US20180195184A1 - Electrolytic System And Reduction Method For Electrochemical Carbon Dioxide Utilization, Alkali Carbonate Preparation And Alkali Hydrogen Carbonate Preparation - Google Patents

Electrolytic System And Reduction Method For Electrochemical Carbon Dioxide Utilization, Alkali Carbonate Preparation And Alkali Hydrogen Carbonate Preparation Download PDF

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US20180195184A1
US20180195184A1 US15/739,736 US201615739736A US2018195184A1 US 20180195184 A1 US20180195184 A1 US 20180195184A1 US 201615739736 A US201615739736 A US 201615739736A US 2018195184 A1 US2018195184 A1 US 2018195184A1
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carbon dioxide
cathode
catholyte
alkali metal
space
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Maximilian Fleischer
Philippe Jeanty
Ralf Krause
Erhard Magori
Anna Maltenberger
Sebastian Neubauer
Christian Reller
Bernhard Schmid
Günter Schmid
Elena Volkova
Kerstin Wiesner-Fleischer
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Siemens Energy Global GmbH and Co KG
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Siemens AG
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Publication of US20180195184A1 publication Critical patent/US20180195184A1/en
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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
    • C25B3/04—
    • 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 disclosure relates to electrolysis.
  • the teachings thereof may be embodied in a reduction process and/or an electrolysis system for electrochemical carbon dioxide utilization wherein carbon dioxide is introduced into an electrolysis cell and reduced at a cathode.
  • Natural carbon dioxide degradation proceeds, for example, via photosynthesis. This involves conversion of carbon dioxide to carbohydrates in a process subdivided into many component steps over time and, at the molecular level, in terms of space. As such, this process cannot easily be adapted to the industrial scale. No copy of the natural photosynthesis process with photocatalysis on the industrial scale to date has had adequate efficiency.
  • reaction products As can also be inferred from table 1, at a copper cathode for instance, a multitude of hydrocarbons are formed as reaction products.
  • One aspect of particular economic interest is, for example, the electrochemical production of methane or ethylene, ethanol or monoethylene glycol. These are higher-energy products than carbon dioxide.
  • an improved solution for the electrochemical utilization of carbon dioxide would avoid the disadvantages known from the prior art. More particularly, the solution may enable continuous carbon dioxide conversion.
  • the teachings of the present disclosure may provide an improved reduction process and electrolysis system for carbon dioxide utilization.
  • some embodiments may include electrolysis systems for carbon dioxide utilization, comprising an electrolyzer (E 1 -E 5 ) having an anode (A) in an anode space (AR) and a cathode (K) in a cathode space (KR).
  • the cathode space (KR) has at least one entrance for carbon dioxide (CO 2 ) and is configured to bring the carbon dioxide (CO 2 ) that has entered into contact with the cathode (K).
  • the cathode space (KR) comprises or can accommodate a catholyte which can enter the cathode space (KR) through the same entrance or a separate entrance and which includes alkali metal cations.
  • the anode space (AR) has at least one entrance for an anolyte and comprises an anolyte or can accommodate it via this entrance, wherein the anolyte includes chlorine anions.
  • a deposition tank (AB), wherein the deposition tank (AB) is configured for crystallization of an alkali metal hydrogencarbonate and/or alkali metal carbonate out of the catholyte and has a product outlet (PA3).
  • the deposition tank (AB) has a cooling apparatus.
  • At least one reservoir (PR) is configured and arranged with connection to the cathode space (KR) and/or the deposition tank (AB) such that it serves to buffer the catholyte.
  • the catholyte comprises at least one solvent, especially water.
  • the anolyte includes at least one water-soluble alkali metal salt.
  • the anode space (AR) is connected to a gas separation unit for separation of chlorine gas from the anolyte.
  • anode space (AR) and cathode space (KR) are separated from one another by a cation-conducting membrane (M).
  • some embodiments may include a reduction process for carbon dioxide utilization by means of an electrolysis system as described above.
  • a catholyte and carbon dioxide (CO 2 ) are introduced into a cathode space (KR) and brought into contact with a cathode (K). Carbon dioxide (CO 2 ) is reduced at the cathode (K).
  • An anolyte including chloride anions (Cl ⁇ ) is introduced into an anode space (AR) and brought into contact with an anode (A). Chloride anions (Cl ⁇ ) are oxidized at the anode (A) to chlorine (Cl 2 ) and the latter is separated from the anolyte as chlorine gas by means of a gas separation unit.
  • the anolyte includes alkali metal cations that migrate into the catholyte. At least a portion of the catholyte volume is introduced into a deposition tank, where an alkali metal hydrogencarbonate and/or alkali metal carbonate crystallizes out.
  • the hydroxide ions (OH ⁇ ) formed in the carbon dioxide reduction are converted to hydrogencarbonate ions (HCO 3 ⁇ ) with carbon dioxide (CO 2 ) present in excess.
  • At least a portion of the catholyte volume is introduced into a deposition tank, where it is cooled down by at least 15 kelvin, preferably at least 20 kelvin.
  • At least a portion of the catholyte volume is introduced into a deposition tank, where the pH thereof is lowered from above 8 to a pH of 6 or less by blowing in carbon dioxide (CO 2 ).
  • At least a portion of the catholyte volume is introduced into a deposition tank, where an alkali metal hydrogencarbonate is crystallized and is subsequently converted to an alkali metal carbonate by heating.
  • FIG. 1 shows a schematic diagram of an electrolysis system with a carbon dioxide reservoir and deposition tank, according to teachings of the present disclosure
  • FIG. 2 shows a schematic diagram of an electrolysis system with a gas diffusion electrode, according to teachings of the present disclosure
  • FIG. 3 shows a schematic diagram of a PEM setup of an electrolysis cell, according to teachings of the present disclosure
  • FIG. 4 shows a schematic diagram of a PEM half-cell coupled to a gas diffusion electrode, according to teachings of the present disclosure
  • FIG. 5 shows a schematic diagram of a PEM half-cell coupled to a cathode with backflow, according to teachings of the present disclosure.
  • FIG. 6 shows a Hagg diagram
  • the electrolysis system of the present disclosure may allow improved carbon dioxide utilization.
  • Some embodiments include at least one electrolyzer having an anode in an anode space and a cathode in a cathode space.
  • the cathode space has at least one entrance for carbon dioxide and is configured to bring the carbon dioxide that has entered into contact with the cathode.
  • the cathode space comprises a catholyte or is configured to be able to accommodate a catholyte.
  • the catholyte can access the cathode space through the same entrance as the carbon dioxide or via a separate second entrance.
  • At least the anode space also includes alkali metal cations in the operation of the cell anode and cathode space.
  • Catholyte refers to an electrolyte which directly affects the cathode in the electrolysis.
  • anolyte when referring to an electrolyte directly affecting the anode in an electrolysis.
  • Alkali metal cations refer to positively charged ions having at least one element of the first main group of the Periodic Table.
  • the anode space of the electrolyzer has at least one entrance for an anolyte and comprises an anolyte or is at least configured to accommodate an anolyte via this entrance, said anolyte including chlorine anions.
  • the anode space and the cathode space are separated from one another by a membrane.
  • the membrane here may include at least one mechanically separating layer, for example a diaphragm, which separates the electrolysis products formed in the anode space and cathode space from one another. They could then also be referred to as separator membrane or separation layer.
  • the membrane may have a high bubble point of 10 mbar or higher.
  • the “bubble point” is a defining parameter for the membrane used, which describes the pressure difference ⁇ P between the two sides of the membrane from which gas flow through the membrane would set in.
  • the membrane may also be a proton- or cation-conducting or -permeable membrane. While molecules, liquids or gases are being separated, proton or cation flow from the anode space to the cathode space is assured.
  • the membrane comprises sulfonated polytetrafluoroethylene, e.g. Nafion.
  • the electrolysis system further comprises at least one deposition tank for crystallization of an alkali metal hydrogencarbonate and/or alkali metal carbonate out of the catholyte.
  • this deposition tank has a product outlet. According to the product, whether an alkali metal hydrogencarbonate and/or alkali metal carbonate is to be taken from the catholyte, and according to the alkali metal, a second deposition tank may also be provided for a crystallization process. The latter is then typically arranged downstream of the first deposition tank in catholyte circulation direction.
  • the reduction of carbon dioxide gives rise to different products: for example, carbon monoxide, ethylene, methane, ethanol, or monoethylene may be formed.
  • hydroxide ions also form, which may be neutralized to hydrogencarbonate by excess carbon dioxide.
  • the source of the alkali metal cations is in the anode space. A cation stream through the membrane compensates for the electrical current resulting from the voltage applied.
  • the alkali metal cations and the chloride anions may be metered into the anolyte in the form of a chloride salt. While the chloride anions are oxidized at the anode to chlorine and leave the anolyte circuit as chlorine gas, the alkali metal cations migrate through the membrane into the catholyte circuit, where they react in the cathode space with the carbonate or hydrogencarbonate formed there to give an alkali metal carbonate or alkali metal hydrogencarbonate and may leave the catholyte circuit via the separate product outlet of the deposition tank.
  • the electrolysis systems of the present disclosure may have produce not only chlorine but at least one alkali metal carbonate and/or alkali metal hydrogencarbonate as a chemical material of value. Whether alkali metal carbonate or alkali metal hydrogencarbonate is formed depends, for example, on the alkali metal and the utilization method. In aqueous solution, for instance, the solubility is crucial. The sparingly soluble carbonate or hydrogencarbonate crystallizes out. In the case of sodium and potassium it is the hydrogencarbonate 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 in which carbon monoxide and, in a direct manner, sodium carbonate Na 2 CO 3 are produced.
  • the electrolysis system may utilize carbon dioxide and it is thus also typically possible to provide at least one third material of value, for example carbon monoxide, ethylene, methane, ethanol or monoethylene glycol.
  • the exploitation of the compensating current of the cations thus creates an electrolysis system which enables continuous hydrogencarbonate production.
  • 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 especially neutralized by excess carbon dioxide to hydrogencarbonate (HCO 3 ⁇ ).
  • This firstly has the effect that the pH in the cathode space is thus buffered within a pH range from 6 to 8. It also has the effect that the electrolyte concentration rises considerably. But if the catholyte is conducted into a catholyte circuit, i.e. pumped into the cathode space and led out of it again, the hydrogencarbonate formed in the cathode space can be taken from the catholyte.
  • at least one pump in each case may be arranged in the catholyte circuit, or else, for example, in the anolyte circuit, and this ensures electrolyte circulation.
  • alkali metal cations present in the cathode space come from the anode space, into which they were initially introduced especially in the form of alkali metal chloride as oxidation reactant or in the form of another alkali metal salt, for increasing the conductivity for example.
  • the alkali metal cations in the anode space may be replenished in the form of alkali metal chloride.
  • the membrane between the anode space and cathode space may be chosen such that the cation flow from the anode space toward the cathode in the electrical field of the electrolyzer is assured.
  • the effect of the temperature and also pH dependence of the solubility of alkali metal hydrogencarbonates is then that different processes for crystallization or for withdrawal from the catholyte are undertaken:
  • the deposition tank may comprise a cooling apparatus, by means of which the catholyte is cooled down by several degrees Kelvin compared to the temperature range that prevails in the electrolyzer.
  • the temperature difference set from the deposition tank to the electrolyzer is at least 15 K, especially at least 20 K.
  • a temperature difference between 30 K and 50 K may also be particularly suitable.
  • the temperature difference between the electrolyzer and deposition tank may be within a temperature range between 5 K and 70 K.
  • the lowering of the temperature in the deposition tank may provide cooling in the catholyte circuit precedes the recycling of the catholyte into the cathode space.
  • excessively high systemic evolution of heat, specifically in the electrolyzer is avoided.
  • pH buffers provided, for example, in a buffer reservoir to the deposition tank and/or to the catholyte circuit and/or to the cathode space, to correspondingly buffer the catholyte volume.
  • the pH of the catholyte can also be employed as such for the control of the operation of deposition of the alkali metal hydrogencarbonate out of the electrolyte.
  • the pH in the cathode space is at first kept at a higher value, for example 8 or higher. This can shift the equilibrium in favor of the alkali metal carbonate and away from the alkali metal hydrogencarbonate.
  • the pH is then lowered, e.g., to a value of 6 or less, which leads to formation and crystallization of the alkali metal hydrogencarbonate.
  • the lowering of the pH is typically accomplished by blowing carbon dioxide into the deposition tank.
  • alkali metal hydrogencarbonate or an alkali metal carbonate it is at first possible to form an alkali metal hydrogencarbonate or an alkali metal carbonate. More particularly, the two procedures described for withdrawal of the desired product from the catholyte can also be combined. In some cases, for example in the case of formation of sodium hydrogencarbonate NaHCO 3 , it is also possible, for example, to obtain the sodium carbonate Na 2 CO 3 subsequently from the sodium hydrogencarbonate NaHCO 3 that has crystallized out by heating. In that case, hydrogencarbonate may be first produced and deposited, and subsequently the desired proportion thereof is processed further to give carbonate.
  • the pH dependence of the hydrogencarbonate or carbonate ions is shown, for example, in FIG. 6 in a Hagg diagram for a sodium carbonate solution.
  • a buffer reservoir may be provided in the anolyte circuit, which can especially also serve for introduction or replenishment of alkali metal chloride into the electrolyte, to maintain the salt content in the anolyte.
  • the catholyte includes at least one solvent, especially water.
  • aqueous electrolytes and correspondingly water-soluble conductive salts may be employed.
  • the conductive salt content can be increased by the addition of further carbonates, hydrogencarbonates, but also sulfates or other conductive salts, to increase the conductivity of the electrolyte in the catholyte circuit and also in the anolyte circuit, which leads to an increase in the conversion of matter in the overall system.
  • the crystallization process is adjusted correspondingly to extract the desired product with maximum purity.
  • Conductive salts used may be chosen such that the solubility thereof differs significantly from that of the alkali metal hydrogencarbonate or the alkali metal carbonate.
  • the electrolysis system has a gas separation unit on the anolyte side, which is configured to undertake the separation of chlorine gas from the anolyte.
  • a gas separation unit may be provided, for example when it is directed to carbon monoxide gas production via use of a silver-containing cathode.
  • additional units for inlets or outlets from the system or additional buffer reservoirs may be provided.
  • the nature and quality of the membrane used in the electrolyzer ultimately makes a significant contribution to how pure the crystallized product is. If the membrane used is merely a separator, it is also possible, for example, for chloride anions to diffuse into the cathode space, even counter to the electrical field in the electrolyzer, such that not only hydrogencarbonate but possibly also chlorides are formed. Therefore, in some embodiments, there is a cation-conducting membrane through which virtually exclusively cations can pass. A purely anion-conducting membrane may be less useful.
  • the reduction process described for carbon dioxide utilization by means of an electrolysis system as described above comprises the following steps: a catholyte and carbon dioxide are introduced into a cathode space, where they are contacted with a cathode. Within the cathode space, this catholyte includes alkali metal cations which migrate through the membrane that separates anode space and cathode space. At least a portion of the catholyte volume may be introduced into a deposition tank, where an alkali metal hydrogencarbonate and/or an alkali metal carbonate crystallizes out.
  • an anolyte including chloride anions is brought into contact with an anode.
  • the chloride anions are oxidized at the anode to chlorine and the latter is separated from the anolyte as chlorine gas by means of a gas separation unit.
  • this reduction process is effected such that anolyte and catholyte are each conducted into a separate circuit, meaning that two pumps are provided in the electrolysis system, which bring about transport of the catholyte through the cathode space and transport of the anolyte through the anode space at least at one point in the circuit.
  • the circuits are separated from one another by the membrane in the electrolyzer, which may permit exclusively transport of cations from the anode space into the cathode space. More particularly, the alkali metal cations required in the cathode space may be obtained from the anode space.
  • the anolyte may include an alkali metal chloride; the latter may be used as conductive salt, or else likewise as electrolysis reactant.
  • the alkali metal chloride in the anolyte can be used as electrolysis reactant, and an additional conductive salt, for example a sulfate, a phosphate et cetera, e.g, an alkali metal sulfate, can be used.
  • an additional conductive salt for example a sulfate, a phosphate et cetera, e.g, an alkali metal sulfate, can be used.
  • the reduction of the carbon dioxide at the cathode produces carbon monoxide, ethylene, methane, ethanol and/or monoethylene glycol.
  • an appropriate cathode may be used as catalyst for these reactions.
  • the cathode may include copper.
  • this reduction process produces, in addition to carbon dioxide utilization, chemical substances of value.
  • the hydroxide ions formed in the carbon dioxide reduction can be converted to hydrogencarbonate ions with carbon dioxide present in excess. Hydrogencarbonate production directly in the cathode space allows these to react further directly with alkali metal cations present in the cathode space to give a further material of value which is of interest, which would otherwise have to be produced in separate production processes.
  • to withdraw this material of value from the system at least a portion of the catholyte volume is introduced into a deposition tank, where it is cooled down by at least 15 K, and/or by at least 20 K.
  • the temperature dependence of the carbonate solubility is thus exploited to withdraw the material of value from the catholyte circuit.
  • the temperature differential from deposition tank to electrolyzer may also be more than 30 K, especially also more than 50 K, according to the present alkali metal hydrogencarbonate to be extracted and also depending on which further salts are present in the circuit.
  • the temperature differential between electrolyzer and deposition unit may be between 5 K and 70 K.
  • the dependence of the solubility on the pH is exploited. This process can be combined with the temperature-dependent process.
  • At least a portion of the catholyte volume is introduced into a deposition tank, where the pH thereof is lowered, especially by means of blowing in carbon dioxide, from above 8 to a pH of 6 or less.
  • the buffering of the pH to a value of more than 8 in the cathode space prevents the precipitation of the alkali metal hydrogencarbonate in the cathode space itself.
  • the reduction process can be undertaken such that the precipitated alkali metal hydrogencarbonate is converted to alkali metal carbonate by heating. This can be effected directly after the crystallization of the hydrogencarbonate in the deposition tank or separately from the electrolysis system described.
  • the process can also be run such that the pH in the cathode space is kept at the upper limit of the reaction of around 8 or higher, such that the equilibrium is at first shifted in favor of sodium carbonate:
  • the carbon dioxide supply to the system must be very well controlled, to arrive at and maintain this basic regime.
  • the pH would then be lowered for optimal deposition of the sodium hydrogencarbonate by blowing in carbon dioxide, and hence the equilibrium reaction would again be shifted in favor of sodium hydrogencarbonate.
  • the process is not restricted to sodium hydrogencarbonate.
  • Analogously to the deposition process described for sodium hydrogencarbonate it is also possible to crystallize the potassium hydrogencarbonate out of a pure potassium hydrogencarbonate electrolyte by lowering the temperature in the deposition tank. At 20° C. the solubility of potassium hydrogencarbonate is 337 g/l, and at 60° C. it is 600 g/l.
  • potassium sulfate K 2 50 4
  • K 2 50 4 potassium sulfate
  • KHCO 3 potassium hydrogencarbonate
  • the electrolyte volume from which the potassium sulfate K 2 SO 4 has already been removed is then concentrated, preferably in a further deposition tank, meaning that the water is removed from the potassium hydrogencarbonate solution, for example by cooling, to obtain the crystalline material.
  • this process is also applicable to other cations or mixtures of cations.
  • the migration of the cations results in concentration of the catholyte to such an extent that the most sparingly soluble salt or double salt separates out. It is important here that the process of concentration and deposition does not proceed in the cathode space, i.e. not in the electrolysis cell itself, but that the catholyte is transported for the purpose into a deposition tank integrated within the electrolysis system.
  • a deposition tank integrated within the electrolysis system.
  • a suitable pressure differential between electrolysis cell and deposition tank may be up to 100 bar.
  • a pressure differential between 2 bar and 20 bar would preferably be chosen.
  • An elevated pressure in the deposition tank would promote hydrogencarbonate formation.
  • FIGS. 1 and 2 show, in a schematic representation, examples of electrolysis systems for carbon dioxide reduction, which can equally be read as flow diagrams for the reduction process described. Shown on the left-hand side in each case is the anolyte circuit AK, and on the right-hand side the catholyte circuit KK. These two circuits AK, KK are connected via the electrolyzer E 1 , E 2 , the anode space AR and cathode space KR of which are connected to one another and separated from one another by means of a membrane M.
  • the membrane M used may be a cation-conducting membrane M.
  • In the anode space AR is disposed an anode A, and in the cathode space KR a cathode K, which are electrically connected by a voltage source U.
  • Each of the circuits AK, KK may include a pump P 1 , P 2 , which pump the electrolytes through the electrolyzer.
  • units N 1 , N 2 , N 3 in the two circuits AK, KK may be present at different points in the flow direction, which may be additional inlets or outlets or in the form of buffer reservoirs.
  • at least one gas separation unit G 2 with a product outlet PA 2 is provided, by means of which the chlorine gas product Cl 2 can be withdrawn.
  • the catholyte circuit KK is at least one gas separation unit G 1 with a product outlet PA 1 , by means of which, for example, the carbon monoxide electrolysis product CO, and, for example, hydrogen H 2 as well can be withdrawn.
  • further electrolysis products such as ethylene, methane, ethanol, monoethylene glycol, to be withdrawn from the system via this or, for example, via a further product outlet.
  • the electrolyzer E 1 , E 2 has, for example, a gas diffusion electrode GDE for the carbon dioxide inlet.
  • the carbon dioxide CO 2 is introduced into the electrolyte via a reservoir CO 2 —R and upstream of the cathode space KR in circulation direction.
  • the catholyte circuit KK in both cases shown, has a deposition tank AB which may be incorporated directly into the circuit or through which just a portion of the catholyte volume is conducted. For this purpose, as shown in FIGS. 1 and 2 , a branch in the circuit KK may be provided.
  • the deposition tank AB or a plurality of series-connected deposition tanks may be connected, for example, to a cooling unit or to a buffer reservoir PR, such that the crystallization of the hydrogencarbonate is promoted by establishing a temperature differential, pressure differential or pH differential with respect to the electrolyzer E 1 , E 2 .
  • the deposition tank AB may include a product outlet PA 3 . Multiple series-connected deposition tanks would each have a product outlet.
  • FIGS. 1 and 2 thus show electrolysis systems usable for the methods described herein.
  • the electrolytes used are then pumped continuously through the electrolysis cell E 1 , E 2 , i.e. through the anode space AR and through the cathode space KR.
  • one pump P 1 , P 2 is provided in each of the two circuits AK, KK.
  • the setup may include materials made of plastic, plastic-coated metal or glass. Reservoir vessels used may be glass flasks; the cell itself is made, for example, of PTFE, and the hoses of neoprene.
  • the electrolyzer E 1 , E 2 may also have a different setup as shown, for example, in FIGS. 3 to 5 .
  • An alternative electrolysis cell is that according to the polymer electrolyte membrane setup (PEM setup). In this case, at least one electrode directly adjoins the polymer electrolyte membrane PEM.
  • the electrolysis cell can be configured as a PEM half-cell, as shown in FIGS. 4 and 5 , in which the anode side is configured as a PEM half-cell, i.e. 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 porous and at least partly 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 with backflow the cathode space KR of which is connected to a gas reservoir via the cathode K.
  • the gas reservoir here, for its part, has at least one gas inlet GE and optionally a gas outlet GA.
  • Such an embodiment has been used to date, for example, as an oxygen-depolarized electrode, for example in the production of sodium hydroxide solution.
  • the oxygen-depolarized cathode can be used, for example, to avoid hydrogen formation H 2 in the cathode space KR in favor of a reaction to give water H 2 O.
  • the energy of water formation here lowers the necessary system voltage U and thus brings about lower energy consumption of the electrolysis system.
  • the cathode K of an oxygen-depolarized electrode consists primarily of silver, it can also catalyze carbon dioxide reduction. If no oxygen is provided, the oxygen-consuming reaction cannot proceed. Instead, carbon dioxide reduction to carbon monoxide CO takes place with a certain degree of hydrogen formation.
  • the example of sodium may be suitable since sodium hydrogencarbonate can be deposited very efficiently from the electrolyte. Moreover, sodium hydrogencarbonate and sodium carbonate are important chemical materials of value that are frequently required. Global annual sodium carbonate production is about 50 000 000 metric tons, as can be inferred for example from the Roskill market report “Soda Ash: Market Outlook to 2018”, available from Roskill Information Services Ltd, E-Mail: info@roskill.co.uk, www.roskill.co.uk/soda-ash.
  • Table 2 lists further salts, potassium hydrogencarbonate KHCO 3 , potassium sulfate K 2 SO 4 , potassium phosphate K 3 PO 4 , potassium iodide KI, potassium bromide KBr, potassium chloride KCl, sodium hydrogencarbonate NaHCO 3 , sodium sulfate Na 2 SO 4 , which can be used with preference. But other sulfates, phosphates, iodides or bromides can also be used to increase the conductivity in the electrolyte. By constantly supplying the carbon dioxide, it is not necessary to supply carbonates or hydrogencarbonates; instead, they are formed in operation in the cathode space KR.
  • the solubility of sodium hydrogencarbonate 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 by contrast, has comparatively good solubility; the solubility thereof is 217 g/l at 20° C.
  • the sodium hydrogencarbonate NaHCO 3 thus has a tendency to crystallize out in the electrolysis cell E 1 , E 2 . This can be counteracted via an elevated temperature as arises as a result of the operation of the system, and also via corresponding buffering of the pH.
  • the sodium hydrogencarbonate NaHCO 3 is not supposed to crystallize out of the electrolyte until within the deposition tank AB.
  • the sodium hydrogencarbonate NaHCO 3 formed in the cathode space KR is conducted out of it and the catholyte circuit KK can run through a deposition tank AB, or a part-volume of the catholyte is branched into a deposition tank AB in which, for example, the sodium hydrogencarbonate NaHCO 3 crystallizes out as a result of the cooling of the electrolyte and can thus be recovered.
  • the electrolysis cells E 1 , E 2 are in any case heated significantly in operation as a result of process losses, there can be effective crystallization at temperature differentials of up to 70 K between cathode space KR and deposition tank AB. Preference is given to working within a range between temperature differential 30 K and 50 K. Especially with a temperature differential of at least 15 K or even at least 20 K.
  • a hydrogensulfate HSO 4 ⁇ or sulfate SO 4 2 ⁇ is included as a conductive additive. This may, for example, be sodium sulfate Na 2 SO 4 or sodium hydrogensulfate NaHSO 4 .
  • the solubility of sodium hydrogensulfate NaHSO 4 is 1080 g/l at 20° C.
  • sodium sulfate Na 2 SO 4 is 170 g/l at 20° C.; see table 2. Given this great difference in solubility from sodium hydrogencarbonate NaHCO 3 , it is assured that sodium hydrogencarbonate NaHCO 3 will crystallize out preferentially in the deposition tank.
  • This variant of the reduction process may basically replace the Solvay process that has been used as standard to date for sodium hydrogencarbonate production.
  • the Solvay process for sodium hydrogencarbonate production has a great disadvantage, namely that it consumes very large amounts of water.
  • about one kilogram of unusable calcium chloride CaCl 2 is also produced, which is usually released into the wastewater and hence into rivers and seas. Given an annual production of 50 million metric tons of sodium carbonate Na 2 CO 3 , this is thus about 50 million metric tons of calcium chloride CaCl 2 .
  • Sodium hydrogencarbonate NaHCO 3 occurs as the natural mineral nahcolite in the United States of America. It usually occurs in fine distribution in oil shale and can then be produced as a by-product of oil production. Particularly rich nahcolite horizons are being mined in the state of Colorado. However, annual production in 2007 was only 93 440 metric tons.
  • FIG. 6 shows, for illustration of the dependence on the concentration and pH parameters, an example of a Hagg diagram of a 0.05 molar solution of carbon dioxide CO 2 .
  • carbon dioxide CO 2 and salts thereof are present alongside one another.
  • carbon dioxide CO 2 under strongly basic conditions preferentially takes the form of carbonate CO 3 2 ⁇ and preferentially takes the form of hydrogencarbonate HCO 3 ⁇ in the moderate pH region, the hydrogencarbonate ions are driven out of the solution in the form of carbon dioxide CO 2 at low pH values in an acidic medium.

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US11932954B2 (en) 2017-05-22 2024-03-19 Siemens Energy Global GmbH & Co. KG Two-membrane construction for electrochemically reducing CO2
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