WO2023006493A1 - Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse - Google Patents

Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse Download PDF

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Publication number
WO2023006493A1
WO2023006493A1 PCT/EP2022/070140 EP2022070140W WO2023006493A1 WO 2023006493 A1 WO2023006493 A1 WO 2023006493A1 EP 2022070140 W EP2022070140 W EP 2022070140W WO 2023006493 A1 WO2023006493 A1 WO 2023006493A1
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Prior art keywords
electrolytic cell
partition
chamber
solid electrolyte
solution
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PCT/EP2022/070140
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German (de)
English (en)
Inventor
Philip Heinrich REINSBERG
Michael Horn
Original Assignee
Evonik Functional Solutions Gmbh
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Application filed by Evonik Functional Solutions Gmbh filed Critical Evonik Functional Solutions Gmbh
Priority to KR1020247003288A priority Critical patent/KR20240034777A/ko
Priority to CN202280052861.7A priority patent/CN117813419A/zh
Priority to EP22751379.3A priority patent/EP4377498A1/fr
Publication of WO2023006493A1 publication Critical patent/WO2023006493A1/fr

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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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms

Definitions

  • Fracture-resistant partition wall comprising solid electrolyte ceramics for electrolytic cells
  • the present invention relates to an electrolytic cell E comprising a partition wall W which is suitable for use in an electrolytic cell E.
  • the partition W comprises at least two alkali cation-conducting solid electrolyte ceramics F A and F B , which are separated from one another by at least one separating element T.
  • the partition wall W comprises the solid electrolyte in one piece, this arrangement is more flexible and the individual ceramics have more degrees of freedom to react to temperature fluctuations, for example by shrinking or expanding. This increases the stability against mechanical stresses in the ceramic.
  • the electrolytic cell E comprises a cathode chamber K K , which is separated by the partition wall W from the adjacent chamber, which is a middle chamber K of the electrolytic cell E.
  • the present invention relates to a method for producing an alkali metal alkoxide solution in the electrolytic cell E according to the first aspect of the invention.
  • the electrochemical production of alkali metal alkoxide solutions is an important industrial process, which is described, for example, in DE 10360758 A1, US 2006/0226022 A1 and WO 2005/059205 A1.
  • the principle of this process is reflected in an electrolytic cell in whose anode chamber there is a solution of an alkali salt, for example common salt or NaOH, and in whose cathode chamber there is the alcohol in question or a low-concentration alcoholic solution of the alkali metal alcoholate in question, for example sodium methoxide or sodium ethoxide.
  • the cathode compartment and the anode compartment are separated by a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
  • WO 2014/008410 A1 describes an electrolytic process for producing elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from T1O2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally electrolytically converted to elemental titanium and sodium alcoholate.
  • WO 2007/082092 A2 and WO 2009/059315 A1 describe processes for the production of
  • Biodiesel in which triglycerides are first converted into the corresponding alkali metal triglycerides with the aid of alcoholates electrolytically produced via NaSICON and, in a second step, are converted to glycerol and the respective alkali metal hydroxide with electrolytically generated protons.
  • leaks can occur, which can lead to leakage of brine into alcohol or vice versa.
  • the product of the electrolysis - the alcoholate solution - is diluted.
  • the electrolytic cell itself can leak and leak.
  • the object of the present invention was therefore to provide an electrolytic cell which does not have these disadvantages.
  • WO 2012/048032 A2 and US 2010/0044242 A1 describe, for example, electrochemical methods for producing sodium hypochlorite and similar chlorine compounds in such a three-chamber cell.
  • the cathode chamber and the middle chamber of the cell are separated by a cation-permeable solid electrolyte such as NaSICON.
  • the middle chamber is supplied with solution from the cathode chamber, for example.
  • US 2010/0044242 A1 also describes in Figure 6 that solution from the middle chamber can be mixed with solution from the anode chamber outside the chamber in order to obtain sodium hypochlorite.
  • US Pat. No. 5,389,211 A describes a process for purifying alkoxide solutions in which a three-chamber cell is used, in which the chambers are separated from one another by cation-selective solid electrolytes or non-ionic partitions.
  • the middle chamber is used as a buffer chamber to prevent the cleaned
  • Alkoxide or hydroxide solution from the cathode compartment mixes with the contaminated solution from the anode compartment.
  • DE 4233191 A1 describes the electrolytic production of alkoxides from salts and alkoxides in multi-chamber cells and stacks of several cells.
  • WO 2008/076327 A1 describes a process for preparing alkali metal alkoxides.
  • a three-chamber cell is used, the middle chamber of which is filled with alkali metal alkoxide (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1).
  • WO 2009/073062 A1 describes a process for preparing alkali metal alkoxides.
  • this arrangement has the disadvantage that the alkali metal alkoxide solution, which is consumed as a buffer solution and is continuously contaminated, is the desired product.
  • the center chamber is in such a chamber by a diffusion barrier from the anode chamber and by a ion-conducting ceramic separated from the cathode chamber.
  • This inevitably leads to the formation of pH gradients and dead volumes. This can damage the ion-conducting ceramic and consequently increase the voltage requirement of the electrolysis and/or lead to breakage of the ceramic.
  • a further object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide and an electrolytic cell which is particularly suitable for such a process.
  • an electrolytic cell E ⁇ 1> comprising a partition W.
  • the partition wall W ⁇ 16> comprises a side SKK ⁇ 161> with the surface OKK ⁇ 163> and a side SA/MK ⁇ 162> opposite the side SKK ⁇ 161> with the surface OA/MK ⁇ 164>. It also comprises at least two alkali cation-conducting solid electrolyte ceramics F A ⁇ 18> and F B ⁇ 19>, separated from one another by at least one separating element T ⁇ 17>.
  • the alkali cation-conducting solid electrolyte ceramics enclosed by the dividing wall W ⁇ 16>, and in particular also the separating element T ⁇ 17>, can be contacted directly both via the surface OKK ⁇ 163> and via the surface OA/MK ⁇ 164>.
  • the present invention accordingly relates to an electrolytic cell E ⁇ 1>, comprising at least one anode chamber KA ⁇ 11> with at least one inlet ZKA ⁇ 110>, at least one outlet AKA ⁇ 111> and an interior IKA ⁇ 112>, the comprises an anodic electrode E A ⁇ 113>, at least one cathode chamber K K ⁇ 12> with at least one inlet ZKK ⁇ 120>, at least one outlet AKK ⁇ 121> and an interior space I K K ⁇ 122>, which comprises a cathodic electrode E K ⁇ 123>, and at least one in between Central chamber K ⁇ 13> with at least one inlet ZKM ⁇ 130>, at least one outlet A K M ⁇ 131> and an interior space I K M ⁇ 132>, with IKA ⁇ 112> and I K M ⁇ 132> then through a diffusion barrier D ⁇ 14> are separated from one another, and A K M ⁇ 131> is connected to the inlet Z K A ⁇ 110> by
  • IKK ⁇ 122> and I K M ⁇ 132> are separated from one another by the dividing wall W ⁇ 16>, characterized in that the alkali cation-conducting solid electrolyte ceramics enclosed by the dividing wall W ⁇ 16>, and in particular also the separating element T ⁇ 17>, the interior Contact IKK ⁇ 122> directly on the side S K K ⁇ 161> via the surface OKK ⁇ 163>, and the alkali cation-conducting solid electrolyte ceramics enclosed by the partition W ⁇ 16>, and in particular the separating element T ⁇ 17>, the interior I K Contact M ⁇ 132> on the S A /MK ⁇ 162> side directly via the OA/MK ⁇ 164> interface.
  • the present invention relates to a method for preparing a solution Li of an alkali metal alcoholate XOR in the alcohol ROH, where X is an alkali metal cation and R is an alkyl radical having 1 to 4 carbon atoms, in an electrolytic cell E according to the first aspect of the invention, the following simultaneous steps (ß1), (ß2), (ß3) are carried out:
  • aqueous solution L 3 of a salt S comprising X as a cation is passed through K , then via V A M , then through K A ,
  • FIG. 1A shows an electrolytic cell E not according to the invention. This comprises a cathode chamber K K ⁇ 12> and an anode chamber K A ⁇ 11>.
  • the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior I K K ⁇ 122>, an inlet Z K K ⁇ 120> and an outlet AKK ⁇ 121>.
  • the anode chamber K A ⁇ 11> comprises an anodic electrode E A ⁇ 113> in the interior I KA ⁇ 112>, an inlet Z K K ⁇ 110> and an outlet A KA ⁇ 111>.
  • the two chambers are delimited by an outer wall ⁇ 80> of the two-chamber cell E.
  • the interior I K K ⁇ 122> is also separated from the interior I KA ⁇ 112> by a dividing wall, which consists of a disc of a NaSICON solid electrolyte FA ⁇ 18> that is selectively permeable for sodium ions.
  • the NaSICON solid electrolyte F A ⁇ 18> extends over the entire depth and height of the two-chamber cell E.
  • the partition has two sides S K K ⁇ 161> and S VMK ⁇ 162>, whose surfaces are OKK ⁇ 163> and O VMK ⁇ 164> contact the respective interior I K K ⁇ 122> or I KA ⁇ 112>.
  • An aqueous solution of sodium chloride L 3 ⁇ 23> with a pH of 10.5 is fed counter to gravity into the interior space l KA ⁇ 112> via the inlet Z KA ⁇ 110>.
  • a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior I K K ⁇ 122> via the inlet Z K K ⁇ 120>.
  • a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
  • methanol in the electrolyte L 2 ⁇ 22> is reduced to methoxide and H 2 (CH 3 OH + e- - CH 3 0 _ + 1 H 2 ).
  • Sodium ions diffuse from the inner space l KA ⁇ 112> through the NaSICON solid electrolyte FA ⁇ 18> into the inner space I K K ⁇ 122>.
  • Chlorine gas CI2 forms hypochlorous acid and hydrochloric acid in water according to the reaction CI2 + H2O — HOCl + HCl, which react acidically with other water molecules.
  • the acidity damages the NaSICON solid electrolyte F A ⁇ 18>.
  • FIG. 1B shows another electrolytic cell E not according to the invention.
  • This three-chamber cell E comprises a cathode chamber K K ⁇ 12>, an anode chamber K A ⁇ 11> and a central chamber K ⁇ 13> lying in between.
  • the cathode chamber K K ⁇ 12> comprises a cathodic electrode E K ⁇ 123> in the interior IKK ⁇ 122>, an inlet ZKK ⁇ 120> and an outlet AKK ⁇ 121>.
  • the anode chamber K A ⁇ 11> includes an anodic electrode E A ⁇ 113> in the interior IKA ⁇ 112>, an inlet ZKK ⁇ 110> and an outlet A KA ⁇ 111>.
  • the middle chamber K ⁇ 13> comprises an interior space I K M ⁇ 132>, an inlet Z K M ⁇ 130> and an outlet AKM ⁇ 131>.
  • the interior IKA ⁇ 112> is connected to the interior I K M ⁇ 132> via the connection V A M ⁇ 15>.
  • the three chambers are delimited by an outer wall ⁇ 80> of the three-chamber cell E.
  • the interior I K M ⁇ 132> of the middle chamber K ⁇ 13> is also separated from the interior IKK ⁇ 122> of the cathode chamber K K ⁇ by a partition wall, which consists of a disc of a NaSICON solid electrolyte FA ⁇ 18> that is selectively permeable for sodium ions 12> separated.
  • the NaSICON solid electrolyte F A ⁇ 18> extends over the entire depth and height of the three-chamber cell E.
  • the partition has two sides S K K ⁇ 161 > and SA/MK ⁇ 162>, whose surfaces are OKK ⁇ 163> and OA/ MK ⁇ 164> contact the respective interior IKK ⁇ 122> or I K M ⁇ 132>.
  • the interior I K M ⁇ 132> of the middle chamber K ⁇ 13> is additionally separated from the interior IKA ⁇ 112> of the anode chamber K A ⁇ 11> by a diffusion barrier D ⁇ 14>.
  • the NaSICON solid electrolyte F A ⁇ 18> and the diffusion barrier D ⁇ 14> extend over the entire depth and height of the three-chamber cell E.
  • the diffusion barrier D ⁇ 14> is a cation exchange membrane (sulfonated PTFE).
  • connection V A M ⁇ 15> is formed outside the electrolytic cell E, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
  • liquid can flow from the interior I K M ⁇ 132> of the middle chamber K ⁇ 13> into the interior IKA ⁇ 112> of the anode chamber K A ⁇ 11> outside the outer wall W A ⁇ 80> of the three-chamber cell E to be directed.
  • connection V A M ⁇ 15> connects an outlet AKM ⁇ 131>, which breaks through the outer wall W A ⁇ 80> of the electrolytic cell E at the bottom of the central chamber K ⁇ 13>, with a Inlet ZKA ⁇ 110>, which breaks through the outer wall W A ⁇ 80> of the electrolytic cell E at the bottom of the anode chamber K A ⁇ 11>.
  • An aqueous solution of sodium chloride L 3 ⁇ 23> with pH 10.5 is added via the inlet ZKM ⁇ 130> in the same direction as gravity into the interior I KM ⁇ 132> of the middle chamber K ⁇ 13>.
  • the connection V A ⁇ 15> which is formed between an outlet A KM ⁇ 131> of the central chamber K ⁇ 13> and an inlet Z KA ⁇ 110> of the anode chamber K A ⁇ 11>, creates the interior space I KM ⁇ 132> the middle chamber K M ⁇ 13> is connected to the interior l KA ⁇ 112> of the anode chamber K A ⁇ 11>.
  • Sodium chloride solution L 3 ⁇ 23> is conducted through this connection V AM ⁇ 15> from interior I KM ⁇ 132> to interior I KA ⁇ 112>.
  • a solution of sodium methoxide in methanol L 2 ⁇ 22> is fed into the interior I KK ⁇ 122> via the feed Z KK ⁇ 120>.
  • a voltage is applied between the cathodic electrode E K ⁇ 123> and the anodic electrode E A ⁇ 113>.
  • methanol in the electrolyte L 2 ⁇ 22> is reduced to methoxide and H 2 (CH 3 OH + e- - CH 3 0 _ + 1 H2).
  • Sodium ions diffuse from the interior I KM ⁇ 132> of the middle chamber K ⁇ 103> through the NaSICON solid electrolyte FA ⁇ 18> into the interior I KK ⁇ 122>.
  • the acidity would damage the NaSICON solid electrolyte FA ⁇ 18>, but is limited to the anode chamber KA ⁇ 11> by the arrangement in the three-chamber cell and is thus kept away from the NaSICON solid electrolyte FA ⁇ 18> in the electrolytic cell E. This increases its lifespan considerably.
  • FIG. 2 A shows an embodiment of the partition W ⁇ 16> according to the invention.
  • the partition wall W ⁇ 16> includes two NaSICON solid electrolyte ceramics F A ⁇ 18> and F B
  • separating element T ⁇ 17> which are separated from one another by a separating element T ⁇ 17> and are each attached to it without gaps.
  • the separating element T ⁇ 17> has the geometric shape of a cuboid, on the opposite sides of which FA ⁇ 18> and FB ⁇ 19> are attached without gaps ( eg by means of an adhesive).
  • the side SKK ⁇ 161> with the surface OKK ⁇ 163> lies in the image plane
  • the side SA/MK ⁇ 162> with the surface OA/MK ⁇ 164> not visible in Fig. 2A behind the image plane.
  • Figure 2 B shows another embodiment of a partition wall W ⁇ 16> according to the invention.
  • This comprises four NaSICON solid electrolyte ceramics F A ⁇ 18>, F B ⁇ 19>, F c ⁇ 28>, F D ⁇ 29>, which are separated from one another by a separating element T ⁇ 17> and are each attached to it without gaps.
  • the separating element T ⁇ 17> has the shape of a cross, on the opposite sides of which FA ⁇ 18>, FB ⁇ 19>, Fc ⁇ 28> and FD ⁇ 29> are glued.
  • the side SKK ⁇ 161> with the surface OKK ⁇ 163> lies in the image plane
  • Figure 3 A shows the detailed view, which is highlighted in Figures 2 A and 2 B by a dashed circle. As described are the respective
  • Figure 3 B illustrates a further embodiment of the partition wall W according to the invention.
  • the partition element T ⁇ 17> has two concave depressions (grooves) into which the two solid electrolyte ceramics F A ⁇ 18> and F B ⁇ 19> to be fitted.
  • the shape of the edges of the solid electrolyte ceramics F A ⁇ 18> and F B ⁇ 19> can be adjusted mechanically accordingly.
  • a seal Di ⁇ 40> is used, which is attached, for example with an adhesive, to the separating element T ⁇ 17> and the respective solid electrolyte ceramic FA ⁇ 18> or FB ⁇ 19>.
  • the separating element T ⁇ 17> can consist of two or more parts ⁇ 171> and ⁇ 172> which, as indicated by the dashed line in FIG. 3B, can be attached to one another.
  • the latter With a corresponding geometry and adaptation of the shape of the edges of the solid electrolyte ceramics F A ⁇ 18> and F B ⁇ 19>, the latter can be clamped between the two parts ⁇ 171> and ⁇ 172>, which increases the stability of the connection between the separating element T ⁇ 17> / Ceramic F A ⁇ 18> or F B ⁇ 19> and the tightness of the partition wall W ⁇ 16> further improved.
  • Figure 3 C illustrates another inventive embodiment of the partition W. This corresponds to that described in Figure 3 B, except that the depressions (grooves) in the partition T ⁇ 17>, in which the two Solid electrolyte ceramics F A ⁇ 18> and F B ⁇ 19> are fitted, are not concave but tapered.
  • FIG. 4A shows further embodiments of the partition wall W ⁇ 16> according to the invention.
  • Partition W ⁇ 16> shown in Figure 4A is similar to partition W ⁇ 16> shown in Figure 2A except that it also includes a frame member R ⁇ 20>. This completely covers all surfaces of the partition wall W ⁇ 16> except OKK ⁇ 163> and OA/MK ⁇ 164>.
  • the frame element R ⁇ 20> is not made in one piece with the separating element T ⁇ 17>.
  • Figure 4 B shows a further embodiment of the partition wall W ⁇ 16> according to the invention. This corresponds to the embodiment shown in Figure 4A, except that it includes two frame members R ⁇ 20> that define the top and bottom surfaces of the partition W ⁇ 16>.
  • FIG. 4 C shows a further embodiment of the partition wall W ⁇ 16> according to the invention.
  • Partition W ⁇ 16> shown in Figure 4C is similar to partition W ⁇ 16> shown in Figure 2B except that it also includes a frame member R ⁇ 20>. This completely covers all surfaces of the partition wall W ⁇ 16> except OKK ⁇ 163> and OA/MK ⁇ 164>.
  • the frame element R ⁇ 20> is not made in one piece with the separating element T ⁇ 17>.
  • Figure 4D shows a further embodiment of the partition wall W ⁇ 16> according to the invention. This corresponds to the embodiment shown in Figure 4C, except that it includes two frame members R ⁇ 20> that bound the top and bottom surfaces of the partition W ⁇ 16>.
  • Figures 5 A and 5 B shows an electrolytic cell E not according to the invention. This corresponds to the electrolytic cell shown in Figure 1 A with the difference that a partition W ⁇ 16> separates the interior I K K ⁇ 122> of the cathode chamber K K ⁇ 12> from the interior I KA ⁇ 112> of the anode chamber K A ⁇ 11>.
  • the partition is the one shown in Figures 2A and 2B.
  • Figure 5 B shows an electrolytic cell E not according to the invention. This corresponds to the electrolytic cell shown in Figure 1 A with the difference that a partition W ⁇ 16> separates the interior I K K ⁇ 122> of the cathode chamber K K ⁇ 12> is separated from the interior I K A ⁇ 112> of the anode chamber K A ⁇ 11>.
  • the partition W ⁇ 16> is that shown in Figures 4A to 4D.
  • the frame member R ⁇ 20> forms part of the outer wall W A ⁇ 80> so that the solid electrolyte ceramics comprised by the partition W ⁇ 16> are protected from the pressure that would be exerted on them by the partition W ⁇ 16> if they were part of the partition W ⁇ 16> would be protected.
  • the solid electrolyte ceramics are used to completely separate the interior spaces IKK ⁇ 122> and IKA ⁇ 112> within the electrolytic cell, since they are not partially covered by the outer wall.
  • Figure 6 A shows an electrolytic cell E ⁇ 1> according to the first aspect of the invention. This corresponds to the electrolytic cell shown in FIG. 1B with the difference that a partition wall W ⁇ 16> separates the interior space IKK ⁇ 122> of the cathode chamber K ⁇ 12> from the interior space IKM ⁇ 132> of the middle chamber K ⁇ 13>.
  • the partition W ⁇ 16> is that shown in Figures 4A to 4D.
  • Figure 6 B shows an electrolytic cell E ⁇ 1> according to the first aspect of the invention. This corresponds to the electrolytic cell E ⁇ 1> shown in Figure 6 A with the
  • connection V A ⁇ 15> from the interior IKM ⁇ 132> of the middle chamber K ⁇ 13> to the interior l KA ⁇ 112> of the anode chamber K A ⁇ 11> is formed by a perforation in the diffusion barrier D ⁇ 14>.
  • This perforation can be placed in the diffusion barrier D ⁇ 14> or already be present in the diffusion barrier D ⁇ 14> from the outset when it is produced (eg in the case of textile fabrics such as filter cloths or metal fabrics).
  • Figure 7 A shows a further embodiment of a partition W ⁇ 16> according to the invention.
  • the partition wall W ⁇ 16> also comprises a frame element R ⁇ 20>, which also consists of two halves ⁇ 201> and ⁇ 202>.
  • Partition W ⁇ 16> consists of two collapsible parts in which half ⁇ 171> of partition T ⁇ 17> is integral with half ⁇ 201> of frame element R ⁇ 20> and half ⁇ 172> of partition T ⁇ 17 > Present in one piece with half ⁇ 202> of the frame element R ⁇ 20>. These two parts can optionally be connected to one another via a hinge ⁇ 50> and locked in place via the lock ⁇ 60> when folded.
  • F c ⁇ 28> and F D ⁇ 29> are clamped in, with a ring functioning as a seal Di ⁇ 40> being used in each case for sealing.
  • FIG. 7 A shows the frontal view of the side SKK ⁇ 161> with the surface OKK ⁇ 163> of the partition wall W ⁇ 16>.
  • the rings functioning as seal Di ⁇ 40> are indicated with dashed outlines.
  • the right side of the figure shows the side view of the partition W ⁇ 16>.
  • Figure 7 B shows a further embodiment of a partition wall W ⁇ 16> according to the invention. This corresponds to the embodiment described in FIG. 7A, except that it has nine NaSICON solid electrolyte ceramics F A ⁇ 18>, F B ⁇ 19>, F c ⁇ 28>, F D ⁇ 29>, F E ⁇ 30>, F ⁇ 31>, FG ⁇ 32>, FH ⁇ 33>, Fi ⁇ 34>. 4.
  • FIG. 7A shows a further embodiment of a partition wall W ⁇ 16> according to the invention. This corresponds to the embodiment described in FIG. 7A, except that it has nine NaSICON solid electrolyte ceramics F A ⁇ 18>, F B ⁇ 19>, F c ⁇ 28>, F D ⁇ 29>, F E ⁇ 30>, F ⁇ 31>, FG ⁇ 32>, FH ⁇ 33>, Fi ⁇ 34>. 4.
  • FIG. 7A shows a further embodiment of a partition wall W ⁇ 16> according to
  • the present invention relates to an electrolytic cell E comprising the partition wall W.
  • the partition wall W is therefore particularly suitable as a partition wall in an electrolytic cell, in particular an electrolytic cell E.
  • the dividing wall W comprises at least two alkali cation-conducting solid electrolyte ceramics (“alkali cation-conducting solid electrolyte ceramics” is abbreviated to “AFK” below) F A and F B , separated from one another by a separating element T.
  • alkali cation-conducting solid electrolyte ceramics is abbreviated to “AFK” below
  • the partition W includes two sides SKK and S A / MK, which face each other, that is, the side S A K faces the side SKK (and vice versa).
  • the two sides SKK and S V MK comprise planes which are essentially parallel to one another.
  • the geometry of the partition wall W is otherwise not further restricted and can in particular be adapted to the cross section of the electrolytic cell E in which it is used.
  • it may have the geometry of a parallelepiped and thus have a rectangular cross-section, or the geometry of a truncated cone or cylinder and thus have a circular cross-section.
  • the partition W can also have the geometry of a cuboid with rounded corners and/or bulges, which in turn can have holes.
  • the dividing wall W then has bulges ("rabbit ears") with which the dividing wall W can be fixed to electrolytic cells or also frame parts of the dividing wall W can be fixed to one another.
  • the SKK side of the partition W has the surface OKK, and the side S A K of the partition W has the surface O A K .
  • partition means that the partition W is liquid-tight. This means that the AFKs and the at least one separating element T connect to one another without a gap. There are thus no gaps between the separating element T and the AFKs enclosed by the dividing wall W, through which aqueous solution, alcoholic solution, alcohol or water could flow from the side SKK to the side S A K or vice versa.
  • the pair of opposite sides is preferably referred to as SKK and S VMK within the meaning of the invention, which includes the largest surfaces OKK and 0 A /MK.
  • SKK and S VMK within the meaning of the invention, which includes the largest surfaces OKK and 0 A /MK.
  • surfaces of the same size can be selected by a specialist as a pair as SKK and SA/MK with surfaces OKK or OA/MK.
  • partition walls W in which there are two or more pairs of opposite sides, over the surfaces of which the alkali cation conductive materials comprised by the partition wall W are located
  • Solid electrolyte ceramics and in particular also the separating element T are directly contactable, the dividing walls W are preferred in which the surfaces covered by the respective pair of opposite sides are of different sizes, the pair of opposite sides then being referred to as SKK and SA/MK within the meaning of the invention , which includes the largest surfaces OKK and OA/MK.
  • the partition W according to the invention also includes embodiments in which the partition W comprises more than two AFKs, e.g. four or nine or twelve AFKs, with at least two of the AFKs, but not all AFKs, being separated from one another by a separating element T, with the not AFKs separated from one another by a separating element T directly adjoin one another.
  • this requires an exact fit of the respective adjacent AFKs in order to preclude the creation of a gap between them through which aqueous liquid or water or alcohol or alcoholic solution could flow from the SKK side to the SA/MK side.
  • all the AFKs comprised by the partition W are separated from one another by at least one separating element T, i.e. no AFK is directly connected to another AFK, i.e. without a separating element T being in between.
  • the dividing wall W is further characterized in that the AFKs enclosed by the dividing wall W can be contacted directly both via the surface OKK and via the surface OA/MK.
  • Directly contactable means, with regard to the AFKs enclosed by the partition W, that part of the surfaces OKK and OA/MK is formed by the surface of the AFKs enclosed by the partition W, i.e. the AFKs enclosed by the partition W are directly accessible on the two surfaces OKK and OA/MK, so that they can be wetted on the two surfaces OKK and OA/MK, for example with an aqueous solution, alcoholic solution, alcohol or water.
  • the at least one separating element T can also be contacted directly via at least part of the surface OKK and via at least part of the surface OA/MK.
  • “Directly contactable” means, with regard to the at least one separating element T contained by the partition W, that part of the surfaces OKK and OA/MK is formed by the surface of the separating element T, i.e. the separating element T on the two surfaces OKK and OA/MK is directly accessible, so that the separating element T can be wetted on the two surfaces OKK and OA/MK, for example with an aqueous solution, alcoholic solution, alcohol or water.
  • the partition W In a preferred embodiment of the partition W according to the invention, 50% to 95%, more preferably 60 to 90%, even more preferably 70 to 85% of the surface OKK are formed by the AFKs comprised by the partition W, with the remainder of the surface OKK being even more preferably formed by the Separating element T and optionally the frame element R are formed.
  • dividing wall W In a preferred embodiment of the dividing wall W according to the invention, 50% to 95%, more preferably 60 to 90%, even more preferably 70 to 85% of the surface OA/MK are formed by the AFKs comprised by the dividing wall W, with the remainder of the surface being even more preferably formed OA / MK are formed by the separating element T and optionally the frame element R.
  • the dividing wall W comprises at least four AFKs FA, FB, Fc and FD , in which case it more preferably comprises exactly four AFKs FA , FB, Fc and FD .
  • the partition W comprises at least nine AFKs F A , F b , F c , F d , F e , F f , F g , FH and Fi , in which case it is even more preferred to have exactly nine AFKs F A , F B , F c , FD , F e , F f , F g , FH and Fi .
  • the partition W comprises at least twelve AFKs F A , F b , F c , F d , F e , F f , F g , F h , FI, F J , F K and FL , where they then also more preferably exactly twelve AFKs F A , FB, Fc, FD, FE, FF, FG, FH, FI, FJ, FK and FL.
  • This inventive arrangement of at least two AFKs next to each other in the partition wall W results in a further propagation direction for the AFKs in the temperature fluctuations that arise during operation of the electrolytic cell compared to the conventional partition walls in the electrolytic cells of the prior art.
  • the NaSICON disks which act as partitions, are through the outer walls of the electrolytic cell or from solid plastic frames limited. The mechanical stresses that occur within the NaSICON during expansion cannot be dissipated, which can lead to the ceramic breaking.
  • each AFK has at least one additional degree of freedom available, i.e. a dimension in which it can expand can.
  • expansion in the x- and/or y-direction is now also possible, i.e. in the horizontal and vertical direction within the plane the partition wall W.
  • any solid electrolyte through which cations, in particular alkali cations, more preferably sodium cations, can be transported from the SA/MK side to the SKK side can be used as the solid electrolyte ceramics F A , FB etc. which conduct alkali cations and are enclosed by the partition W.
  • Such solid electrolytes are known to the person skilled in the art and are described, for example, in DE 102015013 155 A1, in WO 2012/048032 A2, paragraphs [0035], [0039], [0040], in US 2010/0044242 A1, paragraphs [0040], [ 0041], in DE 10360758 A1, paragraphs [014] to [025].
  • NaSICON LiSICON
  • KSICON KSICON
  • a sodium ion conductive solid electrolyte is preferred, more preferably having a NaSICON structure.
  • NaSICON structures that can be used according to the invention are also described, for example, by N. Anantharamulu, K. Koteswara Rao, G. Rambabu, B. Vijaya Kumar, Velchuri Radha,
  • the alkali cation-conducting solid electrolyte ceramics comprised by the dividing wall W independently of one another have a NaSICON structure of the formula M'i+2w+x- y+ z M" M m x Zr lv 2- -x- y M v y ( SiC>4)z (PC>4)3-z on.
  • M' is selected from Na + , Li + , preferably Na + .
  • M" is a divalent metal cation, preferably selected from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ , Ni 2+ , more preferably selected from Co 2+ , Ni 2+ .
  • M m is a trivalent metal cation, preferably selected from Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ , more preferably selected from Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , particularly preferably selected from Sc 3+ , Y 3+ , La 3+ .
  • M v is a pentavalent metal cation, preferably selected from V 5+ , Nb 5+ , Ta 5+ .
  • w, x, y, z are real numbers, where 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 0 ⁇ w ⁇ 2, 0 ⁇ z ⁇ 3, and where w, x, y, z are so chosen become that 1 + 2w + x - y + z > 0 and 2 - w - x - y > 0.
  • the AFKs comprised by the dividing wall W have the same structure.
  • the separating element T separates at least two alkali cation-conducting solid electrolyte ceramics F A and FB contained in the partition W, ie it is arranged between at least two alkali cation-conducting solid electrolyte ceramics F A and F B contained in the partition W.
  • any body through which the respective AFKs can be arranged separately from one another is suitable as a separating element T, which is encompassed by the separating wall W.
  • the AFKs connect seamlessly to the separating element T so as not to impair the function of the dividing wall, which in the electrolytic cell E is intended to separate the cathode chamber from the adjacent middle or anode chamber in a liquid-tight manner.
  • the shape of the separating element T can be chosen by a person skilled in the art depending on the number of AFKs that the dividing wall W comprises. If the partition W includes, for example, two or three AFKs, these can each be separated by a web arranged between the AFKs as a separating element T (see Figure 1A).
  • the partition W comprises four or more AFKs, these can be separated by a separating element T, which has the shape of a cross (see Figure 1 B and 4 A) or a grid (see Figure 4 B).
  • the dividing wall W comprises at least four AFKs and even more preferred that the separating element T is then cross-shaped or grid-shaped, since it is then ensured that the AFKs have all three dimensions available for thermal expansion/shrinkage.
  • the separating element T can consist of one piece ( Figures 2 A, 2 B).
  • the AFK is then attached without gaps to the separating element, for example using a means known to those skilled in the art, for example using an adhesive, with preference being given to using epoxy resins or phenolic resins.
  • the separating element T can also be shaped in such a way that the respective AFK fits into the separating element can be fitted or pinched. This can already be done during the manufacture of the partition wall W (Section 4.1.4).
  • the dividing wall W in particular between the dividing element T and the AFKs, comprises a seal Di ( Figures 3 B, 3 C). This ensures particularly well that the partition wall W is liquid-tight.
  • the seal Di can be selected by a person skilled in the art for the respective AFK or the respective separating element T.
  • the seal Di comprises a material selected from the group consisting of elastomers, adhesives, preferably elastomers.
  • Rubber is particularly suitable as an elastomer, preferably ethylene-propylene-diene rubber (“EPDM”), fluoropolymer rubber (“FPM”), perfluoropolymer rubber (“FFPM”),
  • EPDM ethylene-propylene-diene rubber
  • FPM fluoropolymer rubber
  • FFPM perfluoropolymer rubber
  • N B R Acry I n it ri I butadiene rubber
  • the separating element T comprises at least two parts Ti and T 2 which can be fastened to one another and thus clamp the AFKs between them.
  • the separating element T preferably comprises a material which is selected from the group consisting of plastic, glass and wood.
  • the separating element T is particularly preferably made of plastic. More preferably, the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, post-chlorinated polyvinyl chloride ("PVC-C").
  • the dividing wall W also includes a frame element R.
  • the frame element R differs from the dividing element T in that it is not arranged between the alkali cation-conducting solid electrolyte ceramics comprised by the dividing wall W, ie it does not separate them from one another.
  • the frame element R delimits in particular the surfaces OKK and OA/MK at least partially, preferably completely. This means in particular: The frame element R encloses the surfaces OKK and OA/MK at least partially, preferably completely.
  • the frame element R can be designed as a part of the surfaces OKK and OA/MK or not.
  • the frame element R is preferably designed as part of the surfaces OKK and OA/MK.
  • the frame element R can be directly contacted or not directly contacted, preferably directly contacted, in particular via the surfaces OKK and OA/MK.
  • “Not directly contactable” means, with regard to the frame element R comprised by the partition wall W, that the frame element R is formed exclusively as at least part of the surfaces of those sides of the partition wall W that are not the sides SKK and SA/MK acts. In particular, the frame element R then forms at least 1%, more preferably at least 25%, more preferably at least 50%, still more preferably 100% of the surfaces of the sides of the partition wall W other than the sides SKK and SA/MK.
  • Directly contactable means, with regard to the frame element R enclosed by the partition W, that part of the surfaces OKK and OA/MK is formed by the surface of the frame element R, i.e. the frame element R enclosed by the partition W is attached to the both surfaces OKK and OA/MK are directly accessible, so that both surfaces OKK and OA/MK can be wetted with an aqueous solution, alcoholic solution, alcohol or water, for example.
  • the frame element R can additionally also be formed as at least a part of the surfaces of those sides of the partition wall W which are not the sides S KK and S A/MK .
  • the frame member R forms at least 1%, more preferably at least 25%, more preferably at least 50%, still more preferably 100% of the surface areas of the sides of the partition wall W other than sides S KK and S A/MK .
  • FIGs. 4B and 4D embodiments are shown in which the frame member R forms part of the surfaces of those sides of the partition wall W other than sides S KK and S A/MK .
  • FIGs. 4A and 4C embodiments are shown in which the frame member R completely forms the surfaces of those sides of the partition wall W other than the sides S KK and SA/MK.
  • the frame element R is in particular made of a material that is selected from the group consisting of plastic, glass, and wood.
  • the frame element R is particularly preferably made of plastic.
  • the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, PVC-C.
  • the frame element R and the partition element T are made of the same material, more preferably both are made of plastic, which is even more preferably selected from polypropylene, polystyrene, polyvinyl chloride, PVC-C.
  • the frame element R can consist of one piece.
  • the AFK is then attached to the frame element R without gaps, for example using a means known to those skilled in the art, for example using an adhesive, with epoxy resins and phenolic resins being particularly suitable.
  • the frame element R can also be shaped in such a way that the respective AFK can be fitted into the frame element R or clamped.
  • the dividing wall W comprises a frame element R, the AFCs, the at least one dividing element T and the frame element R adjoin one another without a gap. There are thus no gaps between the separating element T, the frame element R and the AFKs comprised by the dividing wall W, through which aqueous solution or water could flow from the side SKK to the side S A/ MK or vice versa.
  • the partition W comprises a frame element R, with which the partition element T is at least partially formed in one piece
  • the frame element R can consist of at least two parts that are fastened to one another and thereby clamp the AFKs between them.
  • the partition wall W can then have a hinge on which the two parts of the frame element R can be opened and closed.
  • the dividing wall W can then have a lock on which the two parts of the frame element R can be locked in the closed state (FIG. 7A).
  • the separating element T In the closed state, the AFKs and, if this is not already formed in one piece with the frame element R, the separating element T can be clamped between the frame element R. In this embodiment, a seal can then be attached between the separating element T and AFK or frame element R and AFK in order to ensure liquid tightness.
  • At least part of the separating element T ⁇ 17> is formed in one piece with at least part of the frame element R ⁇ 20>. This means in particular that at least part of the separating element T merges into the frame element R.
  • the separating element T ⁇ 17> and the frame element R ⁇ 20> are preferably present in one piece.
  • the embodiment of a frame element R has the advantage that it can function as part of the outer wall when assembling the electrolytic cell E.
  • This part of the partition wall W does not contact the solutions in the respective inner space IKK, IK A or IKM, which is why it would be wasteful to take the solid electrolyte ceramic FA or F B for this part.
  • the part of the partition wall W which is sandwiched between or forms part of the outer wall is subjected to pressures, for which the brittle solid electrolytic ceramics FA or FB is unsuitable. Instead, a shatterproof and cheaper material is selected for the frame R.
  • the partition wall W can be produced by methods known to those skilled in the art.
  • the AFKs enclosed by the dividing wall can be placed in a mold and the dividing element superfluous plastic can be cast and then allowed to solidify (injection molding process). When it freezes, it then encloses the AFKs.
  • the separating element T is cast separately (or in parts) and then attached (for example glued) to the at least two AFKs without any gaps.
  • the partition wall W according to the invention is suitable as a partition wall in an electrolytic cell E according to the first aspect of the invention.
  • the present invention therefore relates to an electrolytic cell E, comprising at least one anode chamber K A with at least one inlet ZKA, at least one outlet AKA and an interior IKA, which comprises an anodic electrode E A , at least one cathode chamber K K with at least one Inlet ZKK, at least one outlet AKK and an interior I K K, which comprises a cathodic electrode E K , and at least one intermediate chamber K with at least one inlet ZKM, at least one outlet A K M and an interior I K M, wherein then IKA and I K M are separated from one another by a diffusion barrier D, and AKM is connected by a connection V A M to the inlet ZKA, so that liquid can be passed from I K M into IKA through the connection V A M, with
  • IKK and IKM are separated from one another by the partition W according to the invention, characterized in that the alkali cation-conducting solid electrolyte ceramics contained in the partition W, and in particular also the separating element T, make direct contact with the interior IKK on the side S K K via the surface OKK, and the alkali cation-conducting solid electrolyte ceramics comprised by the dividing wall W, and in particular also the dividing element T, directly contact the interior space IKM on the side SA/MK via the surface OA/MK.
  • the electrolytic cell E according to the first aspect of the invention comprises at least one anode chamber K A and at least one cathode chamber K K and optionally at least one intermediate chamber K G in between.
  • This also includes electrolytic cells E, which have more than one anode chamber K A and/or cathode chamber K K and/or central chamber K.
  • electrolytic cells in which these chambers are joined together in a modular manner, are described, for example, in DD 258 143 A3 and US 2006/0226022 A1.
  • the electrolytic cell E according to the first aspect of the invention comprises an anode chamber K A and a cathode chamber K K and, if appropriate, a middle chamber K C lying between them.
  • the electrolytic cell E usually has an outer wall W A .
  • the outer wall W A is in particular made of a material selected from the group consisting of steel, preferably rubberized steel, plastic, in particular Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride ) is selected.
  • W A can be perforated in particular for inlets and outlets.
  • Within W A then lie the at least one anode chamber K A , the at least one cathode chamber K K and, in the embodiments in which the electrolytic cell E comprises such, the at least one intermediate chamber K .
  • the cathode chamber K K has at least one inlet ZKK, at least one outlet AKK and an interior space I KK , which includes a cathodic electrode E K .
  • the interior I K K of the cathode chamber K K is separated from the interior I K M of the central chamber K by the partition wall W according to the invention.
  • the cathode chamber K K includes an interior space I K K which in turn includes a cathodic electrode E K .
  • a cathodic electrode E K Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the second aspect of the invention can be used as such a cathodic electrode E K . Such are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
  • This electrode E K can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "spheres".
  • the cathodic electrode E K comprises in particular a material which is selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium. E K preferably comprises nickel.
  • the cathode chamber K K also includes an inlet ZKK and an outlet AKK. This makes it possible to add liquid, such as the solution L 2 , to the inner space I K K of the cathode chamber K K and to remove liquid therein, such as the solution Li.
  • the inlet ZKK and the outlet AKK are attached to the cathode chamber K K in such a way that the liquid makes contact with the cathodic electrode E K as it flows through the interior I K K of the cathode chamber K K .
  • the ZKK inlet and the AKK outlet can be attached to the electrolytic cell E using methods known to those skilled in the art, e.g. through holes in the outer wall and corresponding connections (valves) that simplify the introduction and removal of liquid.
  • the anode chamber K A has at least one inlet Z KA , at least one outlet A KA and an interior space I KA , which includes an anodic electrode E A .
  • the interior I K A of the anode chamber K A is separated from the interior I K M of the middle chamber K by a diffusion barrier D.
  • the anode chamber K A includes an interior space I KA , which in turn includes an anodic electrode E A .
  • Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the second aspect of the invention can be used as such an anodic electrode E A .
  • This electrode E A can consist of one layer or of several planar, mutually parallel layers, each of which can be perforated or expanded.
  • the anodic electrode E A comprises in particular a material which is selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, noble metals such as platinum in particular, which is deposited on a carrier such as titanium or Kovar® (an iron/nickel/ Cobalt alloy, in which the individual proportions are preferably as follows: 54% by mass iron, 29% by mass nickel, 17% by mass cobalt) is supported.
  • Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
  • the anodic electrode E A preferably comprises a titanium anode (RuQ 2 +Ir0 2 /Ti) coated with ruthenium oxide/iridium oxide. 4.2.2.2 ZKA inlet and AKA outlet
  • the anode chamber K A also includes an inlet ZKA and an outlet A ka .
  • the inlet Z KA and the outlet A KA are attached to the anode chamber K A in such a way that the liquid makes contact with the anodic electrode E A as it flows through the interior l KA of the anode chamber K A .
  • This is the prerequisite for the solution L 4 being obtained at the outlet A KA when the method according to the second aspect of the invention is carried out if the solution L 3 of a salt S is passed through the interior space l KA of the anode chamber KA.
  • the inlet Z KA and the outlet A KA can be attached to the electrolytic cell E by methods known to those skilled in the art, eg through bores in the outer wall and corresponding connections (valves) which simplify the introduction and removal of liquid.
  • the inlet Z KA can also be within the electrolysis cell, for example as a perforation in the diffusion barrier D.
  • the electrolytic cell E has at least one central chamber K.
  • the central chamber K lies between the cathode chamber K K and the anode chamber K A . It comprises at least one inlet Z K M, at least one outlet A K M and an interior space I K M.
  • the interior space l KA of the anode chamber K A is separated from the interior space I K M of the middle chamber K by a diffusion barrier D.
  • a KM is then also connected to the inlet ZKA by a connection V A , so that liquid can be conducted from I K M into IKA through the connection V A M .
  • the interior I K M of the central chamber K is separated from the interior IKA of the anode chamber K A by a diffusion barrier D and is separated from the interior i KK of the cathode chamber K K by the partition W.
  • any material which is stable under the conditions of the method according to the second aspect of the invention and which prevents the transfer of protons from the liquid located in the interior lKA of the anode chamber KA to the interior IKM of the central chamber K can be used for the diffusion barrier D or slowed down.
  • a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D.
  • the diffusion barrier D is preferably a non-ion-specific partition.
  • the material of the non-ion-specific partition wall is in particular selected from the group consisting of fabric, in particular textile fabric or metal fabric, glass, in particular sintered glass or glass frits, ceramic, in particular ceramic frits, membrane diaphragms, and is selected particularly preferably a textile fabric or metal fabric, particularly preferably a textile fabric.
  • the textile fabric preferably comprises plastic, more preferably a plastic selected from PVC, PVC-C, polyvinyl ether (“PVE”), polytetrafluoroethylene (“PTFE”).
  • the diffusion barrier D is a “membrane that is permeable to specific ions”
  • membranes are meant that favor the diffusion through them of ions of a certain type of charge compared to oppositely charged ions. More preferably, specific ion permeable membranes also favor the diffusion of certain ions having one charge type through them over other ions of the same charge type.
  • the diffusion barrier D is a “membrane permeable to specific ions”, the diffusion barrier D is in particular an anion-conducting membrane or a cation-conducting membrane.
  • anion-conducting membranes are those which selectively conduct anions, preferably selectively specific anions. In other words, they favor the diffusion of anions through them over that of cations, especially over protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.
  • cation-conducting membranes are those which selectively conduct cations, preferably selectively specific cations. In other words, they favor the diffusion of cations through them over that of anions, more preferably they additionally favor the diffusion of certain cations through them over the diffusion of other cations through them, much more preferably cations where there is are not protons, more preferably sodium cations, over protons.
  • “Favour the diffusion of certain ions X over the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion species X at a given Temperature for the membrane in question by a factor of 10, preferably 100, preferably 1000 higher than the diffusion coefficient of the ion species Y for the membrane in question.
  • the diffusion barrier D is a “membrane that is permeable to specific ions”, then it is preferably an anion-conducting membrane because this prevents the diffusion of protons from the anode chamber K A into the middle chamber K A particularly well.
  • a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
  • Such membranes are known to those skilled in the art and can be used by them.
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • a membrane selective for halides preferably chloride, is preferably used as the anion-conducting membrane.
  • Anion conducting membranes are available, for example, from M.A. Hickner, A.M. Herring, E.B. Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51 1727-1735, by C.G. Arges,
  • they have covalently bonded functional groups selected from -NH3 + , -NRH2 + , -NR3 + , more preferably selected from -NH3 + , -NR 3 + , even more preferably -NR3 + .
  • the diffusion barrier D is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S.
  • the diffusion barrier D is even more preferably an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
  • Cation-conducting membranes are described, for example, on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003).
  • Organic polymers which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are therefore even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -S0 3 - , -COO-, -PO3 2 -, -PO2H-, preferably -SO3 , (described in DE 102010 062804 A1,
  • This can be, for example, a sulfonated polyperfluoroethylene (Nation® with CAS number: 31175-20-9). These are known to the person skilled in the art, for example from WO 2008/076327 A1,
  • a cation-conducting membrane is used as the diffusion barrier D, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula
  • n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , even more preferably an integer from 10 2 to 10 4 .
  • the middle chamber K also includes an inlet ZKM and an outlet AKM. This makes it possible to add liquid, such as solution L 3 , to the interior I K M of the middle chamber K, and to transfer liquid therein, such as solution L 3 , to the anode chamber K A .
  • the inlet ZKM and the outlet AKM can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through holes in the outer wall and appropriate connections (valves) that simplify the inflow and outflow of liquid.
  • the drain AKM can also be within the electrolytic cell, for example as a perforation in the diffusion barrier D.
  • the outlet AKM is connected to the inlet ZKA SO by a connection V A M so that liquid can be passed from IKM into IKA through the connection V A M ,
  • connection V AM can be formed within the electrolytic cell E and/or outside of the electrolytic cell E, and is preferably formed within the electrolytic cell E.
  • connection V AM is formed within the electrolytic cell E, it is preferably formed by at least one perforation in the diffusion barrier D.
  • This embodiment is particularly preferred when a non-ion-specific dividing wall, in particular a metal fabric or textile fabric, is used as the diffusion barrier D. This acts as a diffusion barrier D and, due to the weaving properties, has perforations and gaps from the outset, which act as a connection V AM .
  • connection V AM is formed outside the electrolytic cell E, and it is preferably formed by a connection running outside of the electrolytic cell E AKM and Z KA is formed, in particular by the fact that an outlet AKM is formed from the interior of the middle chamber IKM through the outer wall W A , preferably at the bottom of the middle chamber K , with the inlet ZKM even more preferably at the top of the middle chamber K, and an inlet Z KA into the interior l KA of the anode chamber K A is formed by the outer wall W A , preferably at the bottom of the anode chamber K A , and this by a line, for example a pipe or hose, which is preferably a material selected from rubber , Plastic covers are connected.
  • the outlet A KA is then even more preferably formed on the upper side of the anode chamber K A .
  • Outflow AKM at the bottom of the middle chamber K means that the outflow AKM SO is attached to the electrolytic cell E, that the solution L 3 leaves the middle chamber K in the same direction as gravity.
  • Inlet Z KA at the bottom of the anode chamber K A means that the inlet Z KA is attached to the electrolytic cell E in such a way that the solution L 3 enters the anode chamber K A against the force of gravity.
  • ZKM inlet at the top of the middle chamber K means that the ZKM SO inlet is attached to the electrolytic cell E, so that the solution L 3 enters the middle chamber K in the same direction as gravity.
  • Outlet AKA at the top of the anode chamber K A means that the outlet AKA SO is attached to the electrolytic cell E, that the solution L 4 leaves the anode chamber K A against the force of gravity.
  • This embodiment is particularly advantageous and therefore preferred if the outlet AKM is formed by the outer wall WA at the bottom of the middle chamber K A and the inlet ZKA is formed by the outer wall WA at the bottom of the anode chamber K A .
  • This arrangement makes it particularly easy to discharge gases formed in the anode chamber K A with L 4 from the anode chamber K A in order to then separate them further.
  • the connection V A M is formed outside of the electrolytic cell E, in particular ZKM and AKM are arranged on opposite sides of the outer wall W A of the central chamber K (e.g. ZKM on the bottom and AKM on the top of the electrolytic cell E or vice versa) and ZKA and AKA arranged on opposite sides of the outer wall W A of the anode chamber K A (i.e.
  • ZKA at the bottom and AKA at the top of the electrolytic cell E or vice versa are shown in particular in Figure 6 A. Due to this geometry, L 3 must flow through the two chambers K and K A .
  • ZKA and ZKM can be formed on the same side of the electrolytic cell E, with AKM and AKA then automatically also being formed on the same side of the electrolytic cell E.
  • ZKA and ZKM can be formed on opposite sides of the electrolytic cell E, with AKM and AKA then automatically also being formed on opposite sides of the electrolytic cell E.
  • connection V A M is formed inside the electrolytic cell E, this can be ensured in particular by one side ("side A") of the electrolytic cell E, which is the top or the bottom of the electrolytic cell E, preferably, as shown in Figure 6 B, is the upper side, includes the inlet ZKM and the outlet AKA and the diffusion barrier D extends from this side ("side A") into the electrolytic cell E, but not quite to that of side A opposite side (“Side B”) of the electrolytic cell E, which is then the bottom or the top of the electrolytic cell E, thereby reaching 50% or more of the height of the three-chamber cell E, more preferably 60% to 99% of the height the three-chamber cell E, more preferably 70% to 95% of the height of
  • Three-chamber cell E more preferably 80% to 90% of the height of the three-chamber cell E, even more preferably 85% of the height of the three-chamber cell E spans.
  • the fact that the diffusion barrier D does not touch side B of the three-chamber cell E results in a gap between the diffusion barrier D and the outer wall W A of side B of the three-chamber cell E. Der The gap is then the connection V A M. Due to this geometry, L 3 must flow through the two chambers K and K A completely.
  • Bottom of the electrolytic cell E is the side of the electrolytic cell E through which a solution (e.g. L 3 in AKM in Figure 6 A) exits the electrolytic cell E in the same direction as gravity or the side of the electrolytic cell E through which a solution (eg L 2 at ZKK in Figures 6 A and 6 B) is fed to the electrolytic cell E against the force of gravity.
  • a solution e.g. L 3 in AKM in Figure 6 A
  • a solution e.g. L 2 at ZKK in Figures 6 A and 6 B
  • top side of the electrolytic cell E is the side of the electrolytic cell E through which a solution (e.g. L 4 for A KA and Li for AKK in Figures 6 A and 6 B) escapes from the electrolytic cell E against the force of gravity or the side of the Electrolytic cell E, through which a solution (e.g. L 3 at ZKM in Figures 6 A and 6 B) is fed to the electrolytic cell E in the same direction as gravity.
  • a solution e.g. L 4 for A KA and Li for AKK in Figures 6 A and 6 B
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramics, which are conductive to alkali cations, contained by the dividing wall W, and preferably also the separating element T, directly contact the interior space I K K on the side S K K via the surface OKK.
  • the partition wall W is arranged in the electrolytic cell E in such a way that when the interior space I K K on the side S K K is completely filled with solution L 2 , the solution L 2 then covers all of the surface OKK of the dividing wall W comprised solid electrolyte ceramics which conduct alkali cations and preferably also contacted the separating element T, so that ions (eg alkali metal ions such as sodium, lithium) from all AFKs that are comprised by the dividing wall W can enter the solution L 2 .
  • ions eg alkali metal ions such as sodium, lithium
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the alkali cation-conducting solid electrolyte ceramics contained by the dividing wall W, and preferably also the separating element T, make direct contact with the interior I K M on the side SA/MK via the surface OA/MK.
  • the partition wall W borders on the interior space I K M of the middle chamber K .
  • the partition wall W in the electrolytic cell E is arranged such that when the interior space I K M on the side SA /MK is completely filled with solution L 3 , the solution L 3 then covers the surface OA/MK all of the solid electrolyte ceramics which conduct alkali cations and comprise the dividing wall W and preferably also the dividing element T contacted, so that ions (eg alkali metal ions such as sodium, lithium) from the solution L 3 in each AFK, which is comprised of the partition W, can occur.
  • ions eg alkali metal ions such as sodium, lithium
  • the present invention relates to a process for preparing a solution Li of an alkali metal alkoxide XOR in the alcohol ROH, where X is an alkali metal cation and R is an alkyl radical having 1 to 4 carbon atoms.
  • the method according to the second aspect of the invention is carried out in an electrolytic cell E according to the first aspect of the invention.
  • R is preferably selected from the group consisting of n-propyl, /so-propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
  • the electrolytic cell E comprises at least one middle chamber K , and the steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are then carried out.
  • the solution L 2 is preferably free of water.
  • “free of water” means that the weight of the water in the solution L 2 based on the weight of the alcohol ROH in the solution L 2 (mass ratio) is ⁇ 1:10, more preferably ⁇ 1:20, more preferably ⁇ 1:100 , more preferably ⁇ 0.5:100.
  • the mass fraction of XOR in the solution L 2 is in particular >0 to 30% by weight, preferably 5 to 20% by weight more preferably at 10 to 20% by weight, even more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
  • the mass ratio of XOR to alcohol ROH in the solution L 2 is in particular in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20, even more preferably in the range 1:12 to 1:8, more preferably at 1:10.
  • step (ß2) a neutral or alkaline, aqueous solution L 3 of a salt S comprising X as a cation is passed through K , then via V A M , then through K A .
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • the pH of the aqueous solution L 3 is >7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
  • the mass fraction of the salt S in the solution L 3 is preferably in the range of >0 to
  • 20% by weight preferably 1 to 20% by weight, more preferably at 5 to 20% by weight, even more preferably at 10 to 20% by weight, most preferably at 20% by weight, based on the total solution L3 .
  • step (831) In step (ß3) a voltage is then applied between E A and E K .
  • the charge source is known to those skilled in the art and is typically a rectifier that converts alternating current into direct current and can generate specific voltages via voltage converters.
  • the area of the solid electrolyte that contacts the anolyte located in the central chamber K is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 .
  • step (ß3) of the method according to the second aspect of the invention is carried out when both chambers K and K A are at least partially loaded with L 3 and K K is at least partially loaded with L 2 , so that both L 3 and L 2 contact the solid electrolytes comprised by the partition wall W and, in particular, also contact the separating element T.
  • step (ß3) The fact that charge transport takes place between E A and E K in step (ß3) implies that KK, KM and K A are simultaneously loaded with L 2 and L 3 , respectively, in such a way that they connect the electrodes E A and E K to the extent cover that the circuit is closed.
  • Electrode E K at least partially, preferably completely covered.
  • step ( ⁇ 1) and step ( ⁇ 2) are carried out continuously and voltage is applied in accordance with step ( ⁇ 3).
  • the solution Li is obtained at the outflow AKK, the concentration of XOR in Li being higher than in L 2 .
  • the concentration of XOR in Li is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, even more preferably 1.077 to 1.4 fold, still more preferably 1.077 to 1.4 fold 1077 to 108 times higher than in L 2 , most preferably 1077 times higher than in L 2 , more preferably the mass fraction of XOR in Li and in L 2 being in the range 10 to 20 wt% , more preferably 13 to 14% by weight.
  • an aqueous solution L 4 of S is obtained, the concentration of S in L 4 being lower than in L 3 .
  • the concentration of the cation X in the aqueous solution L 3 is preferably in the range from 3.5 to 5 mol/l, more preferably 4 mol/l.
  • the concentration of the cation X in the aqueous solution L 4 is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 used in each case.
  • steps ( ⁇ 1) to ( ⁇ 3) of the method according to the second aspect of the invention are carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C more preferably 35°C to 50°C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
  • hydrogen is typically produced in the cathode chamber K K , which can be removed from the cell via the outlet AKK together with the solution Li.
  • the mixture of hydrogen and solution Li can then be separated by methods known to those skilled in the art.
  • the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can form, which can be removed from the cell via the outlet AKK together with the solution L 4 .
  • oxygen and/or carbon dioxide can also be formed, which can also be removed.
  • the mixture of chlorine, oxygen and/or CO2 and solution L 4 can then be used in a special
  • Embodiment of the present invention are separated according to methods known to those skilled in the art. Likewise, after the gases chlorine, oxygen and/or CO2 have been separated from the solution L 4 , these can be separated from one another by methods known to those skilled in the art. 4.3.4 Additional benefits of steps (ß1j to (ß3j
  • steps ( ⁇ 1) to ( ⁇ 3) brings other surprising advantages which were not to be expected in the light of the prior art.
  • steps (ß1) to (ß3) of the method according to the invention the acid-labile solid electrolyte is protected from corrosion without the need for alkoxide solution from the cathode compartment as in the prior art
  • NM Sodium methylate
  • the electrolytic cell consisted of three chambers, which corresponded to those shown in Figure 1B.
  • the connection between the middle and anode chamber was made by a hose that was attached to the bottom of the electrolytic cell.
  • the anode compartment and middle compartment were separated by a 2.83 cm 2 anion exchange membrane (Tokuyama AMX, ammonium groups on polymer).
  • the cathode and middle chamber were separated by a ceramic of the NaSICON type with an area of 2.83 cm 2 .
  • the ceramic had a chemical composition of the formula Na34Zr20Si24P06O12.
  • the anolyte was transferred to the anode compartment through the middle compartment.
  • the flow rate of the anolyte was 1 l/h, that of the catholyte was 90 ml/h and a current of 0.14 A was applied.
  • the temperature was 35°C.
  • the electrolysis was carried out for 500 hours with the voltage remaining constant at 5V.
  • the NaSICON ceramic expands or shrinks due to the heating and cooling effects.
  • the NaSICON membrane can shift in the cell. This is problematic as it increases the tendency of the ceramic to crack and can lead to leakage of electrolyte from the center compartment into the cathode compartment, diluting the product of the electrolysis. In addition, this can lead to leaks in the outer wall of the cell, which lead to leakage of electrolyte to the outside.
  • Comparative example 2 Comparative example 1 was repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by the ceramic of the NaSICON type (FIG. 1A). This electrolytic cell therefore contained no middle chamber. This is reflected in an even more rapid corrosion of the ceramic compared to comparative example 1, which leads to a rapid increase in the stress curve leads. With an initial value of the voltage of ⁇ 5 V, this increases to > 20 V within 100 hours.
  • Comparative example 1 is repeated, using an electrolytic cell according to FIG. 6A, in which a partition comprising two NaSICON ceramics are used in a frame. This arrangement reduces the rate at which the ceramic expands and shrinks, which contributes to the durability of the ceramic and results in a cleaner product solution by eliminating leakage.
  • Comparative example 2 is repeated, using an electrolytic cell according to Figure 6 A, in which a partition comprising four NaSICON ceramics were used in a frame, in which frame element R and partition element T are fused ( Figure 7 A, but without a hinge and without a lock ).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

Dans un premier aspect, la présente invention concerne une cellule d'électrolyse (E) comprenant une paroi de séparation (W) qui convient à une utilisation dans une cellule d'électrolyse (E). La paroi de séparation (W) entoure au moins deux céramiques à électrolyte solide (FA) et (FB) conductrices de cations alcalins, qui sont séparées l'une de l'autre par au moins un élément de séparation (T). Comparativement aux cas selon l'état de la technique, dans lesquels la paroi de séparation (W) entoure l'électrolyte solide en une seule pièce, cet agencement est plus flexible et chaque céramique dispose de davantage de degrés de liberté, afin de réagir à des variations de température en se rétractant ou en se dilatant, par exemple. Il en résulte une augmentation de la stabilité aux contraintes mécaniques dans la céramique. La cellule d'électrolyse (E) comprend une chambre cathodique (KK) qui est séparée de la chambre voisine, qui est une chambre centrale (KM) de la cellule d'électrolyse (E), par ladite paroi de séparation (W). Dans un deuxième aspect, la présente invention concerne un procédé de production d'une solution d'alcoolate de métal alcalin dans la cellule d'électrolyse E selon le premier aspect de l'invention.
PCT/EP2022/070140 2021-07-29 2022-07-19 Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse WO2023006493A1 (fr)

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KR1020247003288A KR20240034777A (ko) 2021-07-29 2022-07-19 전해 셀을 위한 고체 전해질 세라믹을 포함하는 내파단성 파티션
CN202280052861.7A CN117813419A (zh) 2021-07-29 2022-07-19 用于电解池的包含固态电解质陶瓷的抗破裂分隔壁
EP22751379.3A EP4377498A1 (fr) 2021-07-29 2022-07-19 Paroi de séparation résistante à la rupture entourant des céramiques à électrolyte solide pour cellules d'électrolyse

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