the membrane between the anode and cathode compartments is in particular chosen so that the cation current from the anode compartment to the cathode is ensured in the electric field of the electrolyzer.
  • the separation basin preferably comprises a cooling device, by means of which the catholyte is cooled by several degrees Kelvin, in contrast to the temperature range that prevails in the electrolyzer.
  • the set temperature difference between the separation basin and the electrolyzer is preferably at least 15 K, in particular at least 20 K.
  • a temperature difference between 30 K and 50 K can be particularly suitable.
  • the temperature difference between the electrolyzer and the separation basin can be in a temperature range between 5 K and 70 K.
  • the lowering of the temperature in the separation basin has the additional advantage for the overall system that cooling takes place in the catholyte circuit before the catholyte is returned to the cathode compartment. This avoids excessive system-related heat development, especially in the electrolyser. However, a cooling device which may be provided especially for this purpose can be saved.
  • pH buffers are preferably used, which are made available, for example, in a buffer reservoir to the separation basin and / or the catholyte circuit and / or the cathode compartment in order to buffer the catholyte volume accordingly.
  • the pH of the catholyte can also be used as such to control the process of separating the alkali hydrogen carbonate from the electrolyte.
  • the pH value in the cathode compartment in particular is initially kept at a higher value, e.g. 8 or higher. This can shift the equilibrium in favor of the alkali carbonate in contrast to the alkali hydrogen carbonate.
  • the pH is then lowered, preferably to a value of 6 or less, which leads to the formation and crystallization of the alkali hydrogen carbonate.
  • the lowering of the pH value is typically done by blowing carbon dioxide into the separation basin.
  • an alkali hydrogen carbonate or an alkali carbonate can initially be formed.
  • the two procedures described can be used to remove the desired product from the catholyte can also be combined.
  • the sodium carbonate Na 2 CO 3 for example, can also be obtained afterwards from the crystallized sodium hydrogen carbonate NaHCO 3 by heating. Then hydrogen carbonate is even preferably first produced, deposited, and then the desired proportion of it is further processed into carbonate.
  • the pH dependence of the hydrogen carbonate or carbonate ions is, for example, in Figure 6 shown in a Hägg diagram for a sodium carbonate solution.
  • a buffer reservoir is preferably also provided in the anolyte circuit, which can in particular also serve to introduce or replenish alkali chloride in the electrolyte in order to maintain the salt content in the anolyte.
  • the catholyte has at least one solvent, in particular water.
  • aqueous electrolytes and correspondingly water-soluble conductive salts are used.
  • the conductive salt content can be increased by adding further carbonates, hydrogen carbonates, but also sulfates or other conductive salts in order to increase the conductivity of the electrolyte in the catholyte as well as in the anolyte circuit, which leads to an increase in the metabolism in the overall system.
  • the crystallization process must be adapted accordingly in order to extract the desired product in as pure a form as possible.
  • the conductive salts used are therefore typically chosen so that their solubility differs significantly from that of the alkali hydrogen carbonate or the alkali carbonate.
  • the electrolysis system not according to the invention has a gas separation device on the anolyte side, which is designed to separate the chlorine gas from the anolyte.
  • a gas separation device can also be provided in the catholyte circuit, e.g. if it is geared towards the generation of carbon monoxide gas by using a cathode containing silver. Additional devices for inlets or outlets from the system or additional buffer reservoirs can be provided in the anolyte and catholyte circuits.
  • the type and quality of the membrane used in the electrolyser ultimately plays a major role in how pure the product that has crystallized out is. If only a separator is used as the membrane, chloride anions, for example, can also diffuse into the cathode space, even against the electric field in the electrolyzer, so that chlorides may also be formed in addition to hydrogen carbonate. Therefore, in the electrolysis system described, which is not according to the invention, a cation-conducting membrane is preferably used, which can almost exclusively pass cations. A purely anion-conducting membrane is accordingly not advantageous.
  • the described, inventive reduction process for carbon dioxide utilization by means of an electrolysis system is defined in claim 1 and comprises the following steps: A catholyte comprising water and hydroxide ions and carbon dioxide are introduced into a cathode compartment and brought into contact there with a cathode. In the interior of the cathode compartment, this catholyte has alkaline cations which migrate through the cation-conducting membrane that separates the anode and cathode compartments.
  • At least part of the catholyte volume is introduced into a separation basin and an alkali hydrogen carbonate and / or an alkali carbonate is crystallized there.
  • an anolyte, which has chloride anions is introduced into an anode space and brought into contact there with an anode, at the anode the chloride anions are oxidized to chlorine and this is separated from the anolyte as chlorine gas via a gas separation device.
  • this reduction process is carried out in such a way that the anolyte and catholyte are each conducted in a separate circuit, i.e. two pumps are provided in the electrolysis system, which at least at one point in the circuit transport the catholyte through the cathode compartment and transport the anolyte through the anode compartment effect.
  • the circuits are separated from one another by the membrane in the electrolyser, which ideally only allows the transport of cations from the anode compartment into the cathode compartment.
  • the alkali cations required in the cathode compartment are obtained from the anode compartment.
  • the anolyte preferably has an alkali chloride, which can accordingly be used as a conductive salt but also as an electrolysis product.
  • the alkali metal chloride in the anolyte can be used as the electrolysis product and an additional conductive salt, for example a sulfate, a phosphate, etc., preferably an alkali metal sulfate, can be used.
  • an additional conductive salt for example a sulfate, a phosphate, etc., preferably an alkali metal sulfate
  • ammonium salts or their homologues can also be used.
  • Imidazolium salts or other ionic liquids can have a positive effect on the selectivity of the electrode, especially the cathode.
  • carbon monoxide, ethylene, methane, ethanol and / or monoethylene glycol is produced in the reduction process during the reduction of the carbon dioxide at the cathode.
  • a suitable cathode is used as a catalyst for these reactions.
  • the cathode is a silver-containing cathode and mainly forms carbon monoxide, hydroxide ions and only a little hydrogen as products from the carbon dioxide and the catholyte.
  • the cathode is a copper-containing cathode and forms ethylene, methane, ethanol and / or from the carbon dioxide and the catholyte Monoethylene glycol and hydroxide ions as products.
  • the great advantage of this reduction process is that, in addition to the utilization of carbon dioxide, chemical valuable substances can also be generated.
  • the hydroxide ions formed during the carbon dioxide reduction are converted to hydrogen carbonate ions with excess carbon dioxide.
  • the hydrogen carbonate production directly in the cathode compartment has the advantage that it can react further directly with the alkali cations present in the cathode compartment to form another interesting valuable material that would otherwise have to be produced in separate manufacturing processes.
  • At least part of the catholyte volume is introduced into a separation basin and cooled there by at least 15 K, preferably by at least 20 K.
  • the temperature dependence of the carbonate solubility is used here to remove the valuable substance from the catholyte cycle.
  • the temperature difference between the separation basin and the electrolyser can also be more than 30 K, in particular more than 50 K, depending on the alkali hydrogen carbonate to be extracted and also depending on which other salts are present in the circuit.
  • the temperature difference between the electrolyzer and the separation unit can be between 5 K and 70 K.
  • At least part of the catholyte volume is introduced into a separation basin and its pH value there, in particular by blowing in carbon dioxide from above 8 to a pH value lowered by 6 or less. Buffering the pH value to a value above 8 in the cathode compartment has the advantage of preventing the alkali hydrogen carbonate from precipitating in the cathode compartment itself.
  • the reduction process can be carried out so that the precipitated alkali hydrogen carbonate is converted to alkali carbonate by heating. This can be done directly after the hydrogen carbonate has crystallized out in the separation basin or it can be done separately from the electrolysis system described.
  • the process can be run in such a way that the pH value in the cathode compartment is kept at the upper limit of the reaction by 8 or higher, so that the equilibrium is initially shifted in favor of sodium carbonate is: 2 NaHCO 3 ⁇ Na 2 CO 3 + H 2 O + CO 2 .
  • the process is not limited to sodium hydrogen carbonate.
  • potassium hydrogen carbonate can also be produced in this process.
  • the potassium hydrogen carbonate can also be crystallized from a pure potassium hydrogen carbonate electrolyte by lowering the temperature in the separation basin. At 20 ° C the solubility of potassium hydrogen carbonate is 337 g / l, at 60 ° C 600 g / l.
  • potassium sulfate K 2 SO 4
  • KHCO 3 potassium hydrogen carbonate
  • the separation tank AB potassium sulphate K 2 SO 4 preferably crystallizes out, which is then, in the direction of the circulation, after the separation tank AB , can be fed back into the electrolyte.
  • the electrolyte volume from which the potassium sulfate K 2 SO 4 has already been removed is then concentrated, preferably in a further separation basin, ie the water is removed from the potassium hydrogen carbonate solution, for example by cooling, in order to obtain the crystalline material.
  • this method can also be used for other cations or mixtures of cations. Due to the migration of the cations, the catholyte concentrates until the most difficult to dissolve salt or double salt separates. It is important that the process of concentration and separation does not take place in the cathode compartment, i.e. not in the electrolysis cell itself, but rather that the catholyte is transported to a separation basin integrated in the electrolysis system.
  • a further additional physical or chemical difference between the electrolysis cell and the separation basin for example a temperature, pH value or pressure gradient, enables or facilitates the separation in the separation basin.
  • a suitable pressure difference between the electrolysis cell and the separation basin can be up to 100 bar. A pressure difference between 2 bar and 20 bar would preferably be selected. An increased pressure in the separation basin would favor the formation of hydrogen carbonate.
  • a valuable substance such as carbon monoxide, ethylene, methane, ethanol or monoethylene glycol is obtained from the carbon dioxide reduction; and / or sodium carbonate as a by-product and chlorine is produced on the anode side.
  • FIG. 1 and 2 Examples of electrolysis systems not according to the invention for carbon dioxide reduction are shown in a schematic representation, which can also be read as flow charts for the reduction process described.
  • the anolyte circuit AK is shown on the left-hand side and the catholyte circuit KK is shown on the right-hand side.
  • These two circuits AK, KK are connected via the electrolyzer E1, E2, the anode compartment AR and cathode compartment KR of which are connected to one another via a membrane M or are separated from one another via these.
  • a cation-conducting membrane M is preferably used as the membrane M.
  • An anode A is arranged in the anode space AR and a cathode K is arranged in the cathode space KR, which are electrically connected via a voltage source U.
  • Both circuits AK, KK preferably each have a pump P1, P2 which pump the electrolytes through the electrolyzer.
  • devices N1, N2, N3 can be present in both circuits AK, KK at different points in the direction of flow, which can be additional inflows or outflows or as buffer reservoirs.
  • At least one gas separation device G2 with a product outlet PA2, via which the product chlorine gas Cl 2 can be removed, is provided in the anolyte circuit AK.
  • At least one gas separation device G1 with a product outlet PA1 is also provided in the catholyte circuit KK, via which, for example, the electrolysis product carbon monoxide CO, for example also hydrogen H 2 , can be withdrawn.
  • the electrolysis product carbon monoxide CO for example also hydrogen H 2
  • other electrolysis products such as ethylene, methane, ethanol, monoethylene glycol can also be taken from the system via this or, for example, via a further product outlet.
  • the electrolyzer E1, E2 has, for example, a gas diffusion electrode GDE for the carbon dioxide inlet.
  • the electrolyser E1 shown is a two-chamber structure and the carbon dioxide CO 2 is introduced into the electrolyte via a reservoir CO 2 -R and in the direction of the circulation in front of the cathode chamber KR.
  • the catholyte circuit KK has a separation basin AB, which can be integrated directly into the circuit or through which only part of the catholyte volume is passed.
  • a branch of the circuit KK may be provided.
  • the separation basin AB or several separation basins connected in series can be connected, for example, to a cooling device or to a buffer reservoir PR, so that the crystallization of the hydrogen carbonate is promoted by setting a temperature difference, pressure difference or pH value difference to the electrolyzer E1, E2. Furthermore, the separation basin AB has a product outlet PA3. Several separation basins connected in series would each have a product outlet.
  • electrolysis systems are shown as they can be used for carrying out the reduction process according to the invention.
  • care is taken to ensure that separate anolyte AK and catholyte circles KK are available.
  • the electrolytes used are then pumped continuously through the electrolysis cell E1, E2, ie through the anode space AR and through the cathode space KR.
  • a pump P1, P2 is provided in each of the two circuits AK, KK in the structure.
  • the structure can have materials made of plastic, plastic-coated metal or glass. Glass flasks can be used as storage vessels, the cell itself is made of PTFE, for example, and the tubes are made of neoprene.
  • the electrolyzer E1, E2, as it is installed in the electrolysis systems shown, can also have a different structure, as it is, for example, in FIG Figures 3 to 5 is shown.
  • An alternative electrolysis cell is the one based on the polymer electrolyte membrane structure (PEM structure). In this case lies at least one electrode directly on the polymer electrolyte membrane PEM.
  • the electrolysis cell can be designed as a PEM half-cell, as in FIG Figures 4 and 5 in which the anode side is designed as a PEM half-cell, that is, the anode A is arranged in direct contact with the membrane PEM and the anode space AR is arranged on the side of the anode A facing away from the membrane.
  • the cathode K is designed to be porous and at least partially gas-permeable and / or electrolyte-permeable.
  • the anode PEM half-cell is combined with a gas diffusion electrode GDE for introducing the carbon dioxide CO 2 into the cathode space KR.
  • a cathode K flowing behind is shown, the cathode space KR of which is connected to a gas reservoir via the cathode K.
  • the gas reservoir for its part has at least one gas inlet GE and possibly gas outlet GA.
  • Such an embodiment has hitherto been used, for example, as an oxygen-consuming electrode, for example in the production of sodium hydroxide solution.
  • the oxygen-consuming cathode can be used, for example, to avoid the formation of hydrogen H 2 in the cathode chamber KR in favor of a reaction to water H 2 O.
  • the water formation energy lowers the necessary system voltage U and thus results in a lower energy consumption of the electrolysis system.
  • the cathode K of an oxygen-consuming electrode consists primarily of silver, it can also catalyze the carbon dioxide reduction. If no oxygen is made available, the oxygen consumption reaction cannot take place. Instead, the carbon dioxide reduction to carbon monoxide CO takes place with a certain amount of hydrogen formation.
  • the sodium example is particularly suitable because the sodium hydrogen carbonate can be separated out very easily from the electrolyte.
  • sodium hydrogen carbonate and sodium carbonate are important, frequently required chemical substances.
  • Worldwide annual sodium carbonate production is around 50 million tons, such as the Roskill market report " Soda Ash: Market Outlook to 2018 ", available from Roskill Information Services Ltd, email: info@roskill.co.uk, www.roskill.co.uk/soda-ash , can be found.
  • Table 2 shows other salts, potassium hydrogen carbonate KHCO 3 , potassium sulfate K 2 SO 4 , potassium phosphate K 3 PO 4 , potassium iodide KI, potassium bromide KBr, potassium chloride KCl, sodium hydrogen carbonate NaHCO 3 , sodium sulfate Na 2 SO 4 , which can be used with preference.
  • other sulfates, phosphates, iodides or bromides can also be used to increase the conductivity in the electrolyte. Due to the constant supply of carbon dioxide, carbonates or hydrogen carbonates do not have to be supplied, but are formed in the cathode space KR during operation.
  • the solubility of sodium hydrogen carbonate NaHCO 3 in water is 69 g / l at 0 ° C, 96 g / l at 20 ° C, 165 g / l at 60 ° C and 236 g / l at 100 ° C.
  • Sodium carbonate NaCO 3 dissolves comparatively well, its solubility is 217 g / l at 20 ° C.
  • the sodium hydrogen carbonate NaHCO 3 tends to crystallize out in the electrolysis cell E1, E2. This can be counteracted by means of an increased temperature, which is already created by the operation of the system, and also by means of appropriate pH value buffering.
  • the sodium hydrogen carbonate NaHCO 3 should only crystallize out of the electrolyte in the separation basin AB.
  • the sodium hydrogen carbonate NaHCO 3 formed in the cathode chamber KR is led out of this and the catholyte circuit KK can run through a separation basin AB or a partial volume of the catholyte is branched off into a separation basin AB, in which, for example, the cooling of the electrolyte, the sodium hydrogen carbonate NaHCO 3 crystallizes out and can thus be obtained.
  • a hydrogen sulfate HSO 4 - or sulfate SO 4 2- is preferably used as the conductive additive. This can be, for example, sodium sulfate Na 2 SO 4 or sodium hydrogen sulfate NaHSO 4 .
  • the solubility of sodium hydrogen sulfate NaHSO 4 is 1080 g / l at 20 ° C and that of sodium sulfate Na 2 SO 4 is 170 g / l at 20 ° C, see Table 2.
  • This large difference in solubility compared to sodium hydrogen carbonate NaHCO 3 ensures that Sodium hydrogen carbonate NHCO 3 preferably crystallizes out in the separation basin.
  • This variant of the reduction process has the immense advantage that it can basically replace the Solvay process used as standard for the production of sodium hydrogen carbonate.
  • the Solvay process for producing sodium hydrogen carbonate has a major disadvantage, namely that it consumes very large amounts of water. In addition, for every kilogram of soda, i.e.
  • Sodium hydrogen carbonate NaHCO 3 occurs as a natural mineral Nahcolith in the United States of America. It usually occurs finely distributed in oil shale and can then be obtained as a by-product of oil production. Particularly rich Nahcolith horizons are being mined in the state of Colorado. However, the annual production in 2007 was only 93,440 tons. It also occurs, for example, in soda lakes in Egypt, in Turkey in Lake Van, in East Africa, e.g. B.
  • FIG. 6 an example of a Hägg diagram of a 0.05 molar solution of carbon dioxide CO 2 is shown to illustrate the dependence on the concentration and pH value parameters.
  • carbon dioxide CO 2 and its salts are present next to one another.
  • the strongly basic carbon dioxide CO 2 is preferably present as carbonate CO 3 2-
  • the medium pH range preferably as hydrogen carbonate HCO 3 -
  • the hydrogen carbonate ions are expelled from the solution in the form of at low pH values in an acidic environment Carbon dioxide CO 2 .

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EP16733951.4A 2015-07-03 2016-06-30 Reduktionsverfahren zur elektrochemischen kohlenstoffdioxid-verwertung, alkalicarbonat- und alkalihydrogencarbonaterzeugung Active EP3292232B1 (de)

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PCT/EP2016/065277 WO2017005594A1 (de) 2015-07-03 2016-06-30 Elektrolysesystem und reduktionsverfahren zur elektrochemischen kohlenstoffdioxid-verwertung, alkalicarbonat- und alkalihydrogencarbonaterzeugung

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DE102016218235A1 (de) 2016-09-22 2018-03-22 Siemens Aktiengesellschaft Verfahren zur Herstellung von Propanol, Propionaldehyd und/oder Propionsäure aus Kohlendioxid, Wasser und elektrischer Energie
JP6672193B2 (ja) * 2017-02-02 2020-03-25 株式会社東芝 二酸化炭素の電解セルと電解装置
JP6879549B2 (ja) * 2017-04-27 2021-06-02 学校法人慶應義塾 排ガスを電解還元して有価物を回収する装置及び方法
DE102017208610A1 (de) 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
EP3418429A1 (de) * 2017-06-21 2018-12-26 Covestro Deutschland AG Gasdiffusionselektrode zur reduktion von kohlendioxid
DE102017212278A1 (de) * 2017-07-18 2019-01-24 Siemens Aktiengesellschaft CO2-Elektrolyseur
DE102017213471A1 (de) * 2017-08-03 2019-02-07 Siemens Aktiengesellschaft Vorrichtung und Verfahren zur elektrochemischen Nutzung von Kohlenstoffdioxid
DE102017213473A1 (de) * 2017-08-03 2019-02-07 Siemens Aktiengesellschaft Elektrolysevorrichtung und Verfahren zum Betreiben einer Elektrolysevorrichtung
DE102018212409A1 (de) 2017-11-16 2019-05-16 Siemens Aktiengesellschaft Kohlenwasserstoff-selektive Elektrode
DE102018202184A1 (de) * 2018-02-13 2019-08-14 Siemens Aktiengesellschaft Separatorlose Doppel-GDE-Zelle zur elektrochemischen Umsetzung
DE102018207589A1 (de) * 2018-05-16 2019-11-21 Robert Bosch Gmbh Verfahren zur Gewinnung von Gold, Silber und Platinmetallen aus Bestandteilen eines Brennstoffzellenstapels oder eines Elektrolysators
EP3626861A1 (de) * 2018-09-18 2020-03-25 Covestro Deutschland AG Elektrolysezelle, elektrolyseur und verfahren zur reduktion von co2
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CN110344071B (zh) * 2019-08-14 2020-11-17 碳能科技（北京）有限公司 电还原co2装置和方法
EP3805429A1 (de) * 2019-10-08 2021-04-14 Covestro Deutschland AG Verfahren und elektrolysevorrichtung zur herstellung von chlor, kohlenmonoxid und gegebenenfalls wasserstoff
CN110923736A (zh) * 2019-10-23 2020-03-27 安徽中研理工仪器设备有限公司 一种光电催化化学反应电解池装置
CN110983357A (zh) * 2019-12-04 2020-04-10 昆明理工大学 一种电解二氧化碳制一氧化碳同时副产氯气、碳酸氢盐的三室隔膜电解方法
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WO2024129657A1 (en) * 2022-12-12 2024-06-20 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Electrochemical method that facilitates the recovery of carbon dioxide from alkaline water by the acidification of such water sources along with the continuous hydrogen gas production
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PL3292232T3 (pl) 2022-01-10
DK3292232T3 (da) 2021-10-25
WO2017005594A1 (de) 2017-01-12
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CN107735512A (zh) 2018-02-23

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