EP4399349A1 - Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse - Google Patents

Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse

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Publication number
EP4399349A1
EP4399349A1 EP22765897.8A EP22765897A EP4399349A1 EP 4399349 A1 EP4399349 A1 EP 4399349A1 EP 22765897 A EP22765897 A EP 22765897A EP 4399349 A1 EP4399349 A1 EP 4399349A1
Authority
EP
European Patent Office
Prior art keywords
ofa
chamber
solid electrolyte
smf
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22765897.8A
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German (de)
English (en)
Inventor
Philip Heinrich REINSBERG
Michael Horn
Rüdiger TEUFERT
Marc Weiner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
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Evonik Operations GmbH
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Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4399349A1 publication Critical patent/EP4399349A1/fr
Pending legal-status Critical Current

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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
    • C25B13/04—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
    • C25B3/01—Products
    • C25B3/13—Organo-metallic 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
    • 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
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • 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
    • 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
    • C25B9/60—Constructional parts of cells

Definitions

  • the present invention relates to a method for producing an alkali metal alkoxide solution Li in an electrolytic cell E which comprises at least one cathode chamber KK, at least one anode chamber KA and at least one middle chamber KM located in between.
  • F has the surface OF, and part OA/MK of this surface OF directly contacts the inner space IKM, and part OKK of this surface OF directly contacts the inner space IKK.
  • the surface OA/MK and/or the surface OKK comprises at least part of a surface OFA.
  • OFA results from a pre-treatment step in which F is made from an AFK F' with the surface OF'.
  • the surface OF' is removed from F' by compressed air blasting with a solid blasting agent N AFK, and the AFK F with the surface OF is obtained including the surface OFA formed by the compressed air blasting.
  • Electrolysis to produce the alkali metal alkoxides with F instead of F' results in improved conductivity, which means that a lower voltage can be used at a constant current density.
  • the electrochemical production of alkali metal alkoxide solutions is an important industrial process that is described, for example, in DE 103 60 758 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.
  • NaSICON solid electrolytes are also used in the electrochemical production of other compounds:
  • WO 2014/008410 A1 describes an electrolytic process for the production of elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from TiÜ2 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 with electrolytically produced protons to form glycerol and the respective alkali metal hydroxide be implemented.
  • a disadvantage of the electrolytic cells described in the prior art is that the resistance of the solid electrolyte ceramics used therein is relatively high. As a result, the specific energy consumption of the electrolytically produced materials increases and the energy-specific data (current, voltage) of the cell also deteriorate. Eventually the whole process becomes economically unviable.
  • the object of the present invention was therefore to provide a process for preparing an alkali metal alkoxide solution in an electrolytic cell which does not have this disadvantage.
  • a further disadvantage of conventional electrolytic cells in this technical field results from the fact that the solid electrolyte is not stable over the long term with respect to aqueous acids. This is problematic insofar as the pH drops in the anode chamber during electrolysis as a result of oxidation processes (for example when halogens are produced by disproportionation or by oxygen formation). These acidic conditions attack the NaSICON solid electrolyte, so the process cannot be used on an industrial scale.
  • Various approaches have been described in the prior art to address this problem.
  • 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 center compartment is used as a buffer compartment to prevent the purified alkoxide or hydroxide solution from the cathode compartment from mixing with the contaminated solution from the anode compartment.
  • DE 42 33 191 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.
  • a further object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide. This should not have the aforementioned disadvantages and should in particular ensure improved protection of the solid electrolyte against the formation of the pH gradient and more economical use of the educts compared to the prior art.
  • FIG. 1 A illustrate steps (i) and (ii) of the method according to the invention.
  • FIG. 1A shows an alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>, as provided according to step (i).
  • This has a surface OF' ⁇ 190>.
  • the surface OF' ⁇ 190> comprises, for example, two sub-areas, in Fig. 1A these are the opposite surfaces denoted by the reference symbols ⁇ 191> and ⁇ 192>, of which the rear ⁇ 192> is covered.
  • the AFK F' ⁇ 19> is arranged in a process chamber ⁇ 90> opposite a sandblaster ⁇ 40> such that the partial surface area ⁇ 191> is opposite it, while the partial surface area ⁇ 192> is turned away from it .
  • Fig. 1C shows the sandblasting step. A jet of a solid blasting medium N ⁇ 30> is generated with the sandblaster ⁇ 40> and accelerated in the direction of the AFK F' ⁇ 19>. As a result, AFK is removed as particle ⁇ 185> from F' ⁇ 19>.
  • This method step gives an AFK F ⁇ 18> whose surface OF ⁇ 180> comprises a partial surface OA/MK ⁇ 181> facing the sandblaster ⁇ 40> and a partial surface OKK ⁇ 182> facing away from the sandblaster ⁇ 40>.
  • OA/MK ⁇ 181> in turn includes a sub-area OFA ⁇ 183>, which was formed by sandblasting AFK from F' ⁇ 19>.
  • FIG. 1D shows the AFK F ⁇ 18> obtained in this way, which is obtained after step (ii).
  • This has a surface OF ⁇ 180>.
  • the surface OF ⁇ 180> includes the two sub-areas OA/MK ⁇ 181> and OKK ⁇ 182>.
  • F ⁇ 18> corresponds to F' ⁇ 19> or the surface OF ⁇ 180> corresponds to the surface OF' ⁇ 190> with the difference that OA/MK ⁇ 181> includes the partial area OFA ⁇ 183>.
  • SMF that is the mass-related specific surface SM of the AFK F ⁇ 18>
  • SMFS that is the mass-related specific surface SM of the AFK F' ⁇ 19>
  • Figure 2 A shows an embodiment not according to the invention based on an electrolytic cell, which is a two-chamber cell.
  • This electrolytic cell includes a cathode chamber KK ⁇ 12> and an anode chamber KA ⁇ 11>.
  • the anode chamber KA ⁇ 11> includes an anodic electrode EA ⁇ 113> in the interior IKA ⁇ 112>, an inlet ZKA ⁇ 110> and an outlet AKA ⁇ 111>.
  • the cathode chamber KK ⁇ 12> comprises a cathodic electrode EK ⁇ 123> in the interior IKK ⁇ 122>, an inlet ZKK ⁇ 120> and an outlet AKK ⁇ 121>.
  • This electrolytic cell is delimited by an outer wall WA ⁇ 80>.
  • the interior IKK ⁇ 122> is also separated from the interior IKA ⁇ 112> by a partition wall W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte ceramic F' ⁇ 19> that is selectively permeable for sodium ions and has a surface OF' ⁇ 190> .
  • the NaSICON solid electrolyte ceramic F' ⁇ 19> extends over the entire depth and height of the two-chamber cell.
  • the NaSICON solid electrolyte ceramic F' ⁇ 19> contacts the two interiors IKK ⁇ 122> and IKA ⁇ 112> directly via the partial surfaces ⁇ 192> and ⁇ 191>, respectively, so that sodium ions can flow from one interior to the other through the NaSICON solid electrolyte ceramic F ' ⁇ 19> can be routed.
  • the respective alkaline cation conductive Solid electrolyte ceramics F' ⁇ 19> or F ⁇ 18> are arranged in the respective electrolytic cell in such a way that the darkened area in Figures 1A and 1D faces the viewer in Figures 2A and 2B.
  • An aqueous solution of sodium chloride L3 ⁇ 23> with pH 10.5 is fed counter to gravity into the interior IKA ⁇ 112> via the inlet ZKA ⁇ 110>.
  • a solution of sodium methoxide in methanol L2 ⁇ 22> is fed into the interior space IKK ⁇ 122> via the inlet ZKK ⁇ 120>.
  • a voltage is applied between the cathodic electrode EK ⁇ 123> and the anodic electrode EA ⁇ 113>.
  • methanol in the electrolyte L2 ⁇ 22> is reduced to methoxide and H2 (CH3OH + e - CH3O + 14 H2).
  • Sodium ions diffuse from the interior IKA ⁇ 112> through the NaSICON solid electrolyte F ⁇ 18> into the interior IKK ⁇ 122>.
  • FIG. 2 B shows a further embodiment of a method not according to the invention.
  • the electrolytic cell corresponds to the arrangement shown in FIG. 2A with the difference that a NaSICON solid electrolyte ceramic F ⁇ 18> with the surface OF ⁇ 180> pretreated with the method according to Figures 1A to 1D is used as the partition W ⁇ 16> becomes.
  • F ⁇ 18> has a partial surface OKK ⁇ 182> directly contacting the interior space IKK ⁇ 122> and a partial surface OA/MK ⁇ 181> directly contacting the interior space IKA ⁇ 112>.
  • the NaSICON solid electrolyte F ⁇ 18> is obtained from the NaSICON solid electrolyte F' ⁇ 19> by the sandblasting process shown in FIGS formed on the partial surface OA/MK ⁇ 181> by the sandblasting process.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> has a larger mass-related specific surface area SMF than that (SMF') of the alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>. This leads to better conductivity, i.e. a reduction in voltage with the same current during electrolysis, which leads to energy savings.
  • FIG. 3 A shows an embodiment of the method according to the invention.
  • the three-chamber electrolytic cell E ⁇ 1> comprises a cathode chamber KK ⁇ 12>, an anode chamber KA ⁇ 11> and a middle chamber KM ⁇ 13> located in between.
  • the anode chamber KA ⁇ 11> includes an anodic electrode EA ⁇ 113> in the interior IKA ⁇ 112>, an inlet ZKA ⁇ 110> and an outlet AKA ⁇ 111>.
  • the cathode chamber KK ⁇ 12> comprises a cathodic electrode EK ⁇ 123> in the interior IKK ⁇ 122>, an inlet ZKK ⁇ 120> and an outlet AKK ⁇ 121>.
  • the middle chamber KM ⁇ 13> includes an interior space IKM ⁇ 132>, an inlet ZKM ⁇ 130> and an outlet AKM ⁇ 131>.
  • the interior IKA ⁇ 112> is connected to the interior IKM ⁇ 132> via the connection VAM ⁇ 15>.
  • the electrolytic cell E ⁇ 1> is delimited by an outer wall WA ⁇ 80>.
  • the interior IKK ⁇ 122> is also separated from the interior IKM ⁇ 132> by a partition wall W ⁇ 16>, which consists of a disk of a NaSICON solid electrolyte ceramic F ⁇ 18> that is selectively permeable for sodium ions and has the surface OF ⁇ 180>.
  • This has a partial surface OKK ⁇ 182> directly contacting the interior space IKK ⁇ 122> and a partial surface OA/MK ⁇ 181> directly contacting the interior space IKM ⁇ 132>.
  • F ⁇ 18> extends over the entire depth and height of the three-chamber cell E ⁇ 1>.
  • F ⁇ 18> is obtained from the NaSICON solid electrolyte ceramic F' ⁇ 19> by a sandblasting process which corresponds to the process shown in Figures 1 A to 1 D and, in contrast to F' ⁇ 19>, has the partial area OFA ⁇ 183> , which has formed on the partial surface OA/MK ⁇ 181> by the sandblasting process.
  • the surface area OFA ⁇ 183> obtained through process step (ii) is larger in the NaSICON solid electrolyte ceramic F ⁇ 18> according to FIG. 3A.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> has an even greater mass-related specific surface area SMF than that (SMF') of the alkali cation-conducting solid electrolyte ceramic F' ⁇ 19>. This leads to even better conductivity.
  • the NaSICON solid electrolyte ceramic F ⁇ 18> contacts the two interiors IKK ⁇ 122> and IKM ⁇ 132> directly, so that sodium ions can be conducted from one interior to the other through the NaSICON solid electrolyte ceramic F ⁇ 18>.
  • the interior space IKM ⁇ 132> of the middle chamber KM ⁇ 13> is additionally separated from the interior space IKA ⁇ 112> of the anode chamber KA ⁇ 11> by a diffusion barrier D ⁇ 14>.
  • the NaSICON solid electrolyte F ⁇ 18> and the diffusion barrier D ⁇ 14> extend over the entire depth and height of the three-chamber cell E ⁇ 1>.
  • the diffusion barrier D ⁇ 14> is a cation exchange membrane (sulfonated PTFE).
  • connection VAM ⁇ 15> is formed outside the electrolytic cell E ⁇ 1>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
  • liquid can be conducted from the interior IKM ⁇ 132> of the middle chamber KM ⁇ 13> into the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11> outside the three-chamber cell E ⁇ 1>.
  • connection VAM ⁇ 15> connects an outlet AKM ⁇ 131>, which breaks through the outer wall WA ⁇ 80> of the electrolytic cell E ⁇ 1> at the bottom of the central chamber KM ⁇ 13>, with an inlet ZKA ⁇ 110>, which is at the bottom of the anode chamber KA ⁇ 11> breaks through the outer wall WA ⁇ 80> of the electrolytic cell E.
  • An aqueous solution of sodium chloride L3 ⁇ 23> with a pH of 10.5 is fed via the inlet ZKM ⁇ 130> in the same direction as gravity into the interior space IKM ⁇ 132> of the central chamber KM ⁇ 13>.
  • the connection VAM ⁇ 15> which is formed between the outlet AKM ⁇ 131> of the middle chamber KM ⁇ 13> and an inlet ZKA ⁇ 110> of the anode chamber KA ⁇ 11>, creates the interior space IKM ⁇ 132> of the middle chamber KM ⁇ 13 > connected to the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11>.
  • Sodium chloride solution L3 ⁇ 23> is conducted through this connection VAM ⁇ 15> from the interior IKM ⁇ 132> to the interior IKA ⁇ 112>.
  • a solution of sodium methoxide in methanol L2 ⁇ 22> is fed into the interior space IKK ⁇ 122> via the inlet ZKK ⁇ 120>.
  • a voltage is applied between the cathodic electrode EK ⁇ 123> and the anodic electrode EA ⁇ 113>.
  • methanol in the electrolyte L2 ⁇ 22> is reduced to methoxide and H2 (CH3OH + e • -» CHsO- + 1 H2).
  • Sodium ions diffuse from the interior IKM ⁇ 132> of the central chamber KM ⁇ 103> through the NaSICON solid electrolyte F ⁇ 18> into the interior IKK ⁇ 122>.
  • FIG. 3 B shows a further embodiment of the method according to the invention. This is carried out in an electrolytic cell E ⁇ 1>, which corresponds to the electrolytic cell E ⁇ 1> shown in Figure 3 A with the following difference:
  • connection VAM ⁇ 15> from the interior IKM ⁇ 132> of the middle chamber KM ⁇ 13> to the interior IKA ⁇ 112> of the anode chamber KA ⁇ 11> is not made outside but through a perforation in the diffusion barrier D ⁇ 14> inside the electrolytic cell E ⁇ 1> formed.
  • This perforation can be introduced into the diffusion barrier D ⁇ 14> subsequently (e.g. by stamping, drilling) or be present in the diffusion barrier D ⁇ 14> from the outset due to the production thereof (e.g. in the case of textile fabrics such as filter cloths or metal fabrics).
  • Figure 4 shows the increase in conductivity of a NaSICON ceramic that was sandblasted according to step (ii).
  • the three ceramics are pieces of a large pottery, two of which have been sandblasted while one has been left untreated.
  • the x-axis shows the current (in mA), the y-axis shows the voltage (in volts).
  • A indicates the stress curve of an untreated NaSICON ceramic (comparison). and indicate the stress curve of the two sandblasted NaSICON ceramics. 4. Detailed Description of the Invention
  • “AFK” alkali cation-conducting solid electrolyte ceramic
  • step (i) The AFK F' provided in step (i) is subjected to step (ii) in the method according to the invention, and after step (ii) the AFK F with the surface OF is obtained. Since F is essentially obtained from F' by removing a portion of AFK from F' in step (ii) to arrive at F, F' and F have essentially the same chemical structure.
  • any solid electrolyte through which cations, in particular alkali cations, more preferably sodium cations, can be transported from IKM to IKK can be used as the alkali cation-conducting solid electrolyte ceramic F', and in particular also F.
  • Such solid electrolytes are known to the person skilled in the art and are known, for example, in DE 10 2015 013 155 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]. They are sold commercially under the names NaSICON, LiSICON, KSICON.
  • a sodium ion conductive solid electrolyte ceramic F' is preferred, which more preferably has 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, M. Vithal, J Mater Sei 2011, 46, 2821-2837.
  • the alkali cation-conducting solid electrolyte ceramic F' has a NaSICON structure of the formula M'i+2w+x- y +z M"w M'"x Zr lv 2-wxy M v y (SiO 4 ) z (PO 4 ) 3 -z.
  • M 1 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 111 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 alkali cation-conducting solid electrolyte ceramics F' and F have the same structure.
  • step (ii) of the method according to the invention part of the alkali cation-conducting solid electrolyte ceramic F' is removed by compressed air blasting with a solid blasting agent N.
  • step (ii) part of F' is removed by sandblasting AFK.
  • compressed air blasting with a solid blasting medium N includes inflation, in particular with compressed air.
  • AFK AFK is removed from F'
  • the extent to which AFK is removed from F' can be controlled by a person skilled in the art, for example via the selection of the solid blasting medium N, the pressure set and the time over which F' is sandblasted.
  • the pressure here is in particular >1 bar, preferably 2 to 10 bar, even more preferably 6 bar.
  • All solid blasting media customary in industry in particular sand, blast furnace slag, glass granules, corundum, steel, plastic granules, nut shells, fruit stones, soda, ice crystals or CO2 snow pellets can be used as solid blasting media N.
  • Glass granules are preferred, which are even more preferably spherical glass granules.
  • the duration over which the surface OF' is sandblasted with the solid blasting medium N is in particular >1 min, preferably more than 30 min, preferably more than 60 min, even more preferably more than 120 min.
  • the AFK F' when treating the surface of a specific body, in the context of the invention the AFK F', this is arranged in a suitable process chamber and then the solid blasting agent is applied via a suitable nozzle.
  • the entire surface OF' can be treated. This is possible, for example, by first treating a part of the surface OF' in a first sub-step, in particular blasting it with the solid blasting agent N under compressed air and removing AFK from this part of the surface OF', and then in a second sub-step the in the first Sub-step not compressed air blasted side of F 'is blasted with the fixed blasting agent N and AFK is removed there.
  • the surface OF of the resulting AFK F differs completely from OFS, ie OF and OFA are identical.
  • only part of the surface OF' can also be treated in step (ii). This is possible, for example, by only treating part of the surface OF', in particular by blasting it with the solid blasting medium N, and removing AFK from only this part of the surface OF'.
  • part of the surface OF' can also be covered with a stencil, so that only part of the surface OF' is removed from those in step (ii). In this case, an AFK F is obtained whose surface OF is still partially identical to the surface OF' of F' and differs from OF' in part OFA.
  • the shape of OFA is as long as OFA is at least partially comprised by OA/MK and/or OKK, not further limited.
  • OFA can form a contiguous sub-area on the surface OF.
  • OFA can be formed by several unconnected partial areas on the surface OF, so that their shape is pronounced of the shape of the black spots (corresponds to OFA) on the white fur (corresponds to OF) of the dog breed "Dalmatian".
  • step (ii) gives an AFK F which, compared to the AFK F' used in step (ii) when used in the electrolytic cell E according to step (iii) and step (iv- ß) has a higher conductivity.
  • SMF' is the mass-related specific surface area SM of the alkali cation-conducting solid electrolyte ceramic F' before step (ii) is carried out, and where SMF is the mass-related specific surface area SM of the alkali cation-conducting solid electrolyte ceramic F after carrying out step (ii).
  • SMF' is the mass-related specific surface area SM of the alkali cation-conducting solid electrolyte ceramic F after carrying out step (ii).
  • the comparison of the mass-related specific surface areas SMF' and SMF i.e. the examination of the condition whether SMF' ⁇ SMF, can be determined using methods known to those skilled in the art for measuring the BET (Brunauer-Emmett-Teller) surface area, as long as both AFK F and F' can be measured under the same conditions. Even if the ratio of the two parameters SMF' and SMF is determined under different measurement conditions, the SMF/SMF' ratio measured under certain measurement conditions will be substantially the same as the SMF/SMF' ratio measured under other measurement conditions.
  • BET Brunauer-Emmett-Teller
  • the mass-related specific surface areas are carried out via BET measurements according to ISO 9277:2010 with N2 (purity 99.99% by volume) as the adsorbent at 77.35 K.
  • Quantachrome NOVA 2200e Quantachrome Instruments.
  • Sample preparation degassing of the sample at 60 °C at 1 Pa.
  • the evaluation is carried out in particular using the static volumetric method (according to point 6.3.1 of the ISO 9277:2010 standard).
  • the ratio SMF' and SMF i.e. the quotient SMF/SMFS:
  • SMF/ SMF' S 1.01 preferably SMF/ SMF' S 1.1, preferably SMF/ SMF' S 1.5, preferably SMF/ SMF' S 2.0, preferably SMF/ SMF' S 3.0, preferably SMF/ SMF' S 5.0, preferably SMF/ SMF' S 10, preferably SMF/ SMF' S 20, preferred SMF/ SMF' S 50, preferred SMF/ SMF' S 100, preferred SMF/ SMF' S 150, preferred SMF/ SMF' S 200, preferred SMF/ SMF' S 500, preferred SMF/ SMF' S1000.
  • the quotient SMF/SMF' is in the range from 1.01 to 1000, preferably in the range from 1.1 to 50, more preferably in the range from 1.2 to 20, more preferably in the range from 1.3 to 15. more preferably in the range from 1.4 to 10, more preferably in the range from 1.5 to 5, more preferably in the range from 2.0 to 3.5, more preferably in the range from 2.8 to 3.2.
  • step (iii) of the process according to the invention the AFK F obtained in step (ii) is arranged in an electrolysis cell E.
  • the electrolytic cell E comprises at least one anode chamber KA and at least one cathode chamber KK and at least one intermediate chamber KM. This also includes electrolytic cells E which have more than one anode chamber KA and/or more than one cathode chamber KK and/or more than one middle chamber KM. Such 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 comprises an anode chamber KA and a cathode chamber KK and a middle chamber KM lying between them.
  • the electrolytic cell E usually has an outer wall WA.
  • the outer wall WA is in particular made of a material which is selected from the group consisting of steel, preferably rubberized steel, plastic, which is in particular made of Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride) is selected.
  • WA can be perforated in particular for inlets and outlets.
  • Within WA then lie the at least one anode chamber KA, the at least one cathode chamber KK and, in the embodiments in which the electrolytic cell E includes such a cell, the at least one intermediate chamber KM.
  • the cathode chamber KK has at least one inlet ZKK, at least one outlet AKK and an interior space IKK, which includes a cathodic electrode EK.
  • the interior IKK of the cathode chamber KK is separated by the partition W from the interior IKM of the middle chamber KM.
  • the partition W includes the alkali cation-conducting solid electrolyte ceramic F, and F directly contacts the interior IKK via the surface OKK and the interior IKM via the surface OA/MK.
  • the partition wall W includes the alkali cation-conducting solid electrolyte ceramic F.
  • the feature "partition wall” means that the partition wall W is liquid-tight. This means in particular that the solid electrolyte ceramic F, which conducts alkali cations and is enclosed by the partition wall, completely separates the interior space IKK and the interior space IKM from one another, or comprises several solid electrolyte ceramics which conduct alkali cations and which, for example, adjoin one another without gaps.
  • Direct contact means for the arrangement of the alkali cation-conducting solid electrolyte ceramics in the partition wall W and in the electrolytic cell E as well as for the surfaces OKK and OA/MK that there is an imaginary path from IKK to IKM that goes completely from IKK via OKK through F to OA/MK and finally in IKM.
  • At least 1% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 1% of the surface area OKK is formed by OFA.
  • At least 10% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 10% of the surface area OKK is formed by OFA.
  • At least 25% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 25% of the surface area OKK is formed by OFA.
  • At least 40% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 40% of the surface area OKK is formed by OFA.
  • At least 50% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 50% of the surface area OKK is formed by OFA.
  • At least 60% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 60% of the surface area OKK is formed by OFA.
  • at least 70% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 70% of the surface area OKK is formed by OFA.
  • At least 80% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 80% of the surface area OKK is formed by OFA.
  • At least 90% of the surface area OA/MK is formed by OFA and/or, in particular and, at least 90% of the surface area OKK is formed by OFA.
  • 100% of the surface OA/MK is formed by OFA and/or, in particular and, 100% of the surface OKK is formed by OFA.
  • step (iv- ⁇ ) ie through which the ion flow takes place during the electrolysis, is particularly large.
  • the cathode chamber KK includes an interior IKK, which in turn includes a cathodic electrode EK.
  • a cathodic electrode EK Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the invention can be used as such a cathodic electrode EK. Such are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
  • This electrode EK can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "balls".
  • the cathodic electrode EK 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. EK preferably includes nickel.
  • the cathode chamber KK also includes an inlet ZKK and an outlet AKK- This makes it possible to add liquid, such as the solution L2, to the interior IKK of the cathode chamber KK and to remove liquid therein, such as the solution Li.
  • the inlet ZKK and the outlet AKK are attached to the cathode chamber KK in such a way that the liquid makes contact with the cathodic electrode EK as it flows through the interior IKK of the cathode chamber KK. This is the prerequisite for the solution Li being obtained at the outlet AKK when the method according to the invention is carried out when the solution L2 of an alkali metal alcoholate XOR in the alcohol ROH is passed through the interior IKK of the cathode chamber KK.
  • the inlet ZKK and the outlet AKK can be attached to the electrolytic cell E by methods known to those skilled in the art, for example through bores in the outer wall WA and corresponding connections (valves) which simplify the introduction and removal of liquid.
  • the anode chamber KA has at least one inlet ZKA, at least one outlet AKA and an interior space IKA, which includes an anodic electrode EA.
  • the interior IKA of the anode chamber KA is separated from the interior IKM of the middle chamber KM by a diffusion barrier D.
  • the anode chamber KA includes an interior space IKA, which in turn includes an anodic electrode EA.
  • anodic electrode EA Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the invention can be used as such an anodic electrode EA. Such are described in particular in WO 2014/008410 A1, paragraph [024] or DE 10360758 A1, paragraph [031].
  • This electrode EA can consist of one layer or of several flat, mutually parallel layers, each of which can be perforated or expanded.
  • the anodic electrode EA comprises in particular a material selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, precious 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).
  • Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
  • the anodic electrode EA preferably comprises a titanium anode (RuO2+IrO2/Ti) coated with ruthenium oxide/iridium oxide.
  • the anode chamber KA also includes an inlet ZKA and an outlet AKA- This makes it possible to add liquid, such as the solution L3, to the interior IKA of the anode chamber KA and to remove liquid, such as the solution L4, located therein.
  • the inlet ZKA and the outlet AKA are attached to the anode chamber KA in such a way that the liquid makes contact with the anodic electrode EA as it flows through the interior IKA of the anode chamber KA. This is the prerequisite for the solution L4 being obtained at the outlet AKA when the method according to the invention is carried out if the solution L3 of a salt S is passed through the interior IKA of the anode chamber KA.
  • the inlet ZKA and the outlet AKA can be attached to the electrolytic cell E by methods known to those skilled in the art, eg through bores in the outer wall WA and corresponding connections (valves) which simplify the introduction and removal of liquid.
  • the inlet ZKA 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 middle chamber KM.
  • the central chamber KM lies between the cathode chamber KK and the anode chamber KA.
  • the interior IKA of the anode chamber KA is separated from the interior IKM of the middle chamber KM by a diffusion barrier D.
  • AKM is then also connected to the inlet ZKA by a connection VAM, so that liquid can be conducted from IKM into IKA through the connection VAM.
  • the interior IKM of the middle chamber KM is separated from the interior IKA of the anode chamber KA by a diffusion barrier D and separated from the interior IKK of the cathode chamber KK by the partition W.
  • any material which is stable under the conditions of the method according to the invention and which prevents or slows down the transfer of protons from the liquid located in the interior iKAder the anode chamber KA into the interior IKM of the middle chamber KM can be used for the diffusion barrier D.
  • 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”). If the diffusion barrier D is a “membrane that is permeable to specific ions”, this means according to the invention that the respective membrane favors the diffusion of certain ions through it compared to other ions.
  • 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 compared to the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion type X at a given temperature for the membrane in question is higher by a factor of 10, preferably 100, preferably 1000 as the diffusion coefficient of the ionic 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 KA into the middle chamber KM particularly well.
  • a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
  • 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, V. Ramani, P.N. Pintauro, Electrochemical Society Interface 2010, 19, 31-35, in WO 2007/048712 A2 and on page 181 of the textbook by Volkmar M. Schmidt Electrochemical process engineering: Fundamentals, reaction technology, process optimization, 1st edition (October 8, 2003).
  • they have covalently bonded functional groups selected from -NH 3 + , -NRH 3 + , -NR 3 + , more preferably selected from -NH 3 + , -NR 3 + , even more preferably -NR 3 + .
  • 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.
  • organic polymers which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -SO 3 - , -COO-, -PO 3 2- , -PO2H', preferably -SO 3 -, (described in DE 10 2010 062 804 A1, US Pat. No. 4,831, 146) carry.
  • Neosepta® membranes are described, for example, by SA Mareev, D.Yu. Butylskii, ND Pismenskaya, C Larchet, L Dammak, VV Nikonenko, Journal of Membrane Science 2018, 563, 768-776.
  • 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 PNAFION, where n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 more preferably an integer of 10 2 to 10 4 .
  • the middle chamber KM also includes an inlet ZKM and an outlet AKM- This makes it possible to add liquid, such as the solution L3, to the interior IKM of the middle chamber KM, and liquid therein, such as the solution L3, to the anode chamber KA TO convert.
  • the inlet ZKM and the outlet AKM can be attached to the electrolytic cell E using methods known to those skilled in the art, e.g. through bores in the outer wall WA and corresponding connections (valves), which simplify the introduction and removal of liquid.
  • the drain AKM can also be within the electrolytic cell, for example as a perforation in the diffusion barrier D.
  • connection VAM can be formed inside the electrolytic cell E and/or outside the electrolytic cell E, and is preferably formed inside the electrolytic cell.
  • connection VAM 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 its weaving properties, has perforations and gaps from the outset, which act as a VAM connection.
  • connection VAM is formed outside the electrolysis cell E, with it preferably being formed by a connection running outside of the electrolysis cell E from AKM and ZKA is formed, in particular by forming an outlet AKM from the interior of the central chamber IKM, preferably at the bottom of the central chamber KM, with the inlet ZKM being even more preferably at the top OEM of the central chamber KM, and an inlet ZKA into the interior IKA of the anode chamber KA, preferably at the bottom of the anode chamber KA, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
  • a line for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
  • Outflow AKM at the bottom of the middle chamber KM means in particular that the outflow AKM SO is attached to the electrolytic cell E, that the solution L3 leaves the middle chamber KM in the same direction as gravity.
  • Inlet ZKA at the bottom of the anode chamber KA means in particular that the inlet ZKA SO is attached to the electrolytic cell E, that the solution L3 enters the anode chamber KA against the force of gravity.
  • Inlet ZKM on the top OEM of the middle chamber KM means in particular that the inlet ZKM is attached to the electrolytic cell E in such a way that the solution L3 enters the middle chamber KM in the same direction as gravity.
  • Outflow AKA on the top OEA of the anode chamber KA means in particular that the outflow AKA SO is attached to the electrolytic cell E, that the solution L4 leaves the anode chamber KA against the force of gravity.
  • This embodiment is particularly advantageous and therefore preferred if the outlet AKM through the bottom of the middle chamber KM and the inlet ZKA through the bottom of the anode chamber KA, is trained.
  • This arrangement makes it particularly easy to discharge gases formed in the anode chamber KA with L4 from the anode chamber KA in order to then separate them further.
  • connection VAM is formed outside of the electrolytic cell E, in particular ZKM and AKM are arranged on opposite sides of the outer wall WA of the central chamber KM (e.g. ZKM on the bottom and AKM on the top OEM of the electrolytic cell E or vice versa) and ZKA and AKA on opposite sides Arranged on the sides of the outer wall WA of the anode chamber KA (ie ZKA on the bottom and AKA on the top OEA of the electrolytic cell E), as shown in particular in Figure 3A. Due to this geometry, L3 must flow through the two chambers KM and KA.
  • 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 VAM is formed within the electrolytic cell E, this can be ensured in particular by one side ("side A") of the electrolytic cell E, which is the top OE, 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 all the way to the side opposite side A ("side B") of the electrolytic cell E, which is then the
  • the bottom of the electrolytic cell E is sufficient and 50% or more of the height of the three-chamber cell E, more preferably 60% to 99% of the height of the three-chamber cell E, even more preferably 70% to 95% of the height of the three-chamber cell E, even more preferably 80% to 90% of the height of the three-chamber cell E, more preferably 85% of the height of the three-chamber cell E spans.
  • Bottom of the electrolytic cell E is, according to the invention, the side of the electrolytic cell E through which a solution (e.g. L3 in the case of AKM in Figure 3 A) exits the electrolytic cell E in the same direction as gravity or the side of the electrolytic cell E through which a solution ( E.g. L2 at ZKK in Figures 2 A, 3 A and 3 B and L3 at AKA in Figures 2 A, 2 B and 3 A) of the electrolytic cell E against gravity.
  • a solution e.g. L3 in the case of AKM in Figure 3 A
  • L4 for AKA and Li for AKK in all figures 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. L3 at ZKM in Figures 3 A and 3 B) is fed to the electrolytic cell E in the same direction as gravity.
  • a solution e.g. L3 at ZKM in Figures 3 A and 3 B
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramic F, which conducts alkali cations and is enclosed by the dividing wall W, makes direct contact with the interior space IKK via the surface OKK.
  • the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space IKK is completely filled with solution L2, the solution L2 contacts (i.e. wets) the surface OKK of the solid electrolyte ceramic F which conducts alkali cations and is enclosed by the dividing wall W. so that ions (e.g. alkali metal ions such as sodium, lithium) from the alkali cation-conducting solid electrolyte ceramic F, which is surrounded by the partition W, can enter the solution L2 via the surface OKK.
  • ions e.g. alkali metal ions such as sodium, lithium
  • the dividing wall W is arranged in the electrolytic cell E in such a way that the solid electrolyte ceramic F, which conducts alkali cations, is enclosed by the dividing wall W and makes direct contact with the interior space IKM via the surface OA/MK.
  • the electrolytic cell E comprises at least one middle chamber KM, and the partition wall W borders on the interior space IKM of the middle chamber KM.
  • the dividing wall W is arranged in the electrolytic cell E in such a way that when the interior space IKM is completely filled with solution L3, the solution L3 then contacts (i.e. wets) the surface OA/MK of the solid electrolyte ceramic F that is enclosed by the dividing wall W and which conducts alkali cations, so that ions (e.g. alkali metal ions such as sodium, lithium) from the solution L3 can enter the alkali cation-conducting solid electrolyte ceramic F, which is surrounded by the partition W, via the surface OA/MK.
  • ions e.g. 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 process is carried out in an electrolytic cell E.
  • 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.
  • Steps ( ⁇ 1), ( ⁇ 2), ( ⁇ 3) running simultaneously are carried out.
  • OKK comprises at least part of OFA
  • the solution L2 contacts the surface OFA directly.
  • the solution L2 then directly contacts the entire surface OFA covered by OKK.
  • the solution L2 is preferably free of water.
  • "free of water” means that the weight of the water in the solution L2 based on the weight of the alcohol ROH in the solution L2 (mass ratio) ⁇ 1:10, more preferably e 1:20, more preferably e 1:100, still more preferably e is 0.5:100.
  • the mass fraction of XOR in the solution L2, based on the total solution L2, is in particular >0 to 30% by weight, preferably 5 to 20% by weight, more preferably 10 to 10% by weight 20% by weight, 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 L2 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 from 1:12 to 1 : 8, more preferably at 1:10. 4.4.2 Step (ß2)
  • step ( ⁇ 2) a neutral or alkaline, aqueous solution L3 of a salt S comprising X as a cation is passed through IKM, then through VAM, then through IKA.
  • aqueous solution L3 of a salt S comprising X as a cation is passed through IKM, then through VAM, then through IKA.
  • the solution L3 thereby contacts the surface OFA directly.
  • the solution L3 then directly contacts the entire surface OFA encompassed by OA/MK.
  • L3 contacts at least a part of the surface OFA, directly, and in the cases where OA/MK covers only a part of the surface OFA, L3 at least directly contacts part of the part of the surface OFA covered by OA/MK.
  • 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 L3 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 L3 is preferably in the range >0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight. -%, most preferably at 20% by weight, based on the total solution L3.
  • step (ß3) a voltage is then applied between EA and EK.
  • 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 certain voltages via voltage converters. This in turn has the following consequences: at outlet AKK the solution Li is obtained, the concentration of XOR in Li being higher than in L2, at outlet AKA an aqueous solution L4 of S is obtained, the concentration of S in L4 being lower than in L3.
  • This can be determined by a person skilled in the art by default.
  • the area of the solid electrolyte that contacts the anolyte located in the interior IKM of the middle chamber KM 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 .
  • both OA/MK and OKK comprise part of the surface OFA.
  • Step (ß3) of the method is carried out even more preferably if the interior IKM is at least loaded with L3 and the interior IKK is loaded with L2 at least to the extent that L3 and L2, the surface OFA covered by the partition W contact alkali cation-conducting solid electrolyte ceramics F directly.
  • the surface OFA obtained by the treatment in step (ii) takes part within both surfaces OA / MK and OKK in the electrolysis process and the advantageous properties of the alkali cation-conducting solid electrolyte ceramic F, which result in an increase in conductivity and thus an increase in Reject amperage at the same voltage, have a particularly positive effect.
  • step (ß3) The fact that charge transport takes place between EA and EK in step (ß3) implies that IKK, IKM and IKA are simultaneously loaded with L2 and L3, respectively, in such a way that they cover the electrodes EA and EK to such an extent that the current circuit is closed is.
  • step ( ⁇ 1) and step ( ⁇ 2) are carried out continuously and voltage is applied in accordance with step ( ⁇ 3).
  • step ( ⁇ 3) After step ( ⁇ 3) has been carried out, solution Li is obtained at outlet AKK, the concentration of XOR in Li being higher than in L2.
  • 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 1,08 times higher than in L2, most preferably 1,077 times higher than in L2, more preferably the mass fraction of XOR in Li and in L2 in the range 10 to 20 wt%, more preferably 13 to 14 wt%.
  • the concentration of the cation X in the aqueous solution L3 is preferably in the range of 3.5 to 5 mol/l, more preferably 4 mol/l.
  • the concentration of the cation X in the aqueous solution L4 is more preferably 0.5 mol/l lower than that of the aqueous solution S3 used in each case.
  • steps (ß1) to (ß3) of the process 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, even 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 interior IKK of the cathode chamber KK, which hydrogen 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 L4.
  • oxygen and/or carbon dioxide can also be formed, which can also be removed.
  • the mixture of chlorine, oxygen and/or CO2 and solution L4 can then be separated by methods known to those skilled in the art.
  • the gases chlorine, oxygen and/or CO2 have been separated from the solution L4, these can be separated from one another by methods known to those skilled in the art.
  • steps ( ⁇ 1) to ( ⁇ 3) brings other surprising advantages which were not to be expected in the light of the prior art.
  • the acid-labile solid electrolyte is protected against corrosion by steps (ß1) to (ß3) of the method according to the invention, without having to sacrifice alcoholate solution from the cathode compartment as a buffer solution, as is the case in the prior art.
  • steps (ß1) to (ß3) of the method according to the invention without having to sacrifice alcoholate solution from the cathode compartment as a buffer solution, as is the case in the prior art.
  • NM Sodium methylate
  • the electrolytic cell consisted of three chambers, as shown in Figure 3 A.
  • 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 33 cm 2 cation exchange membrane (Asahi Kasei, sulfonic acid groups on polymer).
  • the cathodes and middle chamber were separated by a ceramic of the NaSICON type with an area of 33 cm 2 .
  • the ceramic had a chemical composition of the formula Na34Zr2 oSi24P06O12.
  • the NaSICON ceramic used in Comparative Example 1 was cut from the same block together with two other ceramics of the same dimensions.
  • 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 1 l/h.
  • the temperature was 60°C.
  • Comparative example 1 is repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by a ceramic as in comparative example 1.
  • the arrangement is as shown in Figure 2A.
  • this electrolytic cell does not contain a center chamber. This is reflected in even more rapid corrosion of the ceramic compared to Comparative Example 1, which leads to a faster increase in the voltage curve if the electrolysis is to be operated at a constant current intensity over a defined time.
  • the pressure was 6 bar and the distance from the sandblasting nozzle was 20 cm.
  • the mass-related specific surface of the NaSICON ceramic increased by a factor of ⁇ 3.
  • the x-axis shows the current (in mA), the y-axis shows the voltage (in volts).
  • A indicates the current/voltage curve of the non-sandblasted NaSICON ceramic. and indicate the current/voltage curve of the two sandblasted NaSICON ceramics.
  • Comparative example 2 is repeated using an electrolytic cell in which the solid electrolyte ceramics treated in accordance with example 1 according to the invention are used.
  • a voltage that is significantly lower than that in comparative example 2 is required for the same current intensity.
  • the conductivity of the solid electrolyte increases surprisingly due to the pretreatment (sandblasting) of the NaSICON ceramic and the exposure of the sandblasted surfaces on the interior spaces of the anode chamber or middle chamber and the cathode chamber.
  • the use of the three-chamber cell in the method of the invention also prevents corrosion of the solid electrolyte while at the same time not sacrificing an alkali metal alkoxide product for the center chamber and keeping the voltage constant.

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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 Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un procédé de production d'une solution d'alcoolates de métaux alcalins L1 dans une cellule d'électrolyse E qui comprend au moins une chambre cathodique KK, au moins une chambre anodique KA et au moins une chambre centrale KM située entre celles-ci. L'espace intérieur IKK de la chambre cathodique KK est séparé de l'espace intérieur IKM de la chambre centrale KM par une paroi de séparation W comprenant au moins une céramique à électrolyte solide conductrice de cations alcalins (= "AFK") F (p. ex. NaSICON). F présente la surface OF, et une partie OA/MK de cette surface OF est en contact direct avec l'espace intérieur IKM, et une partie OKK de cette surface OF est en contact direct avec l'espace intérieur IKK. La surface OA/MK et/ou la surface OKK comprennent au moins une partie d'une surface OFΔ. OFΔ est obtenue par une étape de prétraitement au cours de laquelle F est produite à partir d'une AFK F' présentant la surface OF'. À cet effet, de l'AFK est enlevée de F' par sablage à air comprimé de la surface OF' avec un abrasif solide N, et l'on obtient l'AFK F présentant la surface OF comprenant la surface OFΔ formée par sablage à air comprimé. Lors de l'électrolyse pour la production des alcoolates de métaux alcalins avec F au lieu de F', on obtient une conductivité améliorée, ce qui permet d'utiliser une tension plus faible avec une densité de courant constante.
EP22765897.8A 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse Pending EP4399349A1 (fr)

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EP21195069.6A EP4144890A1 (fr) 2021-09-06 2021-09-06 Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse
PCT/EP2022/073158 WO2023030920A1 (fr) 2021-09-06 2022-08-19 Procédé de production d'alcoolates de métaux alcalins dans une cellule d'électrolyse

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EP4144888A1 (fr) 2021-09-06 2023-03-08 Evonik Functional Solutions GmbH Procédé de production d'alcoolats alcalins dans une cellule d'électrolyse

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EP4144890A1 (fr) 2023-03-08

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