EP4112779B1 - Three-chamber electrolysis cell for the production of alkali metal alcoholate - Google Patents

Description

In a first aspect, the present invention relates to an electrolytic cell which has three chambers, the middle chamber being separated from the cathode chamber by a solid electrolyte which is permeable to cations, for example NaSICON, and from the anode chamber by a diffusion barrier. The invention is characterized in that the middle chamber comprises a mechanical stirring device.

The electrolytic cell according to the invention solves the problem that a concentration gradient forms in the middle chamber of the electrolytic cell during electrolysis, which leads to locally reduced pH values and thus to damage to the solid electrolyte. The mechanical stirring device can be used to stir the electrolyte solution in the middle chamber during electrolysis, which prevents the formation of a pH gradient.

In a second aspect, the present invention relates to a method for producing an alkali metal alkoxide solution in the electrolytic cell according to the invention.

1. Background of the Invention

The electrochemical production of alkali metal alkoxide solutions is an important industrial process that is used, for example, in DE 103 60 758 A1 , the U.S. 2006/0226022 A1 and the WO 2005/059205 A1 is described. 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. When a current is applied, chlorine is formed at the anode - if a chloride salt of the alkali metal is used - and hydrogen and alcohol ions are formed at the cathode. The charge is equalized by the alkali metal ions migrating from the middle chamber into the cathode chamber via the ceramic that is selective for them. The charge equalization between the middle chamber and the anode chamber takes place through the migration of cations when using cation exchange membranes or the migration of anions when using anion exchange membranes or through the migration of both types of ions when using non-specific diffusion barriers. This increases the concentration of the alkali alcoholate in the cathode chamber and the concentration of the sodium ions in the anolyte decreases.

• WO 2014/008410 A1 beschreibt ein elektrolytisches Verfahren zur Herstellung von elementarem Titan oder Seltenen Erden. Dieses Verfahren beruht darauf, dass Titanchlorid aus TiOz und der entsprechenden Säure gebildet wird, dieses mit Natriumalkoholat zum Titaniumalkoholat und NaCl reagiert und schließlich elektrolytisch zu elementarem Titan und Natriumalkoholat umgesetzt wird.
• WO 2007/082092 A2 und WO 2009/059315 A1 beschreiben Verfahren zur Herstellung von Biodiesel, in denen mithilfe von über NaSICON elektrolytisch hergestellten Alkoholaten zunächst Triglyceride in die entsprechenden Alkalimetalltriglyceride überführt werden und in einem zweiten Schritt mit elektrolytisch erzeugten Protonen zu Glycerin und dem jeweiligen Alkalimetallhydroxid umgesetzt werden.

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 TiOz and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally converted electrolytically to form 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 into glycerol and the respective alkali metal hydroxide with electrolytically produced protons.

Accordingly, methods are described in the prior art which are carried out in electrolytic cells with an ion-permeable layer, such as, for example, NaSiCON solid electrolytes. However, these solid electrolytes typically have the disadvantage that they are not long-term stable 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.

Three-chamber cells have been proposed in the prior art. Such are known in the field of electrodialysis, for example US 6,221,225 B1 .

WO 2012/048032 A2 and US 2010/0044242 A1 describe, for example, electrochemical processes for the production of 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. In order to protect this from the acidic anolyte, the middle chamber is supplied with solution from the cathode chamber, for example. The US 2010/0044242 A1 also describes in Figure 6 that solution from the middle compartment can be mixed with solution from the anode compartment outside the compartment to obtain sodium hypochlorite.

Such cells have also been proposed in the prior art for the production or purification of alkali metal alkoxides.

That's how she describes it US 5,389,211A a process for the purification of alcoholate 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.

The DE 42 33 191 A1 describes the electrolytic production of alcoholates from salts and alcoholates in multi-chamber cells and stacks of several cells.

The 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 ). This protects the solid electrolyte separating the middle chamber and the cathode chamber from the solution in the anode chamber, which becomes more acidic during the electrolysis. A similar arrangement is described in WO 2009/073062 A1 . However, this arrangement has the disadvantage that the alkali metal alkoxide solution is the desired product, but this is consumed as a buffer solution and is continuously contaminated. Another disadvantage of the in the WO 2008/076327 A1 The method described is that the formation of the alcoholate in the cathode chamber depends on the diffusion rate of the alkali metal ions through two membranes or solid electrolytes. This in turn slows down the formation of the alcoholate.

Another problem arises from the geometry of the three-chamber cell. In such a chamber, the central chamber is separated from the anode chamber by a diffusion barrier and from the cathode chamber by an ion-conducting ceramic. During the electrolysis, 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.

While this effect takes place throughout the electrolysis chamber, the drop in pH is particularly critical in the center chamber, which is bounded by the ion-conducting ceramic. Gases are usually formed at the anode and the cathode, so that there is at least a certain degree of mixing in these chambers. On the other hand, such mixing does not take place in the middle chamber, so that the pH gradient develops in it. This undesirable effect is amplified by the fact that the brine is generally pumped relatively slowly through the electrolytic cell.

The object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide and an electrolysis chamber which is particularly suitable for such a process. These 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. Other documents, see EP 3 885 470 A1 , EP 3 885 471 A1 , U.S. 5,425,856 A , U.S. 5,575,901A , U.S. 2007/138020 A1 , U.S. 2019/292668 A1 , CN 108 411 321 A , CN 111 074 288 A .

2. Summary of the Invention

Surprisingly, an electrolytic cell and a method have now been found which achieve the object of the invention.

• wobei K_A <101 > eine anodische Elektrode E_A <104> und einen Ablauf A_KA <106> umfasst, wobei K_K <102> eine kathodische Elektrode E_K <105>, einen Zulauf Z_KK <107> und einen Ablauf A_KK <109> umfasst,
• wobei K_M <103> einen Zulauf Z_KM <108> umfasst, durch eine Diffusionsbarriere D <110> von K_A <101 > abgetrennt ist und durch einen alkalikationenleitenden Festelektrolyten F_K <111> von K_K <102> abgetrennt ist,
• wobei K_M <103> und K_A <101 > durch eine Verbindung V_AM <112> miteinander verbunden sind, durch welche Flüssigkeit aus K_M <103> in K_A <101 > geleitet werden kann,
• und ist dadurch gekennzeichnet, dass die Mittelkammer K_M <103> eine mechanische Rührvorrichtung umfasst.

The electrolytic cell E <100> according to the first aspect of the invention comprises at least one anode chamber K _A <101>, at least one cathode chamber K _K <102> and at least one intermediate chamber K _M <103>,

• where K _A <101> comprises an anodic electrode E _A <104> and an outlet A _KA <106>, where K _K <102> comprises a cathodic electrode E _K <105>, an inlet Z _KK <107> and an outlet A _KK <109> includes,
• where K _M <103> comprises an inlet Z _KM <108>, is separated from K _A <101> by a diffusion barrier D <110> and is separated from _K K <102> by an alkali cation-conducting solid electrolyte _{F K} <111>,
• where K _M <103> and K _A <101> are connected to each other by a connection V _AM <112>, through which liquid can be conducted from K _M <103> to K _A <101>,
• and is characterized in that the central chamber K _M <103> comprises a mechanical stirring device.

• wobei das Verfahren die folgenden, gleichzeitig ablaufenden Schritte (a), (b) und (c) umfasst:
  1. (a) ein Lösung L₂ <113> umfassend den Alkohol ROH wird durch K_K <102> geleitet,
  2. (b) eine neutrale oder alkalische, wässrige Lösung L₃ <114> eines Salzes S umfassend X als Kation wird durch K_M, dann über V_AM , dann durch K_A <101 > geleitet, während die mechanische Rührvorrichtung die Lösung L₃ <114> in K_M <103> verrührt,
  3. (c) zwischen E_A <104> und E_K <105> wird Spannung angelegt,
• wodurch am Ablauf A_KK <109> die Lösung L₁ <115> erhalten wird, wobei die Konzentration von XOR in L₁ <115> höher ist als in L₂ <113>,
• und wodurch am Ablauf A_KA <106> eine wässrige Lösung L₄ <116> von S erhalten wird, wobei die Konzentration von S in L₄ <116> geringer ist als in L₃ <114>,
• wobei X ein Alkalimetallkation ist und Rein Alkylrest mit 1 bis 4 Kohlenstoffatomen ist.

In a second aspect, the present invention relates to a method for preparing a solution L ₁ <115> of an alkali metal alkoxide XOR in the alcohol ROH in an electrolysis cell E <100> according to the first aspect of the invention,

• the method comprising the following concurrent steps (a), (b) and (c):
  1. (a) a solution L ₂ <113> comprising the alcohol ROH is passed through K _K <102>,
  2. (b) A neutral or alkaline aqueous solution L ₃ <114> of a salt S comprising X as a cation is passed through K _M , then over V _AM , then through K _A <101 > while the mechanical stirring device stirs the solution L ₃ <114> mixed into K _M <103>,
  3. (c) voltage is applied between E _A <104> and E _K <105>,
• whereby the solution L ₁ <115> is obtained at the outlet A _KK <109>, the concentration of XOR in L ₁ <115> being higher than in L ₂ <113>,
• and whereby an aqueous solution L ₄ <116> of S is obtained at the outlet A _KA <106>, the concentration of S in L ₄ <116> being lower than in L ₃ <114>,
• where X is an alkali metal cation and Rein is alkyl of 1 to 4 carbon atoms.

3. Pictures

illustration 1 shows a preferred embodiment of an electrolytic cell <100> according to the invention and of the method according to the invention. The three-chamber cell E <100> comprises a cathode chamber K _K <102>, an anode chamber K _A <101> and a middle chamber K _M <103> lying between them.

The cathode chamber K _K <102> comprises a cathodic electrode E _K <105>, an inlet Z _KK <107> and an outlet A _KK <109>.

Anode chamber K _A <101> comprises an anodic electrode E _A <104> and drain A _KA <106> and is connected to middle chamber K _M <103> via connection V _AM <112>.

The middle chamber K _M <103> includes an inlet Z _KM <108>.

The three chambers are delimited by an outer wall <117> of the three-chamber cell E <100>. The cathode chamber K _K <102> is also separated from the middle chamber K _M <103> by a NaSICON solid electrolyte F _K <111> that is selectively permeable for sodium ions. The middle chamber K _M <103> is additionally in turn separated from the anode chamber K _A <101> by a diffusion barrier D <110>. The NaSICON solid electrolyte F _K <111> and the diffusion barrier D <110> extend over the entire depth and height of the three-chamber cell E <100>. The diffusion barrier D <110> is made of glass.

In the embodiment according to illustration 1 the connection V _AM <112> is formed outside the electrolytic cell E <100>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic. Through the connection V _AM <112>, liquid can be conducted from the middle chamber K _M <103> into the anode chamber K _A <101> outside the outer wall _WA <117> of the three-chamber cell E <100>. The connection V _AM <112> connects an outlet A _KM <118>, which breaks through the outer wall _WA <117> of the electrolysis cell E <100> at the bottom of the central chamber K _M <103>, with an inlet Z _KA <119>, which breaks through the outer wall W _A <117> of the electrolytic cell E <100> at the bottom of the anode chamber K _A <101>.

An aqueous solution of sodium chloride L ₃ <114> with a pH of 10.5 is added via the inlet Z _KM <108> in the same direction as gravity into the middle chamber _KM <103>. The connection V _AM <112>, which is formed between an outlet A _KM <118> of the middle chamber K _M <103> and an inlet Z _KA <119> of the anode chamber _KA <101>, creates the middle chamber K _M <103 > connected to the anode chamber K _A <101 >. Sodium chloride solution L ₃ <114> is conducted through this connection V _AM <112> from the middle chamber _KM <103> into the anode chamber _KA <101>.

A solution of sodium methoxide in methanol L ₂ <113> is fed into the cathode chamber K _K <102> via the inlet Z _KK <107>.

A voltage is applied between the cathodic electrode E _K <105> and the anodic electrode E _A <104>. As a result, in the cathode chamber K _K <102> methanol im Electrolyte L ₂ <113> reduced to methoxide and H ₂ (CH ₃ OH + e ^- → CH ₃ O ^- + ½ H ₂ ). Sodium ions diffuse from the middle chamber K _M <103> through the NaSICON solid electrolyte F _K <111> into the cathode chamber K _K <102>. Overall, this increases the concentration of sodium methoxide in the cathode chamber K _K <102>, as a result of which a methanolic solution of sodium methoxide L ₁ <115> is obtained, whose concentration of sodium methoxide is increased compared to L ₂ <113>.

In the anode chamber K _A <101 >, the oxidation of chloride ions to molecular chlorine takes place (Cl ^- → ½ Cl ₂ + e). At outlet A _KA <106>, an aqueous solution L ₄ <116> is obtained in which the NaCl content is reduced compared to L ₃ <114>. Chlorine gas Cl ₂ forms hypochlorous acid and hydrochloric acid in water according to the reaction Cl ₂ + H ₂ O → HOCl + HCl, which reacts acidically with other water molecules. The acidity damages the NaSICON solid electrolyte <111>, but is limited by the arrangement according to the invention in the anode chamber K _A <101> and is thus kept away from the NaSICON solid electrolyte F _K <111> in the electrolytic cell E <100>. This increases its lifespan considerably.

In the middle chamber K _M <103> there is also a mechanical stirring device in the form of a propeller stirrer <121>, which is operated by an electric motor <122>, the propeller stirrer being connected to the electric motor via a transmission element <124>. The propeller stirrer <121> hangs freely in the middle chamber K _M <103>, but can also be attached to the inside of the outer wall W _A <117>. The transmission element <124> extends through an opening <125> in the outer wall of the central chamber K _M <103> into the electrolytic cell E <100>. The aqueous solution L ₃ <114> supplied through the inlet Z _KM <108> is mixed by the operation of the propeller stirrer <121>, which leads to eddies and turbulence. These turbulences in the solution L ₃ <114> prevent a pH gradient building up in the central chamber K _M <103> as the electrolysis progresses and prevent the formation of a low pH value in the area immediately adjacent to the NaSICON solid electrolyte <111> Solution. This further increases the durability of the NaSICON solid electrolyte <111>.

Figure 2 shows a further embodiment of the electrolytic cell according to the invention and the method according to the invention, which is in illustration 1 shown. The difference is that the mechanical stirring device instead of the in illustration 1 The propeller stirrer <121> described comprises a magnetic stirrer bar <123-1>, which can be operated with a magnetic stirrer drive <123-2> located outside the central chamber K _M <103>. As in the in illustration 1 embodiment shown, the aqueous solution L ₃ <114> supplied through the inlet Z _KM <108> is swirled by this mechanical stirring device. These turbulences in the solution L ₃ <114> destroy the pH gradient that builds up in the central chamber K _M <103> as the electrolysis progresses.

4. Detailed Description of the Invention 4.1 Electrolytic Cell E

The first aspect of the invention relates to an electrolytic cell E <100>. The electrolytic cell E <100> according to the first aspect of the invention comprises at least one anode chamber K _A <101>, at least one cathode chamber K _K <102> and at least one intermediate chamber K _M <103>. This also includes electrolytic cells E <100> which have more than one anode chamber _KA <101> and/or cathode chamber _KK <102> and/or middle chamber KM _- <103>. Such electrolytic cells, in which these chambers are joined together in a modular manner, are, for example, in DD 258 143 A3 and the U.S. 2006/0226022 A1 described.

The anode chamber K _A <101> includes an anodic electrode E _A <104>. 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 <104>. Such are in particular in WO 2014/008410 A1 , paragraph [024] or DE 10360758 A1 , paragraph [031]. This electrode E _A <104> can consist of one layer or of several planar layers parallel to one another, each of which can be perforated or expanded. The anodic electrode E _A <104> comprises in particular a material 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). Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride. The anodic electrode E _A <104> preferably comprises a titanium anode (RuO ₂ +IrO ₂ /Ti) coated with ruthenium oxide/iridium oxide.

The cathode chamber K _K <102> includes a cathodic electrode E _K <105>. Any electrode familiar to a person skilled in the art that is stable under the conditions can be used as such a cathodic electrode E _K <105>. Such are in particular in WO 2014/008410 A1 , paragraph [025] or DE 10360758 A1 , paragraph [030]. This electrode E _K <105> can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "balls". The cathodic electrode E _K <105> comprises in particular a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium. E _K <105> preferably comprises nickel.

The at least one middle chamber K _M <103> is located between the anode chamber K _A <101> and the cathode chamber K _K <102>.

The electrolytic cell E <100> usually has an outer wall W _A <117>. The outer wall W _A <117> 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. W _A <117> can be perforated in particular for inlets and outlets. The at least one anode chamber K _A <101>, the at least one cathode chamber K _K <102> and the at least one intermediate chamber K _M <103> are then located within W _A <117>.

K _M <103> is separated from K _A <101> by a diffusion barrier D <110> and separated from K _K <102> by an alkali cation-conducting solid electrolyte F _K <111>.

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 in the anode chamber K _A <101> to the middle chamber K _M can be used for the diffusion barrier D <110><103> prevented or slowed down.

In particular, a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D <110>. The diffusion barrier D <110> 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 glass.

If the diffusion barrier D <110> is a “membrane 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. In particular, 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.

If the diffusion barrier D <110> is a “membrane permeable to specific ions”, the diffusion barrier D <110> is in particular an anion-conducting membrane or a cation-conducting membrane.

According to the invention, 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 protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.

According to the invention, 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 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.

If the diffusion barrier D <110> is a "membrane that is permeable to specific ions", it is preferably an anion-conducting membrane, because this is particularly good at preventing the diffusion of protons from the anode chamber K _A <101> into the middle chamber K _M <103>.

In particular, 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, more preferably chloride, is preferably used as the anion-conducting membrane.

Anion-conducting membranes are, for example, from MA Hickner, AM Herring, EB Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51, 1727-1735 , from Arges CG, Ramani V, Pintauro PN, Electrochemical Society Interface 2010, 19, 31-35 , in WO 2007/048712 A2 as well as on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003 ) described.

Organic polymers, which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, are therefore even more preferably used as anion-conducting membrane, these covalently bonded functional groups selected from -NH ₃ ⁺ , - NRH ₂ ⁺ , -NR ₃ ⁺ , =NR ⁺ ;-PR ₃ ⁺ , where R is an alkyl group preferably having 1 to 20 carbon atoms, or other cationic groups. Preferably they have covalently bonded functional groups selected from -NH ₃ ⁺ , -NRH ₂ ⁺ , -NR ₃ ⁺ , more preferably selected from -NH ₃ ⁺ , -NR ₃ ⁺ , even more preferably -NR ₃ ⁺ .

If the diffusion barrier D <110> is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S. Even more preferably, the diffusion barrier D <110> is 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 ).

Accordingly, 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-, _-PO3 ^2- , _-PO2 ^H- ; preferably -SO ₃ ^- , (described in DE 10 2010 062 804 A1 , U.S. 4,831,146 ) carry.

This can be, for example, a sulfonated polyperfluoroethylene (Nafion ^® with CAS number: 31175-20-9 ) be. These are the expert, for example, from WO 2008/076327 A1 , paragraph [058], US 2010/0044242 A1 , paragraph [0042] or the U.S. 2016/0204459 A1 known and commercially available under the trade names ^Nafion® , ^Aciplex® F, ^Flemion® , ^Neosepta® , ^Ultrex® , PC- ^SK® . 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 .

If a cation-conducting membrane is used as the diffusion barrier D <110>, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula P _NAFION , 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 from 10 ² to 10 ⁴ .

Any solid electrolyte which can transport cations, in particular alkali cations, more preferably sodium cations, from the central chamber K _M <103> into the cathode chamber K _K <102> can be used as the alkali cation-conducting solid electrolyte _F K <111>. Such solid electrolytes are known to those skilled in the art and, for example, in DE 10 2015 013 155 A1 , in the WO 2012/048032 A2 , paragraphs [0035], [0039], [0040], in the US 2010/0044242 A1 , paragraphs [0040], [0041], in which DE 10360758 A1 , paragraphs [014] to [025]. They are sold commercially under the names NaSICON, LiSICON, KSICON. A sodium ion conductive solid electrolyte F _K <111> 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 Anantharamulu N, Koteswara Rao K, Rambabu G, Vijaya Kumar B, Velchuri Radha, Vithal M, J Mater Sci 2011, 46, 2821-2837 .

• M^I ist ausgewählt aus Na⁺, Li⁺, bevorzugt Na⁺.
• M" ist ein zweiwertiges Metallkation, bevorzugt ausgewählt aus Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Co²⁺, Ni²⁺, bevorzugter ausgewählt aus Co²⁺, Ni²⁺.
• M^III ist ein dreiwertiges Metallkation, bevorzugt ausgewählt aus Al³⁺, Ga³⁺, Sc³⁺, La³⁺, Y³⁺, Gd³⁺, Sm³⁺, Lu³⁺, Fe³⁺, Cr³⁺, bevorzugter ausgewählt aus Sc³⁺, La³⁺, Y³⁺, Gd³⁺, Sm³⁺, besonders bevorzugt ausgewählt aus Sc³⁺, Y³⁺, La³⁺.
• M^V ist ein fünfwertiges Metallkation, bevorzugt ausgewählt aus V⁵⁺, Nb⁵⁺, Ta⁵⁺.

NaSICON preferably has a structure of the formula M ^I _1+2w+x-y+z M ^II _w M ^III _x Zr ^IV _2-wxy M ^V _y (SiO ₄ ) _z (PO ₄ ) _3-z.

• M ^I 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 ^III 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 sind reelle Zahlen, wobei gilt, dass 0 ≤ x < 2, 0 ≤ y < 2, 0 ≤ w < 2, 0 ≤ z < 3,
• und wobei w, x, y, z so gewählt werden, dass gilt 1 + 2w + x - y + z ≥ 0 und 2 - w - x - y ≥ 0.

The Roman indices I, II, III, IV, V indicate the oxidation numbers in which the respective metal cations are present.

• 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 chosen such that 1 + 2w + x - y + z ≥ 0 and 2 - w - x - y ≥ 0.

More preferably, according to the invention, NaSICON has a structure of the formula Na _(1+v) Zr ₂ Si _v P _(3-v) O ₁₂ , where v is a real number such that 0≦v≦3. Most preferably v = 2.4

The cathode chamber K _K <102> also comprises an inlet Z _KK <107> and an outlet A _KK <109>, which allows liquid, such as the solution L ₂ <113>, to flow into the cathode chamber K _K <102>. to add and liquid contained therein, such as the solution L ₁ <115> to remove. The inlet Z _KK <107> and the outlet A _KK <109> are attached to the cathode chamber K _K <102> in such a way that the liquid contacts the cathodic electrode E _K <105> as it flows through the cathode chamber K _K <102>. This is the prerequisite for the solution L ₁ <115> being obtained when the method according to the invention is carried out according to the second aspect of the invention at the outlet A _KK <109> if the solution L ₂ <113> of an alkali metal alkoxide XOR in the alcohol ROH is passed through K _K <102>.

The anode chamber K _A <101> also includes an outlet A _KA <106>, which makes it possible to remove liquid located in the anode chamber K _A <101>, for example the aqueous solution L ₄ <116>. In addition, the middle chamber K _M <103> includes an inlet Z _KM <108>, while K _A <101> and K _M <103> are connected to one another by a connection V _AM <112>, through which liquid from K _M <103> can be directed into K _A <101 >. As a result, a solution L ₃ <114> can be added to K _M <103> via the inlet Z _KM <108> and this can be conducted through K _M <103>, then via V _AM <112> into the anode chamber K _A <101> , and finally through the anode chamber K _A <101 >. V _AM <112> and the drain A _KA <106> are attached to the anode chamber K _A <101> in such a way that the solution L ₃ <114> when flowing through the anode chamber K _A <101> the anodic electrode E _A <104 > contacted. This is the prerequisite for the aqueous solution L ₄ <116> being obtained when the method according to the invention is carried out according to the second aspect of the invention at the outflow A _KA <106> if the solution L ₃ <114> is first divided by K _M <103>, then V _AM <112>, then K _A <101>.

The inflows Z _KK <107>, Z _KM <108>, Z _KA <119> and outflows A _KK <109>, A _KA <106>, A _KM <118> can be processed according to methods known to those skilled in the art on the electrolytic cell E <100 > be attached.

The connection V _AM <112> can be formed within the electrolytic cell E <100> and/or outside of the electrolytic cell E <100>.

If the connection V _AM <112> is formed within the electrolytic cell E <100>, it is preferably formed by at least one perforation in the diffusion barrier D <110>.

If the connection V _AM <112> is formed outside of the electrolytic cell E <100>, it is preferably formed by a connection of K _M <103> and K _A <101> running outside of the electrolytic cell E <100>, in particular by the fact that in the middle chamber K _M <103> an outlet A _KM <118> through the outer wall W _A <117>, preferably at the bottom of the middle chamber K _M <103>, with the inlet Z _KM <108> even more preferably at the top of the middle chamber K _M <103> is formed, and in the anode chamber K _A <101> an inlet Z _KA <119> through the outer wall W _A <117>, preferably at the bottom of the anode chamber K _A <101>, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic. The outlet A _KA <106> is then even more preferably at the top of the anode chamber K _A <101>.

"Outflow A _KM <118> at the bottom of the middle chamber K _M <103>" means that the outflow A _KM <118> is attached to the electrolytic cell E <100> in such a way that the solution L ₃ <114> fills the middle chamber K _M <103> leaves in the same direction as gravity.

"Inlet Z _KA <119> at the bottom of the anode chamber K _A <101>" means that the inlet Z _KA <119> is attached to the electrolytic cell E <100> in such a way that the solution L ₃ <114> flows into the anode chamber K _A <101 > occurs against gravity.

"Inlet Z _KM <108> at the top of the middle chamber K _M <103>" means that the inlet Z _KM <108> is attached to the electrolytic cell E <100> in such a way that the solution L ₃ <114> enters the middle chamber K _M <103> in the same direction as gravity.

"Drain A _KA <106> at the top of the anode chamber K _A <101>" means that the drain A _KA <106> is attached to the electrolytic cell E <100> in such a way that the solution L ₄ <116> fills the anode chamber K _A <101> leaves against gravity.

This embodiment is particularly advantageous and therefore preferred if the outlet A _KM <118> through the outer wall _WA <117> at the bottom of the middle chamber _KM <103>, and the inlet Z _KA <119> through the outer wall _WA <117> at the bottom of the anode chamber K _A <101>. This arrangement makes it particularly easy to discharge gases with L ₄ <116> formed in the anode chamber K _A from the anode chamber K _A <101> in order to then separate them further.

In particular, when the connection V _AM <112> is formed outside the electrolytic cell E <100>, Z _KM <108> and A _KM <118> are arranged on opposite sides of the outer wall W _A <117> of the central chamber K _M <103> ( eg Z _KM <108> at the bottom and A _KM <118> at the top of the electrolytic cell E <100> or vice versa) and Z _KA <119> and A _KA <106> on opposite sides of the outer wall W _A <117> of the Anode chamber K _A <101> arranged (i.e. Z _KA <119> on the bottom and A _KA <106> on the top of the electrolytic cell E <100> or vice versa), as is particularly the case in illustration 1 is shown. L ₃ <114> must flow through the two chambers _KM <103> and _KA <101> through this geometry. In this case, Z _KA <119> and Z _KM <108> can be formed on the same side of the electrolytic cell E <100>, with A _KM <118> and A _KA <106> then automatically also being formed on the same side of the electrolytic cell E <100> are. Alternatively, as in illustration 1 shown, Z _KA <119> and Z _KM <108> may be formed on opposite sides of the electrolytic cell E <100>, then A _KM <118> and A _KA <106> are automatically also formed on opposite sides of the electrolytic cell E <100>.

In particular, when the connection V _AM <112> is formed inside the electrolytic cell E <100>, this can be ensured by one side ("side A") of the electrolytic cell E <100>, which is the top or the bottom of the electrolytic cell E <100>, preferably as in Figure 2 shown is the top, comprises the inlet Z _KM <108> and the outlet A _KA <106> and the diffusion barrier D <110> extends from this side ("side A") into the electrolytic cell E <100>, but does not quite reach the opposite side of side A ("side B") of electrolytic cell E <100>, which is then the bottom or top of electrolytic cell E <100>, being 50% or more the height of the three-chamber cell E <100>, more preferably 60% to 99% of the height of the three-chamber cell E <100>, even more preferably 70% to 95% of the height of the three-chamber cell E <100>, even more preferably 80% to 90% of the height of the three-chamber cell E <100>, even more preferably 85% of the height of the three-chamber cell E <100>. Because the diffusion barrier D <110> does not touch side B of the three-chamber cell E <100>, a gap is created between the diffusion barrier D <110> and the outer wall _WA <117> of side B of the three-chamber cell E <100>. The gap is then the connection V _AM <112>. Due to this geometry, L ₃ <114> must flow completely through the two chambers _KM <103> and _KA <101>.

These embodiments best ensure that the aqueous salt solution L ₃ <114> flows past the acid-sensitive solid electrolyte before it comes into contact with the anodic electrode _EA <104>, which leads to the formation of acids.

"Bottom of the electrolytic cell E <100>" is, according to the invention, the side of the electrolytic cell E <100> through which a solution (e.g. L ₃ <114> at A _KM <118> in illustration 1 ) 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. L ₂ <113> at Z _KK <107> in Figures 1 and 2 and L ₃ <114> at A _KA <119> in illustration 1 ) of the electrolytic cell E is fed against gravity.

According to the invention, "top side of the electrolytic cell E" is the side of the electrolytic cell E through which a solution (eg L ₄ <116> at A _KA <106> and L ₁ <115> at A _KK <109> in Figures 1 and 2) is opposed exits the electrolytic cell E under gravity or the side of the electrolytic cell E through which a solution (e.g. L ₃ <114> at Z _KM <108> in Figures 1 and 2) is fed to the electrolytic cell E in the same direction as gravity.

According to the invention, the middle chamber K _M comprises a mechanical stirring device. According to the invention, the mechanical stirring device is in the solid state of aggregation. Any stirring device known to those skilled in the art that is sufficiently inert to the electrolysis conditions is suitable as such a mechanical stirring device.

In particular, the mechanical stirring device comprises at least one material selected from rubber; Plastic chosen in particular from polystyrene, polypropylene, PVC, PVC-C; Glass; Porcelain; Metal. The metal is in particular a metal or an alloy of several metals selected from titanium, iron, molybdenum, chromium, nickel, platinum, gold, silver, preferably an alloy comprising at least two metals selected from titanium, iron, molybdenum and chromium , nickel, platinum, gold, silver, more preferably a steel alloy comprising, in addition to iron, at least one other metal selected from titanium, molybdenum, chromium, nickel, platinum, gold, silver, and most preferably it is stainless steel.

Even more preferably, the mechanical stirring device comprises magnetic material so that it can be operated with a magnetic stirrer.

The mechanical stirring device is selected in particular from a propeller stirrer, inclined blade stirrer, disc stirrer, swashplate stirrer, hollow blade stirrer, impeller stirrer, cross bar stirrer, anchor stirrer, blade stirrer, grid stirrer, helical stirrer, toothed disc stirrer, residue stirrer, preferably a propeller stirrer.

The mechanical stirring device is typically powered by a motor, which is preferably an electric motor external to the electrolytic cell E <100>. For example, this can be a motor <122>, which is connected to the propeller stirrer <121> via a transmission element <124>, with the transmission element <124> passing through an opening <125> in the outer wall of the central chamber K _M <103> in the electrolytic cell E <100> reaches in, as in illustration 1 illustrated.

Alternatively, the propeller stirrer can also be magnetic, so that it is a magnetic stirrer bar <123-1> (another word "magnetic stirrer bar"), which is operated by a magnetic stirrer drive <123-2> located outside the central chamber K _M <103>, like it in Figure 2 is illustrated.

The mechanical stirring device can hang loosely in the middle chamber K _M <103>, as in illustration 1 shown.

Alternatively, the mechanical stirring device can also be attached, for example to the solid electrolyte F _K <111>, to the diffusion barrier D <110> or to the outer wall <117> delimiting the inside of the central chamber K _M <103>. The attachment can be done by methods known to those skilled in the art, for example by screwing, clamping, gluing (plastic adhesive, PVC adhesive).

In a preferred embodiment of the electrolytic cell E <100> according to the first aspect of the invention, the mechanical stirring device comprises a propeller which is aligned parallel to the alkali cation-conducting solid electrolyte F _K <111>.

In a preferred embodiment of the electrolytic cell E <100> according to the first aspect of the invention, the mechanical stirring device makes a proportion ζ of 1 to 99%, more preferably 2 to 50%, even more preferably 3 to 40%, even more preferably 4 to 30% preferably 5 to 20%, most preferably 6 to 10% of the volume comprised by the central chamber K _M .

The proportion ζ (in %) is calculated according to ζ = [( V _o - V _M )/ V _o ]*100.

In this case, V _o is the maximum volume of liquid, eg the electrolyte L ₃ <114>, which the middle chamber K _M <103> can hold if it does not comprise a mechanical stirring device. Here V _M is the maximum volume of liquid, eg the electrolyte L ₃ <114>, which the central chamber K _M <103> can hold if it comprises the mechanical stirring device.

It was surprisingly found that the mechanical stirring device in the middle chamber K _M <103> leads to turbulence and turbulence in the electrolyte L ₃ <114> flowing through the middle chamber K _M <103> during the method according to the invention. This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte F _K <111> and thus enables the electrolysis to run longer or extends the service life of the electrolysis cell E <100>.

It goes without saying that the mechanical stirring device is placed in the middle chamber K _M <103> in such a way that it allows the flow of the electrolyte L ₃ <114> through the middle chamber K _M <103> and the anode chamber K _A <101> in allows sufficient extent or not completely blocked.

In a preferred embodiment of the electrolytic cell according to the invention, the mechanical stirring device interrupts the direct path in the central chamber K _M between inlet Z _KM <108> and connection V _AM <112>.

1. 1. Ein Faden wird durch die Öffnung geführt, durch welche der Zulauf Z_KM <108> in die Mittelkammer K_M mündet, und aus der Öffnung geführt, durch welche die Verbindung V_AM <112> in die Mittelkammer K_M mündet. Dabei ist der Faden so lang, dass seine Enden außerhalb der Mittelkammer K_M liegen.
2. 2. Auf das jeweilige Fadenende wird in entgegengesetzter Richtung eine Kraft ausgeübt, so dass sich der Faden strafft, ohne zu zerreißen.
3. 3. Wenn es mindestens einen Faden gibt, der die mechanische Rührvorrichtung während ihres Betriebs berührt, wenn er entsprechend den Schritten 1. und 2.in die Mittelkammer eingeführt und gestrafft wird, so ist das Merkmal, dass der direkte Weg zwischen Zulauf Z_KM <108> und Verbindung V_AM <112> in der Mittelkammer K_M unterbrochen wird, erfüllt.
4. 4. Wenn kein Faden, der, wenn er entsprechend den Schritten 1. und 2. in die Mittelkammer eingeführt und gestrafft wird, die mechanische Rührvorrichtung während ihres Betriebsberührt, dann ist das Merkmal, dass der direkte Weg zwischen Zulauf Z_KM <108> und Verbindung V_AM <112> in der Mittelkammer K_M unterbrochen wird, nicht erfüllt.

The following "thread test" is used to determine whether the direct path between inlet Z _KM <108> and connection V _AM <112> in the middle chamber _KM is interrupted:

1. 1. A thread is passed through the opening through which the inlet Z _KM <108> opens into the middle chamber K _M and out of the opening through which the connection V _AM <112> in the middle chamber K _M opens. The thread is so long that its ends lie outside the central chamber K _M .
2. 2. A force is applied in the opposite direction to the respective end of the thread so that the thread tightens without breaking.
3. 3. If there is at least one thread that touches the mechanical stirring device during its operation when it is inserted and tightened according to steps 1. and 2. in the middle chamber, then the feature is that the direct path between inlet Z _KM <108> and connection V _AM <112> in the middle chamber K _M is interrupted.
4. 4. If no filament which, when inserted and tightened according to steps 1. and 2. in the middle chamber, touches the mechanical stirring device during its operation, then the characteristic is that the direct path between inlet Z _KM <108> and Connection V _AM <112> in the middle chamber K _M is interrupted, not fulfilled.

The thread is selected in particular from sewing thread (e.g. from the Gütermann company), fishing line, twine.

A fishing line with a diameter of 0.2 mm, such as that sold by the companies Hemingway or Nexos, is most preferably used for the thread test.

1.1 Process steps according to the invention

The method according to the second aspect of the invention is one for preparing a solution L ₁ <115> of an alkali metal alkoxide XOR in the alcohol ROH in an electrolytic cell E <100> according to the first aspect of the invention.

The method according to the second aspect of the invention comprises the following steps (a), (b) and (c) occurring simultaneously.

In step (a), a solution L ₂ <113> comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through K _K <102>. X is an alkali metal cation and R is an alkyl group of 1 to 4 carbon atoms.

Preferably X is selected from the group consisting of Li ⁺ , K ⁺ , Na ⁺ , more preferably from the group consisting of K ⁺ , Na ⁺ . Most preferably X = Na ⁺ .

R is preferably selected from the group consisting of n -propyl, iso -propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.

The solution L ₂ <113> is preferably free of water. According to the invention, "free of water" means that the weight of the water in the solution L ₂ <113>, based on the weight of the alcohol ROH in the solution L ₂ <113> (mass ratio) ≦1:10, more preferably ≦1:20, more preferably ≦1:100, even more preferably ≦0.5:100.

If the solution L ₂ <113> includes XOR, the mass fraction of XOR in the solution L ₂ <113>, based on the entire solution L ₂ <113>, 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.

If the solution L ₂ <113> comprises XOR, then in the solution L ₂ <113> in particular the mass ratio of XOR to alcohol ROH is still in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20 more preferably in the range 1:12 to 1:8, even more preferably at 1:10.

In step (b), a neutral or alkaline aqueous solution L ₃ <114> of a salt S comprising X as a cation is passed through K _M <103>, then over V _AM <112>, then through K _A <101> while the mechanical stirring device stirs the solution L ₃ <114> in K _M <103>.

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 <114> 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 <113> 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 L ₃ <113>.

In step (c) a voltage is then applied between E _A <104> and E _K <105>.

This leads to a current transport from the charge source to the anode, to a charge transport via ions to the cathode and finally to a current transport back to the charge source. 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.

• am Ablauf A_KK <109> wird die Lösung L₁ <115> erhalten, wobei die Konzentration von XOR in L₁ <115> höher ist als in L₂ <113>,
• am Ablauf A_KA <106> wird eine wässrige Lösung L₄ <116> von S erhalten, wobei die Konzentration von S in L₄ <116> geringer ist als in L₃ <114>.

This in turn has the following consequences:

• at the outlet A _KK <109> the solution L ₁ <115> is obtained, the concentration of XOR in L ₁ <115> being higher than in L ₂ <113>,
• at outlet A _KA <106> an aqueous solution L ₄ <116> of S is obtained, the concentration of S in L ₄ <116> being lower than in L ₃ <114>.

In the method according to the second aspect of the invention, such a voltage is applied in particular that a current flows such that the current density (= ratio of the current flowing to the electrolytic cell to the area of the solid electrolyte, which corresponds to the area in the central chamber K _M <103 > anolyte contacted) is in the range of 10 to 8000 A/ m ² , more preferably in the range of 100 to 2000 A/ m ² , even more preferably in the range of 300 to 800 A/ m ² , even more preferably at 494 A/ m ² lies. 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 middle chamber K _M <103> 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 .

It goes without saying that step (c) of the method according to the second aspect of the invention is carried out when both chambers K _M <103> and K _A <101> are at least partially loaded with L ₃ <114> and K _K <102> is at least partially loaded with L ₂ <113>.

The fact that in step (c) charge transport takes place between E _A <104> and E _K <105> implies that K _K <102>, K _M <103> and K _A <101 > simultaneously with L ₂ <113> or L ₃ <114> are loaded in such a way that they cover the electrodes _EA <104> and _EK <105> to such an extent that the current circuit is closed.

This is particularly the case when there is a continuous liquid flow from L ₃ <114> through _KM <103>, V _AM <112> and _KA <101> and a liquid flow from L ₂ <113> through _KK <102> and the liquid flow from L ₃ <114> covers the electrode E _A <104> and the liquid flow from L ₂ <113> covers the electrode E _K <105> at least partially, preferably completely.

Due to the fact that the flow of electrolyte L ₃ <114> is stirred by the mechanical stirring device in the central chamber K _M <103>, a typical pH gradient does not form in this chamber. This effect is even stronger when the mechanical stirring device interrupts the direct path in the central chamber K _M between inlet Z _KM <108> and connection V _AM <112>, since the mechanical stirring device then flows through the electrolyte L ₃ <114> through the Center chamber K _M <103> and disturbs the free flow.

This desired effect can be enhanced in the method according to the second aspect of the invention by varying the agitation speed of the mechanical agitation device during the implementation of step (b), whereby further turbulence can be generated which disrupts the formation of a pH gradient.

In a further preferred embodiment, the method according to the second aspect of the invention is carried out continuously, ie step (a) and step (b) are carried out continuously and voltage is applied in accordance with step (c).

After step (c) has been carried out, solution L ₁ <115> is obtained at outlet A _KK <109>, the concentration of XOR in L ₁ <115> being higher than in L ₂ <113>. If L ₂ <113> already comprised XOR, the concentration of XOR in L ₁ <115> is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, still more preferably 1.077 to 1.4 fold more preferably 1077 to 1.08 times higher than in L ₂ <113>, most preferably 1077 times higher than in L ₂ <113>, more preferably the mass fraction of XOR in L ₁ <115> and in L ₂ <113> is in the range of 10 to 20% by weight, more preferably 13 to 14% by weight.

At outlet A _KA <106>, an aqueous solution L ₄ <116> of S is obtained, the concentration of S in L ₄ <116> being lower than that in L ₃ <114>.

The concentration of the cation X in the aqueous solution L ₃ <114> 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 L ₄ <116> is more preferably 0.5 mol/l lower than that of the aqueous solution L ₃ <114> used in each case.

In particular, the method according to the second aspect of the invention is 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.

When the method according to the invention is carried out, hydrogen is typically produced in the cathode chamber K _K <102>, which hydrogen can be discharged from the cell together with the solution L ₁ <115> via the outlet A _KK <109>. In a particular embodiment of the present invention, the mixture of hydrogen and solution L ₁ <115> can then be separated by methods known to those skilled in the art. In the anode chamber K _A <101>, if the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can be produced, which can escape from the cell via the outlet A _KK <106> together with the solution L ₄ <116> can be discharged. In addition, oxygen and/or carbon dioxide can also be formed, which can also be removed. The mixture of chlorine, In a particular embodiment of the present invention, oxygen and/or COz and solution L ₄ <116> can then be separated by 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 <116>, these can be separated from one another by methods known to those skilled in the art.

These results were surprising and not to be expected in the light of the prior art. The method according to the invention protects the acid-labile solid electrolyte from corrosion without having to sacrifice alcoholate solution from the cathode compartment as a buffer solution, as is the case in the prior art. The method according to the invention is thus more efficient than in WO 2008/076327 A1 described procedure in which the product solution is used for the middle chamber, which reduces the overall turnover. In addition, the acid-labile solid electrolyte is stabilized by preventing the formation of a pH gradient due to the mechanical stirring device.

examples Comparative example 1

Sodium methylate (NM) was produced via a cathodic process, with 20% by weight NaCl solution (in water) being fed into the anode chamber and 10% by weight methanolic NM solution being fed into the cathode chamber. The electrolytic cell consisted of three chambers, which illustration 1 shown, except that the electrolytic cell did not have a mechanical agitation device in the central chamber, ie not the in illustration 1 shown propeller stirrer <121> (and thus also not the motor <122> and the transmission element <124>). 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 Na _3.4 Zr _2.0 Si _2.4 P _0.6 O ₁₂ .

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.

It was observed that a pH gradient formed in the middle chamber over a longer period of time, which can be attributed to the migration of the ions to the electrodes in the course of the electrolysis and the propagation of the protons formed at the anode in subsequent reactions. This local increase in the pH value is undesirable since it can attack the solid electrolyte and can lead to corrosion and breakage of the solid electrolyte, especially over very long running times.

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. Thus, this electrolytic cell did not contain a center chamber. This is reflected in an even more rapid corrosion of the ceramic compared to comparative example 1, which leads to a rapid rise in the stress curve. With an initial value of the voltage of < 5 V, this increases to > 20 V within 100 hours.

Inventive Example 1

Comparative example 1 is repeated, with the central chamber comprising a propeller stirrer <121> which is aligned parallel to the NASICON solid electrolyte. By this arrangement the uniform flow of electrolyte through the center chamber is disrupted and turbulence occurs in the electrolyte. This makes it difficult for a pH gradient to build up during electrolysis.

Inventive example 2

Comparative example 1 is repeated with the central chamber K _M <103> comprising a cross-shaped magnetic stir bar <123-1> operated by a magnetic stirrer drive <123-2>. This arrangement also disrupts the uniform flow of electrolyte through the center chamber and creates turbulence. This makes it difficult for a pH gradient to build up during electrolysis.

Result

The use of a three-chamber cell according to the invention in the method according to the invention prevents corrosion of the solid electrolyte, while at the same time no alkali alcoholate product has to be sacrificed for the middle chamber and the voltage is kept constant. These advantages, which are already apparent from the comparison of the two comparative examples 1 and 2, underscore the surprising effect of the present invention.

In addition, the weakening or destruction of the pH gradient that builds up as the electrolysis progresses due to the turbulence and turbulence in the electrolyte in the middle chamber leads to an extension of the service life of the electrolysis chamber. This gradient can make electrolysis even more difficult, especially in the case of very long running times, and can lead to corrosion and ultimately fracture of the solid electrolyte. In the embodiment according to Examples 1 and 2 according to the invention, this pH gradient is destroyed, which, in addition to the stated advantages that a three-chamber cell has over a two-chamber cell, further increases the stability of the solid electrolyte.

Claims (15)

1. Electrolysis cell E <100> comprising at least one anode chamber K_A <101>, at least one cathode chamber K_K <102> and at least one interposed middle chamber K_M <103>,

   wherein K_A. <101> comprises an anodic electrode E_A <104> and an outlet A_KA <106>,

   wherein K_K <102> comprises a cathodic electrode E_K <105>, an inlet Z_KK <107> and an outlet A_KK <109>,

   wherein K_M <103> comprises an inlet Z_KM <108>, is divided from K_A <101> by a diffusion barrier D <110> and is divided from K_K <102> by an alkali metal cation-conducting solid-state electrolyte F_K <111>,

   wherein K_M <103> and K_A <101> are connected to one another by a connection V_AM <112> through which liquid can be routed from K_M <103> into K_A <101>,

   characterized in that the middle chamber K_M <103> comprises a mechanical stirring device <120>.
2. Electrolysis cell E <100> according to Claim 1, wherein the alkali metal ion-conducting solid-state electrolyte F_K <111> has a structure of the formula M^I _1+2w+x-y+z M^II _w M^III _x Zr^IV _2-w-x-y M^V _y (SiO₄)_z (PO₄)_3-z,

   where M^I is selected from Na⁺ and Li⁺,

   M^II is a divalent metal cation,

   M^III is a trivalent metal cation,

   M^V is a pentavalent metal cation,

   the Roman indices I, II, III, IV, V indicate the oxidation numbers in which the respective metal cations exist,

   and 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 chosen such that 1 + 2w + x - y + z ≥ 0 and 2 - w - x - y ≥ 0.
3. Electrolysis cell E <100> according to Claim 1 or 2, wherein the mechanical stirring device comprises a propeller aligned parallel to the alkali metal cation-conducting solid-state electrolyte F_K <111>.
4. Electrolysis cell E <100> according to any of Claims 1 to 3, wherein the connection V_AM <112> is formed within the electrolysis cell E <100>.
5. Electrolysis cell E <100> according to any of Claims 1 to 4, wherein the mechanical stirring device <120> accounts for a proportion ζ of 1% to 99% of the volume encompassed by the middle chamber K_M,
   wherein $$\mathrm{\zeta }=\left[\left({\mathbf{V}}_O-{\mathbf{V}}_M\right)/{\mathbf{V}}_O\right]*100,$$

   

   and wherein V_o is the maximum volume of liquid that can be accommodated by the middle chamber K_M <103> if it does not comprise a mechanical stirring device <120>,

   and wherein V_M is the maximum volume of liquid that can be accommodated by the middle chamber K_M <103> if it comprises the mechanical stirring device <120>.
6. Electrolysis cell E <100> according to any of Claims 1 to 5, wherein the mechanical stirring device <120> interrupts the direct pathway in the middle chamber K_M between inlet Z_KM <108> and connection V_AM <112> according to the thread test stated in the description.
7. Process for producing a solution L₁ <115> of an alkali metal alkoxide XOR in the alcohol ROH in an electrolysis cell E <100> according to any of Claims 1 to 6,

   wherein the process comprises the following steps (a), (b) and (c) that proceed simultaneously:

   (a) a solution L₂ <113> comprising the alcohol ROH is routed through K_K <102>,

   (b) a neutral or alkaline, aqueous solution L₃ <114> of a salt S comprising X as cation is routed through K_M <103>, then via V_AM <112>, then through K_A <101>, while the mechanical stirring device <120> stirs the solution L₃ <114> in K_M <103>,

   (c) voltage is applied between E_A <104> and E_K <105>, which affords the solution L₁ <115> at the outlet A_KK <109>, with a higher concentration of XOR in L₁ <115> than in L₂ <113>,

   and which affords an aqueous solution L₄ <116> of S at the outlet A_KA <106>, with a lower concentration of S in L₄ <116> than in L₃ <114>,

   wherein X is an alkali metal cation and R is an alkyl radical having 1 to 4 carbon atoms.
8. Process according to Claim 7, wherein X is selected from the group consisting of Li⁺, Na⁺, K⁺.
9. Process according to Claim 7 or 8, wherein S is a halide, sulfate, sulfite, nitrate, hydrogencarbonate or carbonate of X.
10. Process according to any of Claims 7 to 9, wherein R is selected from the group consisting of methyl and ethyl.
11. Process according to any of Claims 7 to 10, wherein L₂ <113> comprises the alcohol ROH and an alkali metal alkoxide XOR.
12. Process according to Claim 11, wherein the mass ratio of XOR to alcohol ROH in L₂ <113> is in the range from 1:100 to 1:5.
13. Process according to Claim 11 or 12, wherein the concentration of XOR in L₁ <115> is 1.01 to 2.2 times higher than in L₂ <113>.
14. Process according to any of Claims 7 to 13, which is performed at a temperature of 20 to 70°C and a pressure of 0.5 to 1.5 bar.
15. Process according to any of Claims 7 to 14, wherein the stirrer speed of the mechanical stirring device is varied during the performance of step (b).

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