EP3292232A1 - Système d'électrolyse et procédé de réduction aux fins de valorisation électrochimique de dioxyde de carbone, de production de carbonate alcalin et d'hydrogénocarbonate alcalin - Google Patents

Système d'électrolyse et procédé de réduction aux fins de valorisation électrochimique de dioxyde de carbone, de production de carbonate alcalin et d'hydrogénocarbonate alcalin

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Publication number
EP3292232A1
EP3292232A1 EP16733951.4A EP16733951A EP3292232A1 EP 3292232 A1 EP3292232 A1 EP 3292232A1 EP 16733951 A EP16733951 A EP 16733951A EP 3292232 A1 EP3292232 A1 EP 3292232A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
cathode
catholyte
alkali
anolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16733951.4A
Other languages
German (de)
English (en)
Other versions
EP3292232B1 (fr
Inventor
Günter Schmid
Maximilian Fleischer
Philippe Jeanty
Ralf Krause
Erhard Magori
Anna Maltenberger
Sebastian Neubauer
Christian Reller
Bernhard Schmid
Elena Volkova
Kerstin WIESNER-FLEISCHNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens Energy Global GmbH and Co KG
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Siemens AG
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Publication date
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Priority to PL16733951T priority Critical patent/PL3292232T3/pl
Publication of EP3292232A1 publication Critical patent/EP3292232A1/fr
Application granted granted Critical
Publication of EP3292232B1 publication Critical patent/EP3292232B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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 method and an electrolysis system for electrochemical carbon dioxide utilization. Carbon dioxide is introduced into an electrolyte cell and reduced at a cathode.
  • Natural carbon dioxide degradation occurs, for example, through photosynthesis.
  • carbon dioxide are reacted to form carbohydrates. This process is not so easy on a large scale
  • Electrochemical CO 2 reduction on metal electrodes from Y Electrochemical CO 2 reduction on metal electrodes from Y.
  • carbon dioxide is reduced, for example, to silver, gold or zinc cathodes, almost exclusively carbon monoxide is produced.
  • the table shows Faraday efficiencies [%] of products produced by carbon dioxide reduction on various metal electrodes. The values given apply to a 0.1 M potassium bicarbonate solution as electrolyte and current densities below 10 mA / cm 2 . On a silver cathode, for example, predominantly carbon monoxide and only a little hydrogen would be produced.
  • THE REACTION ⁇ nen at the anode and cathode can be represented by the following reaction sliding ⁇ cations: Cathode: 2 C0 2 + 4 e "+ 4 H + - 2 CO + 2 H 2 0
  • the proposed solution should enable a continuous carbon dioxide conversion. It is an object of the invention to provide an improved reduction process and electrolysis system for carbon dioxide utilization.
  • the electrolyzer system of the invention for carbon dioxide recycling comprises at least one electrolyzer with an anode in an anode compartment and a cathode in a cathode compartment, said cathode compartment comprising at least one access for carbon dioxide and wherein the cathode compartment is ⁇ staltet that, OBTAINED carbon dioxide in contact with the cathode bring to.
  • the cathode compartment comprises a catholyte or is configured to receive a catholyte, wherein the catholyte may be communicated with the cathode compartment via the same access as the carbon dioxide or via a separate second access.
  • at least the anode compartment, in the operation of the cell anode and cathode compartment alkali cations.
  • a catholyte is an electrolyte which is directly influenced by the cathode during the electrolysis. Accordingly, anolyte is also referred to below when an electrolyte is referred to, which is in direct influence of the anode in an electrolysis. With alkali metal cations, positively charged ions are referred to, the at least one element of the ers ⁇ th main group of the periodic system.
  • the anode chamber of the electrolyser comprises at least one To ⁇ gear for an anolyte and comprises an anolyte or at least is adapted to receive an anolyte via this access, whereby this stand-anolyte comprises chlorine anion.
  • the anode compartment and the cathode compartment are separated by a membrane.
  • the membrane is at least one mechanical separating layer, for example a diaphragm, which separates at least the resulting in Ano ⁇ denraum and cathode compartment electrolysis products apart.
  • separator membrane or separating layer Since it is gaseous substances, in particular for the electrolysis ⁇ products, will be ⁇ vorzugt a membrane with a high bubble point of 10 mbar or larger used.
  • bubble point is a defining variable for the membrane used, which describes ⁇ from which pressure difference ⁇ between the two sides of the membrane would use a gas flow through the membrane.
  • the membrane may also be a proton- or cation-conducting or permeable membrane. While molecules, liquids or gases are separated, a proton or cation flow is ensured from the anode compartment to the cathode compartment.
  • a membrane is used which has sulfonated polytetrafluoroethylene, eg Nafion.
  • the electrolysis system further comprises at least one separation basin for the crystallization of an alkali metal bicarbonate and / or alkali metal carbonate from the catholyte.
  • ⁇ sondere has this separation basin on a product outlet.
  • a second separating basin can also be provided for a most advantageous crystallization process. This is then typically in
  • Chloride anions are oxidized at the anode to chlorine and chlorine gas exit as the anolyte, the Alkalika ⁇ functions migrate through the membrane into the catholyte where they in The cathode compartment react with the carbonate or hydrogen carbonate formed there to form an alkali metal carbonate or alkali metal bicarbonate and, in particular, leave the catholyte circuit via the separate product outlet of the separating basin.
  • the electrolysis system according to the invention has the advantage, in addition to chlorine, at least one alkali carbonate and / or alkali bicarbonate to produce as a chemical valuable material. 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, solubility is crucial.
  • the combustion of sodium in carbon dioxide is an example in which Koh ⁇ lenstoffmonoxid directly and sodium carbonate Na 2 Cue 3 is generated.
  • the electrolysis system described serves the
  • Monoethylene glycol are provided.
  • the very advantageous utilization of the compensating current by the cations thus creates an electrolysis system which enables continuous hydrogen carbonate production.
  • the catholyte has the effect of increasing the electrolyte concentration continuously.
  • the catholyte is guided into a catholyte cycle, ie into the cathode space pumped and derived again, the catholyte can be removed from the resulting in the cathode compartment hydrogen carbonate.
  • at least one pump is arranged in particular in the catholyte circuit, for example, but also in the anolyte circuit, which ensures an electrolyte circulation.
  • Alkali cations continue to alkali bicarbonates.
  • the alkali metal cations present in the cathode space are taken from the anode compartment, in which they were initially introduced, in particular as Alkalichlo ⁇ chloride as Oxidationsedukt or in the form of another Alkalisal- zes, for example, to increase the conductivity.
  • the alkalization is preferably carried out in the anode compartment as alkali metal chloride.
  • the membrane between the anode and cathode space is chosen in particular so that the Kat ⁇ ion current is ensured from the anode space to the cathode in the electric field of the electrolyzer.
  • the temperature and pH dependence of the solubility of alkali hydro ⁇ gencarbonaten now leads that different processes are performed to crystallize or for removal from the catholyte:
  • the temperature dependence of the solubility of the desired as electrolysis product alkali metal bicarbonates can be used.
  • the separating basin preferably comprises a cooling device, by means of which the catholyte is cooled by several degrees Kelvin, in contrast to the temperature range which prevails in the electrolyzer.
  • the adjusted temperature difference is from the separating basin to
  • Electrolyzer at least 15 K, in particular at least 20 K.
  • a temperature difference between 30 K and 50 K may be particularly suitable.
  • the temperature difference between The electrolyzer and separating basin can be in a temperature range between 5 K and 70 K.
  • the lowering of the temperature in the separating basin has the additional advantage for the entire system that a cooling takes place in the catholyte circulation before the return of the catholyte into the cathode space.
  • a cooling takes place in the catholyte circulation before the return of the catholyte into the cathode space.
  • Katholyt Vietnameselauf and / or the cathode compartment are made available to the catholyte volume according to puf ⁇ fern.
  • the pH of the catholyte can also be considered as such for the
  • Control of the deposition of the alkali metal bicarbonate can be used from the electrolyte.
  • the pH in the cathode compartment is first increased to a higher value, e.g. kept at 8 or higher. This can shift the equilibrium in favor of the alkali carbonate as opposed to the alkali hydrogen carbonate.
  • Separation tank is then lowered the pH, preferably to a value of 6 or less, which leads to the formation and crystallization of the alkali metal bicarbonate.
  • the pH reduction is typically done by blowing carbon dioxide into the capture tank.
  • an alkali metal bicarbonate or an alkali carbonate may be ge ⁇ forms.
  • the two described procedures for withdrawing the desired product from the catholyte can also be combined.
  • the sodium carbonate Na 2 CC> 3 can be obtained in retrospect from the crystallized sodium bicarbonate NaHCC> 3 by heating. Then, even preferably produced initially bicarbonate, separated, and it rubver ⁇ ⁇ After working in the transition of the desired proportion to carbonate.
  • the pH-dependence of the bicarbonate or carbonate ions is e.g. shown in Figure 6 in a Hägg diagram for a sodium carbonate solution.
  • a buffer reservoir is preferably also provided in the anolyte circulation, which buffer can also be used, in particular, for introducing or delivering alkali metal chloride into the electrolyte in order to maintain the salt content in the anolyte.
  • the catholyte at least one solvent on, insbesonde re ⁇ water.
  • aqueous electrolytes and, accordingly, water-soluble conductive salts are used.
  • the electrolyte content can be increased by the addition of other carbonates, bicarbonates, but also sulfates or other conductive salts, to increase the conductivity of the electrolyte in the
  • the electrolytic system on the anolyte side has a gas separation device which is designed to carry out the chlorine gas separation from the anolyte.
  • a gas separation device can also be provided in the catholyte circuit, for example if it is aligned with the carbon monoxide gas generation by using a cathode containing silver.
  • additional devices for inlets or outlets from the system or additional buffer reservoirs can be provided.
  • anion-membrane is therefore not of pre ⁇ part.
  • the described reduction process for carbon dioxide utilization by means of an electrolysis system comprises the following steps: A catholyte and carbon dioxide is introduced into a cathode space and brought into contact therewith with a cathode. Inside the cathode compartment, this catholyte has alkali cations which migrate through the membrane which separates the anode and cathode compartments. At least part of the Katholytvolumens is introduced into a separation basin, where bicarbonate is an alkali and / or alkaline carbonate auskristalli ⁇ Siert.
  • an anolyte which has chloride anions, introduced into an anode compartment and there brought into contact with an anode, at the anode, the
  • Chloride anions oxidized to chlorine and this separated as chlorine gas via a gas separation device from the anolyte is preferably, this reduction method is performed such that anolyte and catholyte is performed in each case from each other in a ge ⁇ separated circuit, ie two pumps in Provided electrolysis, which cause at least at one point in the circulation transport of the catholyte through the Katho ⁇ denraum and transport of the anolyte through the anode compartment.
  • the circuits are separated from each other by the membrane in the electrolyte, which ideally allows only cation transport from the anode compartment into the cathode compartment.
  • the in the cathode chamber Need Beer ⁇ saturated alkali cations are obtained from the anode chamber.
  • the anolyte preferably has an alkali metal chloride, this can accordingly likewise be used as electrolyte salt but also as electrolysis product.
  • the alkali metal chloride in the anolyte as Elektrolyseedukt and an additional conductive salt, for example, a sulfate, a phosphate et cetera, preferably an alkali metal sulfate, can be used.
  • ammonium salts or their homologues can also be used.
  • Imidazolium salts or other ionic liquids can the selectivity of the electrode, particularly the cathode, posi tive ⁇ influence.
  • the cathode Typically generated in the reduction process in the re ⁇ production of carbon dioxide at the cathode, carbon monoxide, ethylene, methane, ethanol and / or monoethylene glycol.
  • a corresponding cathode is used as a catalyst of these reactions.
  • the cathode preferably has copper for this purpose.
  • the hydroxide ions formed in the reduction of carbon dioxide are converted to hydrogen carbonate ions with excess carbon dioxide.
  • the Hydrogencarbonaterzeugung directly in the cathode compartment has the advantage that they can react directly with existing in the cathode compartment alkali cations to another interesting valuable material, as he would otherwise have to be produced in separate manufacturing processes.
  • a portion of the Katholytvolumens is in particular at least introduced into a deposition tank and ⁇ , preferably where it is cooled by at least 15 K is at least 20 K.
  • the Temperature- is exploited dependence of Carbonatlösige to extract the value ⁇ material from the catholyte.
  • the temperature ⁇ difference of separation tank to electrolyzer may also be more than 30 K, in particular more than 50 K, depending on the present to be extracted alkali metal bicarbonate and also depending on which other salts are present in the cycle.
  • the temperature difference between electrolyzer and separation unit can be between 5 K and 70 K.
  • Hydrogen carbonate product from the catholyte volume the dependence of the solubility of the pH value is exploited.
  • This method can be combined with the temperature-dependent method.
  • the reduction process to at least part of the Katholytvolumens is introduced into a deposition tank and there ⁇ whose pH is less lowered in particular with ⁇ means of injecting carbon dioxide of more than 8 to a pH of 6 or more.
  • Just buffering the pH to a value above 8 in the cathode compartment has the advantage of preventing precipitation of the alkali metal hydrogencarbonate in the cathode compartment itself.
  • the reduction process can be carried out so that the precipitated alkali metal bicarbonate is converted by heating to alkali carbonate. This can be done directly after the crystallization of the bicarbonate in the
  • Separation tanks are made or carried separately from the described electrolysis system.
  • the process can be run in such a way that the pH in the cathode chamber in the upper limit of the reaction to 8 or higher is maintained, so that the equilibrium is shifted to favor nearest ⁇ of sodium carbonate: 2 NaHC0 3 - Na 2 C0 3 + H 2 0 + C0. 2
  • the carbon dioxide feed into the system must be very well controlled to get into and maintain this basic regime.
  • the pH would then be lowered for optimal separation of the sodium bicarbonate by blowing carbon dioxide, and thus shifting the equilibrium reaction again in favor of sodium hydrogen carbonate.
  • the process is not be limited to ⁇ sodium bicarbonate.
  • potassium bicarbonate can also be prepared in this process. Analogous to the described deposition process for sodium bicarbonate and the potassium bicarbonate from a pure Kaliumhydrogen- carbonate electrolyte by lowering the temperature in
  • the separating tank AB preferably crystallized potassium sulfate K 2 S0 4 from which the terminal, that is in circulation direction after Separation tank AB, the electrolyte can be recycled.
  • the volume of electrolyte, the potassium sulfate K 2 S0 4 has been removed, is then, preferably in egg ⁇ nem further separating tank, concentrated, ie the Kaliumhydrogencarbonatties is removed by cooling, for example, the water to obtain the crystalline material.
  • this method is also applicable to other cations or mixtures of cations.
  • the migration of the cations, the catholyte concentrates on so far that the hardest most soluble salt or double ⁇ salt precipitates. It is important that the process of concentration and deposition does not take place in the cathode compartment, that is, not in the electrolysis cell itself, but instead the catholyte is integrated into an electrolysis system
  • Separation tank is transported.
  • the separation in the separating basin is achieved or promoted.
  • a suitable pressure difference between electrolysis cell and the separation tank e.g. Via a temperature, pH or pressure gradient
  • Separation tank can be up to 100 bar. Preferably, a pressure difference between 2 bar and 20 bar would be selected. An increased pressure in the separating basin would be the
  • FIG. 1 shows a schematic illustration of an electrolysis system with carbon dioxide reservoir and separating basin
  • FIG. 2 shows a schematic illustration of an electrolysis system with gas diffusion electrode
  • FIG. 3 shows a schematic representation of a PEM structure of an electrolysis cell
  • FIG. 4 shows a schematic representation of a PEM
  • FIG. 5 shows a schematic illustration of a PEM
  • FIG. 6 shows a Hägg diagram
  • FIG. 1 and 2 Examples of electrolysis systems are shown Carbon Reduction in schematic representation, which can be read as flowcharts for ⁇ be signed reduction process alike.
  • the left side shows the anolyte circuit AK, while the right side shows the catholyte circuit KK.
  • These two circuits AK, KK are connected via the electrolyzer El, E2, whose anode compartment AR and cathode compartment KR are connected to one another via a membrane M or are separated from one another via these.
  • the membrane M a kationenlei ⁇ tend membrane M is preferably employed.
  • an anode A in the cathode space KR, a cathode K is arranged, which are electrically connected via a voltage source U.
  • Both Circuits AK, KK preferably each have a pump PI, P2, which pump the electrolytes through the electrolyzer.
  • devices N1, N2, N3 may be present in both circuits AK, KK at different points in the flow direction, which may be additional inflows or outflows or as buffer reservoirs.
  • a gas separating G2 is ⁇ least provided with a product outlet PA2 over which the product chlorine gas Cl 2 can be removed.
  • a gas separating Gl is provided with product outlet PA1 least the same inlet, of which for example the electrolysis ⁇ product carbon monoxide CO, for example, water ⁇ H 2 material can be removed.
  • other electrolysis products such as ethylene, methane, ethanol, monoethylene glycol can over this or example meadow over another
  • the electrolyzer El, E2 has, for example, a gas diffusion electrode GDE for the carbon dioxide inlet.
  • GDE gas diffusion electrode
  • the carbon dioxide C0 2 is introduced into the electrolyte via a reservoir C0 2 -R and in the direction of circulation in front of the cathode space KR.
  • the catholyte circulation KK has a separation basin AB, which can be integrated directly into the circulation or through which only a part of the catholyte volume is guided.
  • a branch of the circuit can as KK shows ⁇ ge in Figures 1 and 2, may be provided.
  • the separating tank AB or more series-connected separating tank may be connected for example with a cooling device or with a buffer reservoir PR, so that the crystallization of bicarbonate through a ⁇ provide a temperature difference, pressure difference, or pH difference to the electrolyzer El, E2 is favored.
  • the separating basin AB has a product outlet PA3.
  • a plurality of separation basins connected in series would each have a product outlet.
  • electrolysis systems are shown, as they can be used for an embodiment of the invention. Care is taken in this setup that separate anolyte AK and KKK catholyte circuits are present.
  • the electrolytes used are then pumped continuously through the electrolytic cell El, E2, ie through the anode space AR and through the cathode space KR.
  • a pump PI, P2 pre ⁇ see in the structure in each of the two circuits AK, KK in each case a pump PI, P2 pre ⁇ see.
  • the structure can comprise materials made of plastic, plastic-coated metal or glass.
  • Vorratsge ⁇ vessels glass flask can be used, the cell itself is, for example, from PTFE, the tubes made of neoprene.
  • the electrolyzer El, E2 as it is installed in the electrolysis systems shown, may also have a different structure, as shown for example in Figures 3 to 5.
  • An alternative electrolysis cell is the after
  • the electrolysis ⁇ cell can be configured as a PEM half-cell, as shown in Figures 4 and 5, in which the anode side is designed as a PEM half-cell, ie the anode A is arranged in direct contact with the membrane PEM and the anode space AR is arranged on the side facing away from the membrane of the anode A.
  • the cathode K is porous and at least partially gas-permeable and / or electrolyte-permeable.
  • the anode PEM half cell with a gas diffusion electrode GDE is shown in FIG. 4
  • a back-flow cathode K is shown, the cathode space KR is connected via the cathode K with a gas reservoir.
  • the gas reservoir in turn has in this case at least one gas inlet GE and, where appropriate, ⁇ outlet GA.
  • One such embodiment is previously incorporated sets ⁇ for example, as an oxygen-consuming electrode, for example in the production of caustic soda. Then would the cathode K flows behind with oxygen.
  • the oxygen-consuming cathode can be used, for example, to avoid the formation of hydrogen H 2 in the cathode space KR in favor of a reaction towards water H 2 0.
  • the water-forming energy reduces the necessary system voltage U and thus causes a lower energy consumption of the electrolysis system.
  • the cathode K of an oxygen-consuming electrode composed of silver before ⁇ namely, it may also catalyze the oxide reduction Kohlenstoffdi-. If no oxygen to Ver Berg- asked supply, the oxygen-consuming reaction can not take place ⁇ . Instead, the carbon dioxide reduction to carbon monoxide CO takes place with some hydrogen formation. If, for example, sodium is chosen as the alkali metal, the following reactions take place in the cathode space KR when using a copper-containing cathode K:
  • the chlorine gas Cl 2 is formed, as described, by oxidation of the chloride anions Cl ⁇ at the anode A, the other electrolysis products formed at the cathode K or by subsequent reactions in the cathode space KR.
  • the example of sodium is particularly suitable since the sodium bicarbonate can be very easily separated from the electrolyte.
  • sodium bicarbonate and sodium carbonate are important, frequently needed chemical recyclables.
  • Worldwide annual sodium carbonate production is around 50 million tonnes, 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, it can be seen.
  • Table 2 lists further salts, potassium hydrogen carbonate KHCO 3 , potassium sulfate K 2 S0 4 , potassium phosphate K 3 PO 4 , potassium iodide KI, potassium bromide KBr, potassium chloride KCl, sodium hydrogencarbonate NaHCC> 3, sodium sulfate Na 2 SO 4 , which are preferably used can be.
  • other sulfates, Phospha ⁇ te, iodides or bromides can be used to increase the conductivity in the electrolyte.
  • the solubility of sodium bicarbonate NaHCC> 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 NaCC> 3 dissolves comparatively well, with a solubility of 217 g / l at 20 ° C. In continuous electrolysis, therefore, the sodium bicarbonate NaHCC> 3 tends to crystallize in the
  • Electrolysis cell El, E2. This can have an increased tempera ⁇ ture as already produced by the operation of the system and also be counteracted by an appropriate pH Value buffering.
  • the sodium bicarbonate NaHCC> 3 should first crystallize out of the electrolyte in separating tank AB. By pumping the electrolyte into a circuit KK, the sodium bicarbonate NaHCC> 3 formed in the cathode space KR is led out of it and the
  • KK may catholyte by a separating tank AB reciprocated by extending or there is a branch of a Sectionvolu ⁇ mens of the catholyte in a separating tank AB, in which, for example by cooling the electrolyte the Natriumhydrogencar- carbonate NaHCO can be crystallized> 3 and thus recovered.
  • the electrolysis cells E1, E2 in operation by process losses anyway warm up, it can come to the effective crystallization to temperature differences of up to 70 K between the cathode space KR and Ab Abborgebecken. Preference is given to working in a range between 30 K and 50 K Tempe ⁇ temperature difference. In particular with a temperature difference of at least 15 K or even at least 20 K.
  • Electrolytes this must be considered> 3 in the crystallization of the sodium umhydrogencarbonats NaHCO to obtain a mög ⁇ lichst pure product.
  • a hydro ⁇ gensulfat HS0 4 ⁇ or sulfate S0 4 2 ⁇ used as a conductive additive.
  • This may, for example, be sodium sulfate Na 2 S0 4 or sodium hydrogensulfate NaHS0 4 .
  • the solubility of sodium hydrosulfide ⁇ hydrogen sulfate NaHS0 4 is 1080 g / 1 at 20 ° C and that of Natri ⁇ sulfate Na 2 S0 4 is 170 g / 1 at 20 ° C, s. Table 2.
  • Sodium hydrogen carbonate production can replace previously used standard Solvay process.
  • the Solvay process for producing sodium bicarbonate has one major drawback, namely that it consumes very large amounts of water.
  • sodium carbonate Na 2 CC> 3 about one kilogram of unusable Calcium chloride CaCl 2 produced, which is usually discharged into the sewage and thus into rivers and seas.
  • a Jah ⁇ resher ein of 50 million tons of sodium carbonate Na2C03 this is so in about 50 million tons of calcium chloride CaC12.
  • Sodium hydrogen carbonate aHC0 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 extraction. A mining of particularly rich Nahcolith horizons is operated in the state of Colorado. However, the annual production in 2007 was just 93,440 tonnes. It also comes in, for example
  • FIG. 6 shows an example of a Hägg diagram of a 0.05 molar solution of carbon dioxide CO 2 in order to illustrate the dependence on the concentration and pH parameters. Be in a medium pH range

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un système électrolytique comprenant une cellule d'électrolyse, une séparation des côtés anolyte et catholyte, ainsi qu'un dispositif de précipitation et de décharge de carbonate alcalin et/ou d'hydrogénocarbonate alcalin. Le procédé de réduction mentionné permet d'effectuer une valorisation continue de dioxyde de carbone et une génération simultanée de plusieurs matière premières chimiques.
EP16733951.4A 2015-07-03 2016-06-30 Procédé de réduction aux fins de valorisation électrochimique de dioxyde de carbone, de production de carbonate alcalin et d'hydrogénocarbonate alcalin Active EP3292232B1 (fr)

Priority Applications (1)

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PL16733951T PL3292232T3 (pl) 2015-07-03 2016-06-30 Sposób redukcji elektrochemicznej utylizacji dwutlenku węgla, wytwarzanie węglanów metali alkalicznych i wytwarzanie wodorowęglanów metali alkalicznych

Applications Claiming Priority (2)

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DE102015212504.1A DE102015212504A1 (de) 2015-07-03 2015-07-03 Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung
PCT/EP2016/065277 WO2017005594A1 (fr) 2015-07-03 2016-06-30 Système d'électrolyse et procédé de réduction aux fins de valorisation électrochimique de dioxyde de carbone, de production de carbonate alcalin et d'hydrogénocarbonate alcalin

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EP3292232A1 true EP3292232A1 (fr) 2018-03-14
EP3292232B1 EP3292232B1 (fr) 2021-08-11

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US (1) US20180195184A1 (fr)
EP (1) EP3292232B1 (fr)
CN (1) CN107735512B (fr)
DE (1) DE102015212504A1 (fr)
DK (1) DK3292232T3 (fr)
ES (1) ES2897748T3 (fr)
PL (1) PL3292232T3 (fr)
WO (1) WO2017005594A1 (fr)

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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 (fr) * 2017-06-21 2018-12-26 Covestro Deutschland AG Électrode à diffusion de gaz destinée à réduire l'oxyde d'azote
DE102017212278A1 (de) * 2017-07-18 2019-01-24 Siemens Aktiengesellschaft CO2-Elektrolyseur
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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 (fr) * 2018-09-18 2020-03-25 Covestro Deutschland AG Cellule d'électrolyse, électrolyseur et procédé de réduction de co2
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CN113227457A (zh) * 2018-11-28 2021-08-06 欧普斯12股份有限公司 电解装置及使用方法
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EP3805429A1 (fr) * 2019-10-08 2021-04-14 Covestro Deutschland AG Procédé et dispositif d'électrolyse destinés à la fabrication de chlore, de monoxyde de carbone et, le cas échéant, d'hydrogène
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WO2021117164A1 (fr) * 2019-12-11 2021-06-17 日本電信電話株式会社 Appareil de réduction de dioxyde de carbone en phase gazeuse et procédé de réduction de dioxyde de carbone en phase gazeuse
JP7329011B2 (ja) * 2021-03-19 2023-08-17 出光興産株式会社 固体電解質形電解装置、および、そのメンテナンス方法
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DK3292232T3 (da) 2021-10-25
US20180195184A1 (en) 2018-07-12
WO2017005594A1 (fr) 2017-01-12
DE102015212504A1 (de) 2017-01-05
CN107735512B (zh) 2020-06-19
PL3292232T3 (pl) 2022-01-10
ES2897748T3 (es) 2022-03-02
EP3292232B1 (fr) 2021-08-11
CN107735512A (zh) 2018-02-23

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