Fracture-resistant partitions for electrolytic cells containing solid electrolyte ceramics.

Abstract

The present invention relates in a first aspect to an electrolytic cell E comprising a partition wall W suitable for use in the electrolytic cell E. The partition wall W comprises at least two alkali metal cation-conducting solid electrolyte ceramics F separated from one another by at least one separating element T. A and F B Compared to the prior art, where the partition wall W contains an integral solid electrolyte, this arrangement is more flexible and allows greater freedom of application, since the individual ceramics react to temperature variations, e.g. by contracting or expanding. This improves the ceramics' stability against mechanical stress. The electrolytic cell E is divided into a cathode chamber K and an adjacent chamber K by a partition wall W. K The adjacent chambers are the intermediate chamber K of the electrolytic cell E. M It is. In a second aspect, the present invention relates to a method for producing an alkali metal alkoxide solution in an electrolytic cell E according to the first aspect of the invention.

Description

[Technical field]

[0001] The present invention relates in a first aspect to an electrolytic cell E comprising a partition wall W suitable for use in the electrolytic cell E. The partition wall W comprises at least two alkali metal cation-conducting solid electrolyte ceramics F separated from one another by at least one separating element T. A and F B In comparison with the prior art, where the partition wall W contains an integral solid electrolyte, this arrangement is more flexible and allows greater freedom of application, since the individual ceramics react to temperature variations, e.g. by contracting or expanding. This improves the ceramics' stability against mechanical stress.

[0002] The electrolytic cell E is divided into a cathode chamber K and an adjacent chamber K by a partition wall W. K The adjacent chambers are the intermediate chamber K of the electrolytic cell E. M It is.

[0003] In a second aspect, the present invention relates to a method for producing an alkali metal alkoxide in an electrolytic cell E according to the first aspect of the present invention. [Background technology]

[0004] 1. Background of the invention The electrochemical production of alkali metal alkoxide solutions is an important industrial process and is described, for example, in DE 10360758 A1, US 2006 / 0226022 A1 and WO 2005 / 059205 A1. The principle of these processes is reflected in electrolytic cells in which a solution of an alkali metal salt, for example sodium chloride or NaOH, is present in the anode chamber and a solution of the alcohol in question, for example sodium methoxide or sodium ethoxide, with a lower concentration of the alcohol or alkali metal alkoxide in question, is present in the cathode chamber. The cathode and anode chambers are separated by a ceramic that conducts the alkali metal ions used, for example NaSICON or an analogue of potassium or lithium. When an electric current is applied, chlorine is produced at the anode when chloride salts of the alkali metal are used and hydrogen and alkoxide ions are produced at the cathode. The charge is balanced by the migration of the alkali metal ions from the intermediate chamber to the cathode chamber via a ceramic that is selective for them. Charge balance between the intermediate and anodic compartments occurs by migration of cations if a cation exchange membrane is used, or anions if an anion exchange membrane is used, or both types of ions if a non-specific diffusion barrier is used, resulting in an increase in the concentration of alkali metal alkoxide in the cathodic compartment and a decrease in the concentration of sodium ions in the anolyte.

[0005] NaSICON solid electrolytes are also used in the electrochemical production of other compounds.

[0006] WO 2014 / 008410 describes an electrolytic process for producing elemental titanium or rare earths. The basis of this method is to generate titanium chloride from TiO2 and the corresponding acid, which is reacted with sodium alkoxide to obtain titanium alkoxide and NaCl, which is finally electrolyzed to elemental titanium and sodium alkoxide.

[0007] WO 2007 / 082092 and WO 2009 / 059315 describe methods for the production of biodiesel, in which triglycerides are first converted with the aid of electrolytically generated alkoxides using NaSICON to the corresponding alkali metal triglycerides, which in a second step react with electrolytically generated protons to give glycerol and the respective alkali metal hydroxide.

[0008] However, these solid electrolyte ceramics usually have some drawbacks: during operation of the electrolytic cell, temperature fluctuations within the cell are unavoidable, which results in the solid electrolyte ceramics expanding or contracting, which may lead to breakage of the ceramics, as these ceramics are brittle.

[0009] This problem occurs especially during the constant start-up and stop process that is unavoidable in electrolysis operations. During heating and cooling, there are expansion and contraction phases that cause the ceramic to move back and forth within the electrolysis cell. These movements can cause the ceramic to break, as the distribution of forces within the ceramic is uncontrolled.

[0010] This can lead to loss of integrity, leading to leakage of the salt water into the alcohol or vice versa, resulting in a dilution of the electrolysis product, the alkoxide solution. Additionally, the electrolysis cell itself can lose integrity and develop leaks.

[0011] The object of the present invention is therefore to provide an electrolytic cell which does not have these drawbacks.

[0012] A further drawback of conventional electrolytic cells in this technical field arises from the fact that the solid electrolyte does not have long-term stability towards aqueous acids. This is problematic in that during electrolysis in the anode chamber, as a result of oxidation processes (e.g. when heterogenizing or forming oxygen to produce halogens), the pH drops. These acidic conditions attack the NaSICON solid electrolyte to such an extent that the process cannot be used on an industrial scale. To address this problem, different approaches have been described in the prior art.

[0013] For example, three-compartment cells have been proposed in the prior art and are known in the field of electrodialysis, for example in U.S. Pat. No. 6,221,225.

[0014] For example, WO 2012 / 048032 and US 2010 / 0044242 describe electrochemical processes for producing sodium hypochlorite and similar chlorine compounds in such three-compartment cells. The cathode and intermediate compartments of the cell are separated by a cation-permeable solid electrolyte, e.g. NaSICON. To protect it from the acidic anolyte, the intermediate compartment is supplied, for example, with the solution of the cathode compartment. Figure 6 of US 2010 / 0044242 also describes that the solution of the intermediate compartment can be mixed with the solution of the anolyte compartment outside the compartments to obtain sodium hypochlorite.

[0015] Such cells have also been proposed in the prior art for the production or purification of alkali metal alkoxides.

[0016] For example, U.S. Patent No. 5,389,211 describes a method for purifying an alkoxide solution using a three-compartment cell, in which the compartments are separated from each other by a cation-selective solid electrolyte or a non-ionic partition wall, and the middle compartment is used as a buffer compartment to prevent the purified alkoxide or hydroxide solution from the cathode compartment from mixing with the contaminating solution from the anode compartment.

[0017] DE 42 33 191 A1 describes the electrolytic recovery of alkoxides from salts and alkoxides in multi-compartment cells and in stacks of multiple cells.

[0018] WO 2008 / 076327 describes a method for the production of alkali metal alkoxides. It uses a three-compartment cell, the middle compartment of which is filled with alkali metal alkoxide (see, for example, paragraphs

[0008] and

[0067] of WO 2008 / 076327). This protects the solid electrolyte separating the middle compartment from the cathode compartment from the solution in the anode compartment, which becomes more acidic in the course of electrolysis. A similar arrangement is described in WO 2009 / 073062. However, this arrangement has the disadvantage that the desired product is an alkali metal alkoxide solution, which is consumed as a buffer and is constantly contaminated. A further disadvantage of the method described in WO 2008 / 076327 is that the production of the alkoxide in the cathode compartment depends on the diffusion rate of the alkali metal ions through the two membranes or solid electrolytes. This in turn slows down the production of the alkoxide.

[0019] Further problems arise from the geometry of three-compartment cells, where the middle compartment is separated from the anode compartment by a diffusion barrier and from the cathode compartment by an ionically conductive ceramic. During electrolysis, this inevitably creates pH gradients and dead volumes. This can damage the ionically conductive ceramic, resulting in increased voltages required for electrolysis and / or leading to ceramic breakage.

[0020] This effect occurs throughout the electrolysis chambers, but the drop in pH is especially significant in the intermediate chamber because it is bounded by an ionically conductive ceramic. Typically, gases are produced at the anode and cathode and are mixed at least to some extent in these chambers. In contrast, no such mixing occurs in the intermediate chamber, creating a pH gradient therein. This undesirable effect is exacerbated by the fact that the brine is generally pumped relatively slowly through the electrolysis cell. [Prior art documents] [Patent documents]

[0021] [Patent Document 1] DE 10360758 A1 [Patent Document 2] US Patent Application Publication No. 2006 / 0226022 [Patent Document 3] International Publication No. 2005 / 059205 Brochure [Patent Document 4] International Publication No. 2014 / 008410 Brochure [Patent Document 5] International Publication No. 2007 / 082092 Brochure [Patent Document 6] International Publication No. 2009 / 059315 Brochure [Patent Document 7] U.S. Patent No. 6,221,225 [Patent Document 8] International Publication No. 2012 / 048032 Brochure [Patent Document 9] US Patent Application Publication No. 2010 / 0044242 [Patent Document 10] U.S. Pat. No. 5,389,211 [Patent Document 11] DE 4233191 A1 [Patent Document 12] International Publication No. 2008 / 076327 Brochure [Patent Document 13] International Publication No. 2009 / 073062 Brochure Summary of the Invention [Problem to be solved by the invention]

[0022] It was therefore a further object of the present invention to provide an improved process for the preparation of alkali metal alkoxides by electrolysis, and electrolytic cells particularly suitable for such a process, which do not have the abovementioned drawbacks and in particular which improve the protection of the solid electrolyte before the pH gradient is generated and which ensure a more economical use of reactants compared to the prior art. [Means for solving the problem]

[0023] 2. Brief description of the invention The problem addressed by the present invention is to provide an electrolytic cell E according to a first aspect of the invention, which comprises a partition wall W. <1> This is solved by partition wall W <16> is the surface O KK <163> One side S has KK <161> And, surface O A / MK <164> With side S KK <161> and the opposite side S A / MK <162> The partition wall includes at least one separation element T <17> At least two alkali metal cation conducting solid electrolyte ceramics F separated from each other by A <18> and F B <19> Also includes partition wall W <16> The alkali metal cation conducting solid electrolyte ceramics contained in <17> is the surface O KK <163> and surface O A / MK <164> You can have direct contact with both.

[0024] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: At least one entrance Z KA <110> and at least one exit A KA <111> and the anode electrode E A <113> Internal structure I including KA <112> At least one anode chamber K having A <11> and, At least one entrance Z KK <120> and at least one exit A KK <121> and the cathode electrode E K <123> Internal structure I including KK<122> At least one cathode chamber K having K <12> and, At least one entrance Z KM <130> and at least one exit A KM <131> and Internal Structure I KM <132> At least one intermediate chamber K having M <13> and Including, I KA <112> and I KM <132> is the diffusion barrier D <14> are separated from each other by Liquid connection V AM <15> via I KM <132> From I KA <112> A KM <131> is the connection V AM <15> By Entrance Z KA <110> Connected to I KK <122> and I KM <132> Partition wall W <16> are separated from each other by Partition wall W <16> and in particular the separation element T <17> is the surface O KK <163> Via S KK side <161> Internal Structure I KK <122> Direct contact with Partition wall W <16> The alkali metal cation conducting solid electrolyte ceramics contained in A / MK <164> Via S A / MK <162> Side internal structure I KM <132> Direct contact with electrolytic cell E <1> Regarding.

[0025] In a second aspect, the present invention provides a method for producing a composition comprising the steps of: A method for producing an alcohol ROH solution L1 of an alkali metal alkoxide XOR, X is an alkali metal cation, R is an alkyl group having 1 to 4 carbon atoms, The following are happening at the same time: Solution L2 containing alcohol ROH is K(β1), A neutral or alkaline aqueous solution L3 of salt S containing X as a cation is added to K M Then through V AM Then, via K A A process (β2) of passing the E A <113> and E K <123> A step (β3) of applying a voltage between in an electrolytic cell E according to the first aspect of the invention, As a result, the solution L1, which has a higher XOR concentration than L2, flows to the outlet A. KK and L3 <23> The aqueous solution L4 of S, which has a lower S concentration than KA This relates to a method of

[0026] 3. Drawings 3.1 Figures 1A and 1B FIG. 1A shows a non-inventive electrolytic cell E. It includes a cathode chamber K K <12> and anode chamber K A <11> It is equipped with:

[0027] Cathode chamber K K <12> The internal structure I KK <122> Cathode electrode E K <123> And, Entrance Z KK <120> And Exit A KK <121> It is equipped with: Anode chamber K A <11> The internal structure I KA <112> Anode electrode E A <113> And, Entrance Z KK <110> And Exit A KA <111> It is equipped with:

[0028] The two chambers are the outer walls of the two-chamber tank E. <80> It is bounded by. Internal Structure I KK <122> The NaSICON solid electrolyte F is also selectively permeable to sodium ions. A <18> The inner structure I is made of a partition wall made of sheets. KA<112> It is partitioned from NaSICON solid electrolyte F A <18> extends over the entire depth and height of the two-chambered chamber E. The partition wall is KK <161> and S A / MK <162> and its surface O KK <163> and O A / MK <164> The internal structure of each KK <122> or I KA <112> is in contact with.

[0029] Sodium chloride solution at pH 10.5 L3 <23> But, in the opposite direction to gravity, at the entrance Z KA <110> Via Internal Structure I KA <112> will be introduced.

[0030] Sodium methoxide in methanol L2 <22> But the entrance Z KK <120> Via Internal Structure I KK <122> will be sent.

[0031] At the same time, the cathode electrode E K <123> and anode electrode E A <113> A voltage is applied between the electrolyte L2 <22> The methanol in the inner structure is reduced, and the inner structure I KK <122> Methoxide and H2 are produced in the - →CH3O - +1 / 2H2). At the same time, sodium ions enter the inner structure I KA <112> From NaSICON solid electrolyte F K <18> Through the internal structure I KK <122> Overall, this results in the internal structure I KK <122> The sodium methoxide concentration in the L2 <22> The sodium methoxide concentration is higher than that of the methanol solution L1. <21> is obtained.

[0032] Internal structure I KA <112> In the case of chlorine, oxidation of chloride ions occurs, producing chlorine molecules (Cl- →1 / 2Cl2+e - ). Exit A KA <111> So, what is the NaCl content of L3? <23> Reduced aqueous solution L4 compared to <24> The chlorine gas (Cl2) in the water generates hypochlorous acid and hydrochloric acid according to the reaction Cl2+H2O→HOCl+HCl, which then reacts with water molecules to produce acidic acid. A <18> Damage to.

[0033] FIG. 1B shows another non-inventive electrolytic cell E. This three-compartment cell E has a cathode chamber K K <12> and anode chamber K A <11> And, the intermediate room K M It is equipped with: Cathode chamber K K <12> The internal structure I KK <122> Cathode electrode E K <123> And, Entrance Z KK <120> And Exit A KK <121> It is equipped with: Anode chamber K A <11> The internal structure I KA <112> Anode electrode E A <113> And, Entrance Z KK <110> And Exit A KA <111> It is equipped with: Intermediate room K M <13> The internal structure I KM <132> And, Entrance Z KM <130> And Exit A KM <131> It is equipped with:

[0034] Internal structure I KA <112> is the connection V AM <15> Internal structure I KM <132> is connected to

[0035] The three chambers are the outer walls of the three chambers E <80> The middle room is bounded by M <13> Internal Structure I KM <132> The NaSICON solid electrolyte F is also selectively permeable to sodium ions.A <18> The cathode chamber K is separated by a partition wall made of a sheet of K <13> Internal Structure I KA <122> It is partitioned from NaSICON solid electrolyte F A <18> extends over the entire depth and height of the three-chamber tank E. The partition wall is KK <161> and S A / MK <162> and its surface O KK <163> and O A / MK <164> The internal structure of each KK <122> or I KM <132> is in contact with.

[0036] Intermediate room K M <13> Internal Structure I KM <132> is further defined as a diffusion barrier D <14> By the anode chamber K A <11> Internal Structure I KA <112> The NaSICON solid electrolyte F A <18> and diffusion barrier D <14> extends throughout the depth and height of the three-chamber chamber E. The diffusion barrier D <14> is a cation exchange membrane (sulfonated PTFE).

[0037] In the embodiment according to FIG. AM <15> is formed on the outside of the electrolytic cell E, in particular by a tube or hose, the material of which may be selected from rubber, metal and plastic. AM <15> is the partition wall of the three-chamber tank W A <80> Outside the intermediate chamber K M <13> Internal Structure I KM <132> From anode chamber K A <11> Internal Structure I KA <112> The liquid can be guided to the connection V AM <15> is the intermediate chamber K M <13> At the bottom of the electrolytic cell E, the outer wall W A <80> Exit A through KM <131> Anode chamber K A <11> At the bottom of the outer wall W of the electrolytic cell EA <80> Entrance Z through KA <110> is connected to.

[0038] Sodium chloride solution at pH 10.5 L3 <23> But in the direction of gravity, the entrance Z KM <130> via intermediate chamber K M Internal Structure I KM <132> Introduced into the intermediate chamber K M <13> Exit A from KM <131> and anode chamber K A <11> Entrance to Z KA <110> The connection formed between V AM <15> is the intermediate chamber K M <13> Internal Structure I KM <132> Anode chamber K A <11> Internal Structure I KA <112> Connect to sodium chloride solution L3 <23> This connection V AM <15> Through the internal structure I KM <132> From Internal Structure I KA <112> Sodium methoxide in methanol L2 <22> is the entrance Z KK <120> Via Internal Structure I KK <122> will be sent.

[0039] At the same time, the cathode electrode E K <123> and anode electrode E A <113> A voltage is applied between the electrolyte L2 <22> The methanol in the inner structure is reduced, and the inner structure I KK <122> Methoxide and H2 are produced in the - →CH3O - +1 / 2H2). At the same time, sodium ions enter the middle chamber K M <13> Internal Structure I KM <132> From NaSICON solid electrolyte F A <18> Through the internal structure I KK <122> Overall, this results in the internal structure I KK<122> The sodium methoxide concentration in the L2 <22> The sodium methoxide concentration is higher than that of the methanol solution L1. <21> is obtained.

[0040] Internal structure I KA <112> In the case of chlorine, oxidation of chloride ions occurs, producing chlorine molecules (Cl - →1 / 2Cl2+e - ). Exit A KA <111> So, what is the NaCl content of L3? <23> Reduced aqueous solution L4 compared to <24> The chlorine gas (Cl2) in the water forms hypochlorous acid and hydrochloric acid according to the reaction Cl2+H2O→HOCl+HCl, which then reacts with water molecules to produce an acidic reaction. The acidity is caused by the NaSICON solid electrolyte F A <18> However, due to the arrangement in the three-chamber tank, the anode chamber K A <11> Limited to NaSICON solid electrolyte FK in electrolytic cell E <18> This significantly extends the life of the electrolytic cell E.

[0041] 3.2 Figures 2A and 2B FIG. 2A shows the partition wall W <16> The embodiment of the present invention is shown. <16> is the separation element T <17> Two NaSICON solid electrolyte ceramics F are fixed to each other without gaps by a A <18> and F B <19> The separating element T <17> has a rectangular parallelepiped geometry, F A <18> and F B <19> is fixed (e.g. by adhesive) with no gaps on either side. Face O KK <163> Side S with KK <161> is in the plane of the figure, and the surface O A / MK <164> Side S with A / MK <162> is not visible in FIG. 2A but is behind the plane of the figure.

[0042] FIG. 2B shows the partition wall W <16> 1 shows another embodiment of the present invention, which is a separation element T <17> Four NaSICON solid electrolyte ceramics F are fixed to each other without gaps by separating them from each other by A <18> , F B <19> , F C <28> , F D <29> The separating element T <17> is a cross shape with F on both sides. A <18> , F B <19> , F C <28> and F D <29> is glued in place. Face O KK <163> Side S with KK <161> is in the plane of the figure, and the surface O A / MK <164> Side S with A / MK <162> is not visible in FIG. 2B but is behind the plane of the figure.

[0043] 3.3 Figures 3A to 3C FIG. 3A shows a detailed view of the portion highlighted by the dotted circle in FIGS. 2A and 2B. As explained, each solid electrolyte ceramic F A <18> and F B <19> However, the separating element T <17> is fixed at.

[0044] FIG. 3B shows a further inventive embodiment of a partition wall W. <17> Two solid electrolyte ceramics F A <18> and F B <19> For this purpose, the solid electrolyte ceramic F A <18> and F B <19> The shape of the end of the seal Di can be mechanically adjusted accordingly. <40> is used, which can be attached, for example by means of an adhesive, to the separating element T <17> and each solid electrolyte ceramic F A <18> or F B<19> The separation element T <17> is two or more parts that can be fixed to each other as shown by the dotted lines in FIG. 3B. <171> and <172> When a suitable shape is given, the solid electrolyte ceramic F A <18> and F B <19> When the shape of the edge of the solid electrolyte ceramic F A <18> and F B <19> It consists of two parts <171> and <172> This allows the separating element T <17> / Ceramic F A <18> or F B <19> The stability of the connection and the partition wall W <16> The integrity of the system will be further improved.

[0045] FIG. 3C shows a further embodiment of the partition wall W according to the invention. It is made up of two solid electrolyte ceramics F A <18> and F B <19> The separation element T <17> 3B, except that the recess (groove) is not concave but points to a point.

[0046] 3.4 Figures 4A to 4D 4A to 4D show the partition wall W <16> 1 shows a further embodiment of the present invention.

[0047] The partition wall W shown in FIG. <16> is the frame element R <20> The partition wall W shown in FIG. 2A, except that it also includes <16> This corresponds to O KK <163> and O A / MK <164> Excluding partition wall W <16> The frame element R completely covers all sides of the frame. <20> is the separation element T <17> It is not a one-piece shape.

[0048] FIG. 4B shows the partition wall W <16> This shows a further embodiment of the present invention, which is a partition wall W <16> Two frame elements R bounding the top and bottom of <20> 4B corresponds to the embodiment shown in FIG. 4A, except that

[0049] FIG. 4C shows the partition wall W <16> A further embodiment of the present invention is shown in FIG. <16> is the frame element R <20> The partition wall W shown in FIG. 2B, except that it also includes <16> This corresponds to O KK <163> and O A / MK <164> Excluding partition wall W <16> Completely covers all surfaces of frame element R. <20> is the separation element T <17> It is not a one-piece shape.

[0050] FIG. 4D shows the partition wall W <16> This shows a further embodiment of the present invention, which is a partition wall W <16> Two frame elements R bounding the top and bottom of <20> 4C, except that it includes:

[0051] 3.5 Figures 5A and 5B FIG. 5A shows a non-inventive electrolytic cell E, which corresponds to the electrolytic cell shown in FIG. 1A, but without a partition wall W <16> But, anode chamber K A <11> Internal Structure I KA <112> From cathode chamber K K <12> Internal Structure I KK <122> The partition wall is the one shown in Figures 2A and 2B.

[0052] FIG. 5B shows a non-inventive electrolytic cell E, which corresponds to the electrolytic cell shown in FIG. 1A, but without a partition wall W <16> But, anode chamber K A <11> Internal Structure I KA <112> From cathode chamber K K <12> Internal Structure I KK <122> The partition wall is shown in Fig. 4A to Fig. 4D. <20> The exterior wall W A <80> This forms part of the partition wall W <16> The solid electrolyte ceramics contained in the partition wall W <16> If it is part of the partition wall W <16> In addition, the solid electrolyte ceramic is not partially hidden by the outer wall, so the inner structure I KK <122> and I KA<112> The electrolytic cell is inserted completely into the electrolytic cell to separate the

[0053] 3.6 Figures 6A and 6B FIG. 6A shows an electrolytic cell E according to a first embodiment of the invention. <1> This shows the partition wall W <16> is the middle room K M <13> Internal Structure I KM <132> From cathode chamber K K <12> Internal Structure I KK <122> 1B, except that it is separated by a partition wall W <16> is shown in Figures 4A to 4D.

[0054] FIG. 6B shows an electrolytic cell E according to a first embodiment of the present invention. <1> This is shown in FIG. 6A. <1> corresponds to the intermediate chamber K M <13> Internal Structure I KM <132> From anode chamber K A <11> Internal Structure I KA <112> Connection to V AM <15, diffusion barrier D <14> The difference is that the perforations are formed by the diffusion barrier D <14> or a diffusion barrier D <14> Diffusion barrier D from the beginning during manufacturing <14> The material may already be present within the material (eg, in the case of woven fabrics such as filter fabrics or metal weaves).

[0055] 3.7 Figures 7A and 7B FIG. 7A shows a partition wall W of the present invention. <16> 1 shows a further embodiment of the present invention, which is a two-half <171> and <172> Separation element T <17> Four NaSICON solid electrolyte ceramic Fs are separated from each other by A <18> , F B <19> , F C <28> and F D <29> Partition wall W <16> Similarly, two halves <201> and <202> Frame element R consisting of <20> Also includes.

[0056] Partition wall W <16> is composed of two foldable parts, in which the separation element T <17> Half of <171> is frame element R <20> Half of <201> and is integral with the separation element T <17> Half of <172> is frame element R <20> Half of <202> These two parts can be hinged together as needed. <50> In the folded state, the two parts may be connected to each other via a lock. <60> The locking mechanism may be locked in place by 4 NaSICON solid electrolyte ceramic F A <18> , F B <19> , F C <28> and F D <29> In each case, the sealing Di <40> The halves are clamped between them by a ring which acts as a clamp.

[0057] On the left side of Figure 7A is the partition wall W <16> Face O KK <163> Side S with KK <161> The front view of the seal Di is shown. <40> The ring acting as the partition wall W is shown in dotted outline on the right side of the figure. <16> A side view of the above is shown.

[0058] FIG. 7B shows the partition wall W of the present invention. <16> This shows a further embodiment of the present invention, which is a 9 NaSICON solid electrolyte ceramic F A <18> , F B <19> , F C <28> , F D <29> , F E <30> , F F <31> , F G <32> , F H <33> , F I <34> 7A, except that it includes:

[0059] 4. Detailed Description of the Invention 4.1 Partition wall W The present invention relates in a first aspect to an electrolytic cell E comprising a partition wall W. The partition wall W is therefore particularly suitable as a partition wall in an electrolytic cell, in particular an electrolytic cell E.

[0060] The partition wall W is made up of at least two alkali metal cation conductive solid electrolyte ceramics (hereinafter abbreviated as "ASC") F separated from each other by a separation element T. A and F B Contains:

[0061] The partition wall W has two opposing sides S KK and S A / MK This includes side S A / MK Side S KK and vice versa. KK and S A / MK In particular, includes planes that are essentially parallel to one another. The geometric shape of the partition W is otherwise not subject to further restrictions and may in particular be adapted to the cross-section of the electrolytic cell E in which it is used. For example, the partition W may have the shape of a rectangular parallelepiped and thus a rectangular cross-section, or the shape of a truncated cone or cylinder and thus a circular cross-section.

[0062] If desired, the partition W may also be in the shape of a rectangular parallelepiped with rounded corners or bulges, which may be provided with holes. The partition W has bulges ("rabbit ears") that allow the partition W to be fixed to the electrolytic cell or that allow the frame parts of the partition W to be fixed to each other.

[0063] Side S of Partition Wall W KK is the surface O KK and the side S of the partition wall W A / MK is face O A / MK has.

[0064] The feature "partition wall" means that the partition wall W is liquid-tight. This means that the ASC and at least one separation element T are adjacent to each other without any gaps. Therefore, there are no gaps between the separation element T and the ASC contained in the partition wall W, and the aqueous solution, alcohol solution, alcohol or water can pass through the gap, i.e., S KK S from the sideA / MK It will not flow to one side or the other.

[0065] In the case where there are two or more pairs of sides that face each other via a surface that can contact the alkali metal cation conductive solid electrolyte ceramic contained in the partition wall W and, in particular, the separation element T, it is referred to as S in the context of this specification. KK and S A / MK The pair of opposing sides, called KK and O A / MK When the surface areas of each pair of opposing sides are the same, a person skilled in the art can easily distinguish the surface O KK and O A / MK S with KK and S A / MK One pair can be selected as the

[0066] Among the partition walls W having two or more pairs of opposing sides through a surface that allows direct contact between the alkali metal cation conductive solid electrolyte ceramics contained in the partition walls W and, in particular, the separation element T, it is preferable that the surface areas of the opposing pairs of the partition walls W are different. In this case, in the context of this specification, S KK and S A / MK The pair of opposing sides, called KK and O A / MK It includes.

[0067] The partition W of the present invention also includes embodiments in which the partition W comprises three or more ASCs, for example four or nine or twelve ASCs, and at least two, but not all, of the ASCs are separated from one another by a separation element T, and the ASCs that are not separated from one another by a separation element T are directly adjacent to one another. However, this includes liquids, water, alcohol or alcohol solutions. KK S from the side A / MKIt is necessary that each adjacent ASC fits exactly to exclude the formation of gaps through which the ASC can flow to the side. It is therefore advantageous and preferred that in the partition wall W, all ASCs contained in the partition wall W are separated from each other by at least one separation element T, meaning that no ASC is directly adjacent to another ASC, i.e. there is no separation element T in between.

[0068] Partition wall W is a wall in which the ASC included in the partition wall W is located on the surface O KK and surface O A / MK The present invention is further characterized in that it is capable of directly contacting both the

[0069] Regarding the ASC included in the partition wall W, "direct contact" means that the surface O KK and O A / MK This means that a part of is formed by the surface of the ASC included in the partition wall W, which means that the ASC included in the partition wall W has two faces O KK and O A / MK are directly accessible to the two surfaces O, so that they can be, for example, by aqueous or alcoholic solutions, alcohol or water. KK and O A / MK This means that it can be wetted in

[0070] What this means about the placement of ASCs within partition W is that for each ASC contained within partition W, KK Face O KK From there, completely pass through each ASC and into the side S A / MK Face O A / MK This means that there is a route to

[0071] Typically, at least one separation element T also has a surface O KK and at least a portion of surface O A / MK At least a portion of both of the above may be directly contacted.

[0072] With respect to at least one separating element T included in a partition wall W, "directly accessible" means that the surface O KK and O A / MKis formed by the surface of the separation element T, which means that the separation element T has two surfaces O KK and O A / MK , so that the separation element T can be directly accessed between the two faces O by, for example, an aqueous solution, an alcoholic solution, alcohol or water. KK and O A / MK This means that it can be wetted in

[0073] What this means in particular with regard to the arrangement of the separating elements T of the partition wall W is that for the separating elements T included in the partition wall W, the side S KK Face O KK From there, it passes through the separation element T and possibly through the seal Di, but not through the ASC, and through the side S A / MK Face O A / MK This means that there is a route to In a preferred embodiment of the partition wall W of the present invention, the surface O KK 50% to 95%, more preferably 60% to 90%, and even more preferably 70% to 85% of the surface O is formed by the ASC contained in the partition wall W. KK The remaining part of is more preferably formed by a separating element T and, optionally, a frame element R.

[0074] In a preferred embodiment of the partition wall W of the present invention, the surface O A / MK 50% to 95%, more preferably 60% to 90%, and even more preferably 70% to 85% of the surface O is formed by the ASC contained in the partition wall W. A / MK The remaining part of is more preferably formed by a separating element T and, optionally, a frame element R.

[0075] In a preferred embodiment, the partition wall W is made up of at least four ASCs F A , F B , F C and F D and even more preferably, exactly four ASCs, F A , F B , F C and F D It is equipped with:

[0076] In a further preferred embodiment, the partition W has at least 9 ASCs F A , F B , F C , F D , F E , F F , F G , F H and F I and even more preferably, exactly 9 ASCs, F A , F B , F C , F D , F E , F F , F G , F H and F I It is equipped with:

[0077] In a further preferred embodiment, the partition W comprises at least 12 ASCs F A , F B , F C , F D , F E , F F , F G , F H , F I , F J , F K and F L and even more preferably, exactly 12 ASCs, F A , F B , F C , F D , F E , F F , F G , F H , F I , F J , F K and F L It is equipped with:

[0078] The inventive arrangement of at least two ASCs next to each other in the partition W provides an additional diffusion direction for the ASCs in the event of temperature fluctuations during operation of the electrolytic cell, as compared to conventional partitions in prior art electrolytic cells, in which the NaSICON sheets acting as partitions are framed by the outer wall of the electrolytic cell or by a solid plastic frame. In this way, mechanical stresses occurring during expansion in the NaSICON cannot be dispersed and may lead to fracture of the ceramic.

[0079] In contrast, individual ASCs within a partition wall W of the present invention are adjacent to a separation element T, which provides two advantageous effects, both of which improve the long-term stability of the ASCs. - each ASC has a further degree of freedom available, i.e. the area over which the ASC can expand: not only in the z direction (i.e. expansion perpendicular to the horizontal plane of the partition W beyond the thickness of the ceramic sheet), but also in the x and / or y direction, i.e. horizontal and vertical expansion in the horizontal plane of the partition W. If the ASC, for example as a solid sheet, spans the cross section of the electrolytic cell and abuts the solid wall of the electrolytic cell, this direction of expansion does not exist or is at least strongly limited. - Compared to an equally sized partition containing only one ASC, division into multiple smaller ASCs has the effect that the stresses generated within the smaller ASCs are also smaller in absolute terms and can dissipate more quickly, so that stresses that lead to ASC failure do not build up as quickly.

[0080] 4.1.1 Alkali Metal Cation Conducting Solid Electrolyte Ceramics ("ASC") Useful alkali metal cation conducting solid electrolyte ceramic F contained in partition wall W A , F B etc., by passing cations, particularly alkali metal cations, and even more preferably sodium cations, through S A / MK S from the side KKThe solid electrolytes are all solid electrolytes capable of transporting sodium ions to the side. Such solid electrolytes are known to the person skilled in the art and are described, for example, in DE 10 2015 013 155 A1, WO 2012 / 048032 A1, paragraphs

[0035] ,

[0039] ,

[0040] , US 2010 / 0044242 A1, paragraphs

[0040] ,

[0041] , and DE 10360758 A1, paragraphs

[0014] to

[0025] . They are commercially available under the names NaSICON, LiSICON, KSICON. Sodium ion-conducting solid electrolytes are preferred, more preferably having the NaSICON structure. NaSICON structures that can be used according to the invention are also described, for example, in N. Anantharamulu, K. Koteswara Rao, G. Rambabu, B. Vijaya Kumar, Velchuri Radha, M. Vithal, J Mater Sci 2011, 46, 2821-2837.

[0081] In a preferred embodiment of the partition wall W, the alkali metal cation conducting solid ceramic contained in the partition wall W is independently represented by 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 It has the NaSICON structure. In the formula, M I is Na + , Li + Preferably, it is Na+. M II is a divalent metal cation, preferably Mg 2+ , Ca 2+ , Sr 2+ , B.A. 2+ , Co 2+ , Ni 2+ More preferably, Co 2+ , Ni2+ is selected from. M III is a trivalent metal cation, preferably Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ More preferably, Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ Particularly preferably, Sc 3+ , Y 3+ , La 3+ is selected from. M V is a pentavalent metal cation, preferably V 5+ , Nb 5+ , Ta 5+ is selected from.

[0082] The Roman numerals I, II, III, IV, and V indicate the oxidation numbers in which each metal cation exists.

[0083] w, x, y, z are real numbers with 0≦x<2, 0≦y<2, 0≦w<2, 0≦z<3, and w, x, y, z are selected such that 1+2w+x-y+z≧0 and 2-wxy≧0.

[0084] Even more preferably, according to the present invention, the NaSICON structure is of the formula Na (1+v) Zr2Si v P (3 - v) O 12 wherein v is a real number, 0≦v≦3. Most preferably, v=2.4.

[0085] In a preferred embodiment of the partition W of the present invention, the ASCs contained in the partition W have the same structure.

[0086] 4.1.2 Separation element T According to the invention, the separating element T comprises at least two alkali metal cation-conducting solid ceramics F contained in a partition wall W. A and F B This is a partition wall W containing at least two alkali metal cation conductive solid ceramics F A and F B This means that a separation element T is placed between the

[0087] Suitable separating elements T included in the partition W are all objects by means of which the respective ASCs can be arranged in isolation from one another. The ASCs adjoin the separating elements T with no gaps so as not to impair the function of the partition to separate the cathode chamber from the adjacent intermediate or anode chambers in a liquid-tight manner within the electrolytic cell E.

[0088] The shape of the separation element T can be selected by one skilled in the art depending on the number of ASCs included in the partition wall W.

[0089] For example, if the partition wall W includes two or three ASCs, these may each be separated by lands disposed between the ASCs as separation elements T (see FIG. 1A).

[0090] When the partition wall W includes four or more ASCs, these may be separated by cross-shaped (see Figures 1B and 4A) or lattice-shaped (see Figure 4B) separation elements T.

[0091] It is particularly preferred that the partition wall W comprises at least four ASCs, and it is even more preferred that the separating element T is cross-shaped or lattice-shaped, since all three dimensions are fully available for the thermal expansion / contraction of the ASCs.

[0092] The separation element T may consist of one piece (FIGS. 2A, 2B). In that case, the ASC is tightly fixed to the separation element, for example by adhesive, using compositions known to the person skilled in the art. It is preferred to use epoxy and phenolic resins. Alternatively or additionally, the separation element T may be shaped such that the respective ASC can be fitted or clamped into the separation element. This can already be implemented in a corresponding manner in the manufacture of the partition wall W (section 4.1.4).

[0093] In a preferred embodiment, the partition W, in particular the partition W between the separating element T and the ASC, comprises a seal Di (FIGS. 3B, 3C). This ensures in a particularly efficient manner that the partition W is liquid-tight. The seal Di can be selected for each ASC or each separating element T by the person skilled in the art.

[0094] The seal Di in particular comprises a material selected from the group consisting of elastomers, adhesives, preferably elastomers.

[0095] Useful elastomers are especially rubbers, preferably ethylene-propylene-diene rubbers ("EPDM"), fluoropolymer rubbers ("FPM"), perfluoropolymer rubbers ("FFPM"), or acrylonitrile-butadiene rubbers ("NBR").

[0096] In a further preferred embodiment, the separation element T comprises at least two parts T1 and T2 which can be fixed to each other and thus clamp the ASC between them.

[0097] In this embodiment, it is then particularly preferable to install a seal Di between the separating element T and the ASC in order to ensure liquid-tightness.

[0098] The separating element T preferably comprises a material selected from the group consisting of plastic, glass and wood. More preferably, the separating element T is made of plastic. Even more preferably, the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, post-chlorinated polyvinyl chloride ("PVC-C").

[0099] 4.1.3 Frame element R In a further preferred embodiment, the partition wall W also comprises a frame element R. The frame element R differs from the separating element T in that it is not arranged between the alkali metal cation conducting solid electrolyte ceramics contained in the partition wall W, i.e. it does not separate them from each other. The frame element R is in particular arranged between the faces O KK and O A / MK This means, more specifically, that the frame element R bounds the surface O at least partially, preferably completely. KK and O A / MK By this is meant at least partially, and preferably completely, surrounding the

[0100] Frame element R has face O KK and O A / MK The frame element R is preferably part of the surface O KK and O A / MK is part of.

[0101] The frame element R is, in particular, KK and O A / MK may or may not be directly contactable, preferably directly contactable.

[0102] Regarding the frame element R included in the partition wall W, "not directly contactable" means that the frame element R is not directly contactable with the side S of the partition wall W. KK and S A / MK More specifically, the frame element R in this case is formed only as part of the surface of the side S of the partition wall W. KK and S A / MK The non-adhesive layer forms at least 1%, more preferably at least 25%, more preferably at least 50%, and even more preferably 100% of the surface area of ​​the non-adhesive layer.

[0103] Regarding the frame element R included in the partition wall W, "direct contact is possible" means that the surface O KK and O A / MK This means that a part of is formed by the surface of the frame element R, which means that the frame element R included in the partition wall W has two faces O KK and O A / MK is directly accessible to the two surfaces O, so that it can be, for example, by an aqueous solution, an alcoholic solution, alcohol or water. KK and O A / MK This means that it can be wetted in

[0104] What this means for the arrangement of the frame element R of the partition wall W is that the side S KK Face O KK Then, completely passing through frame element R, A / MK Face O A / MK This means that there is a route to

[0105] This includes the following embodiments: -face O KK and O A / MK A portion of the edge of the frame is formed by a frame element R (as shown in Figures 4B and 4D). -face O KK and O A / MK The ends of the frame are completely formed by the frame element R (as shown in Figures 4A, 4C, 7A and 7B).

[0106] The frame element R is further connected to the side S of the partition wall W. KK and S A / MK More specifically, the frame element R may be formed as at least a part of the surface of the side S of the partition wall W. KK and S A / MK The non-adhesive layer forms at least 1%, more preferably at least 25%, more preferably at least 50%, and even more preferably 100% of the surface area of ​​the non-adhesive layer.

[0107] For example, Figs. 4B and 4D show a frame element R on side S of a partition wall W. KK and S A / MK 4 shows an embodiment forming part of the surface of the side that is not

[0108] For example, Figs. 4A and 4C show a frame element R on side S of a partition wall W. KK and S A / MK 13 shows an embodiment in which the surface on the non-contact side is completely formed.

[0109] The frame element R is in particular chosen from a material selected from the group consisting of plastic, glass, wood, and more preferably, the frame element R is made of plastic. Even more preferably, the plastic is one selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, PVC-C.

[0110] In a further preferred embodiment, the frame element R and the separation element T are made of the same material, even more preferably both made of plastic, which plastic is even more preferably selected from polypropylene, polystyrene, polyvinyl chloride, PVC-C.

[0111] The frame element R may consist of one piece, in which case the ASCs are tightly fixed to the frame element R by means known to the skilled person, for example by adhesives, for which epoxy and phenolic resins are particularly suitable. Alternatively or additionally, the frame element R may be shaped such that each ASC can be snapped or clamped into the frame element R.

[0112] This also means that in the preferred embodiment in which the partition wall W comprises a frame element R, the ASC, the at least one separating element T and the frame element R adjoin one another without gaps. Therefore, between the separation element T, the frame element R, and the ASC contained in the partition wall W, the aqueous solution or water is KK S from the side A / MK There are no gaps through which it can flow to the side or vice versa.

[0113] Furthermore, in particular when the partition wall W comprises a frame element R which is at least partially formed in one piece with the separating element T, the frame element R is composed of at least two parts fixed to each other, between which the ASC is clamped. For example, in this case the partition wall W may have a hinge which allows the two parts of the frame element R to be folded open and closed. Furthermore, the partition wall W in this case may have a lock which allows the two parts of the frame element R to be fixed in position in the folded state (FIG. 7A).

[0114] In the folded state, the ASC and, if not already formed in one piece with the frame element R, the separating element T, can be clamped between the frame element R. In this embodiment, a seal can be provided between the separating element T and the ASC or between the frame element R and the ASC to ensure liquid tightness.

[0115] In a preferred embodiment, the separation element T <17> At least a part of the frame element R <20> This means more specifically that at least a part of the separation element T is integrated with the frame element R. Preferably, the separation element T <17> and frame element R <20> is an integral shape.

[0116] The embodiment of the frame element R has the advantage that it can function as part of the outer wall in the construction of the electrolytic cell E. This part of the partition wall W can be connected to each internal structure I KK , I KA or I KM Since this part does not come into contact with the solution inside, the solid electrolyte ceramic F A or F B Moreover, the portion of the partition wall W which is clamped between the outer walls or forms part of the outer walls is made of brittle solid electrolyte ceramic F A or F B Therefore, instead, a less fragile and less expensive material is selected for the frame R.

[0117] 4.1.4 Construction of Partition Wall W The partition wall W can be fabricated by methods known to those skilled in the art. For example, the ASC contained in the partition wall may be inserted into a mold, optionally equipped with a seal, and the separating element may be cast with liquid plastic, which is then left to solidify (injection molding method), during which it surrounds the ASC.

[0118] Alternatively, the separation element T is cast separately (or partially) and then tightly secured (eg, by adhesive bonding) to at least two ASCs.

[0119] 4.2 Electrolytic cell E The partition wall W of the present invention is suitable as a partition wall of the electrolytic cell E according to the first aspect of the present invention. Thus, in a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: - at least one entrance Z KA and at least one exit A KA and the anode electrode E A Internal structure I including KA At least one anode chamber K having A and, - at least one entrance Z KK and at least one exit A KK and the cathode electrode E K Internal structure I including KK At least one cathode chamber K having K and, - at least one entrance Z KM and at least one exit A KM and Internal Structure I KM At least one intermediate chamber K having M and Including, I KA and I KM are separated from each other by a diffusion barrier D, Liquid connection V AM via I KM From I KA A KM is the connection V AM By Entrance Z KA Connected to I KK and I KM are separated from each other by a partition wall W, Partition wall W <16> and in particular the separating element T, are connected to the surface O KK Through side S KK Internal Structure I KK In direct contact with The alkali metal cation-conducting solid electrolyte ceramic contained in the partition wall W and in particular the separating element T are connected to the surface O A / MK Through side S A / MK Internal Structure I KM With respect to electrolytic cell E, which is in direct contact with

[0120] The electrolytic cell E in the first embodiment of the present invention has at least one anode chamber K A and at least one cathode chamber K K and, if necessary, at least one intermediate chamber K M This includes two or more anode chambers K A and / or cathode chamber K K and / or intermediate chamber K M Also included are electrolytic cells E having a chamber E1, the chamber E2 and the chamber E3 in the form of a module. Such electrolytic cells, the chambers of which are connected to one another in the form of modules, are described, for example, in DE-A 258143 and US-A 2006 / 0226022.

[0121] In a preferred embodiment, the electrolytic cell E in the first aspect of the present invention includes an anode chamber K A and cathode chamber K K And, if necessary, the intermediate room K M Includes.

[0122] The electrolytic cell E is usually A Exterior wall W A is made in particular from a material selected from the group consisting of steel, preferably rubberized steel, plastic, in particular Telene® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride).A The may in particular be perforated for inlets and outlets. A At least one anode chamber K A and at least one cathode chamber K K The electrolytic cell E is placed in the intermediate chamber K. M In the case of an embodiment having at least one intermediate chamber K M There is a saying.

[0123] 4.2.1 Cathode chamber K K Cathode chamber K K At least one inlet Z KK and at least one exit A KK and the cathode electrode E K Internal structure I KK and

[0124] Cathode chamber K K Internal Structure I KK The intermediate chamber K is separated by the partition wall W of the present invention. M Internal Structure I KM is separated from

[0125] 4.2.1.1 Cathode electrode E K Cathode chamber K K is the cathode electrode E K Internal structure I KK This type of useful cathode electrode E K are all electrodes familiar to the skilled artisan that are stable under the conditions of the method according to the invention in the second aspect of the invention. They are in particular described in paragraph

[0025] of WO 2014 / 008410 or in paragraph

[0030] of DE 10360758 A1. This electrode E K may be selected from the group consisting of mesh wool, a three-dimensional matrix structure, and a "ball". The cathode electrode E K In particular, E comprises a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium on carbon, and titanium. K contains nickel.

[0126] Intermediate room K M In an embodiment of the electrolytic cell E according to the first aspect of the invention, the intermediate chamber K M Anode chamber K A and cathode chamber K K It is between.

[0127] 4.2.1.1 Cathode electrode E K Cathode chamber K K is the cathode electrode E K Internal structure I KK This type of useful cathode electrode E K are all electrodes familiar to the skilled artisan that are stable under the conditions of the method according to the invention in the second aspect of the invention. They are in particular described in paragraph

[0025] of WO 2014 / 008410 or in paragraph

[0030] of DE 10360758 A1. This electrode E K may be selected from the group consisting of mesh wool, a three-dimensional matrix structure, and a "ball". The cathode electrode E K In particular, E comprises a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium on carbon, and titanium. K contains nickel.

[0128] Intermediate room K M In an embodiment of the electrolytic cell E according to the first aspect of the invention, the intermediate chamber K M Anode chamber K A and cathode chamber K K It is between.

[0129] 4.2.1.2 Entrance Z KK and Exit A KK Cathode chamber K K is the entrance Z KK and Exit A KK This also includes the cathode chamber K K Internal Structure I KK It is possible to add a liquid, for example solution L2, to the inlet Z and remove a liquid, for example solution L1, present therein.KK and Exit A KK The liquid is in the cathode chamber K K Internal Structure I KK When flowing through the cathode electrode E K In such a way that it comes into contact with the cathode chamber K K This is because the solution L2, which is an alcohol ROH solution of alkali metal alkoxide XOR, is placed in the cathode chamber K K Internal Structure I KK In the implementation of the method according to the invention in the second aspect of the invention, KK This is a prerequisite for obtaining solution L1.

[0130] Entrance Z KK and Exit A KK may be attached to the electrolytic cell E in a manner known to those skilled in the art, for example by means of external wall holes and corresponding connections (valves) that simplify the introduction and discharge of liquids.

[0131] 4.2.2 Anode chamber K A Anode chamber K A At least one inlet Z KA and at least one exit A KA and the anode electrode E A Internal structure I KA and

[0132] Anode chamber K A Internal Structure I KA is separated from the intermediate chamber K by a diffusion barrier D. M Internal Structure I KM is separated from

[0133] 4.2.2.1 Anode electrode E A Anode chamber K A is the anode electrode E A Internal structure I KA This type of useful anode electrode E Aare all electrodes familiar to the skilled artisan that are stable under the conditions of the method according to the invention in the second aspect of the invention. They are in particular described in paragraph

[0024] of WO 2014 / 008410 or in paragraph

[0031] of DE 10360758 A1. This electrode E A may consist of one layer or of multiple parallel planar layers, each of which may be perforated or expanded. A comprises a material selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, titanium or a noble metal, in particular platinum, supported on a support such as Kovar® (an iron-nickel-cobalt alloy, the components of which are preferably 54% iron, 29% nickel and 17% cobalt by weight). Further possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide and titanium diboride. Preferably, the anode electrode E A contains a titanium anode coated with ruthenium oxide / iridium oxide (RuO2+IrO2 / Ti).

[0134] 4.2.2.2 Entrance Z KA and Exit A KA Anode chamber K K is the entrance Z KA and Exit A KA This also includes the cathode chamber K A Internal Structure I KA It is possible to add a liquid, for example solution L3, to the inlet Z and remove a liquid, for example solution L4, present therein. KA and Exit A KA The liquid is in the anode chamber K A Internal Structure I KA As the liquid flows through the anode electrode E A In contact with the anode chamber K A This is because the solution L3 of salt S is A Internal Structure I KAIn the implementation of the method according to the invention in the second aspect of the invention, KA This is a prerequisite for obtaining solution L4.

[0135] Entrance Z KA and Exit A KA may be attached to the electrolytic cell E by methods known to those skilled in the art, for example, by external wall holes and corresponding connections (valves) that simplify the introduction and discharge of liquids. In certain embodiments, the inlet Z KA may also be present in the electrolytic cell, for example in the form of perforations in the diffusion barrier D.

[0136] 4.2.3 Intermediate room K M The electrolytic cell E in the first embodiment of the present invention comprises at least one intermediate chamber K M The intermediate chamber K M Cathode chamber K K and anode chamber K A It is located between at least one entrance Z KM and at least one exit A KM and Internal Structure I KM It is equipped with.

[0137] Anode chamber K A Internal Structure I KA is separated from the intermediate chamber K by a diffusion barrier D. M Internal Structure I KM It is separated from A. KM The liquid is connected to the V AM Through I KM From I KA Connect V so that it can be guided to AM By Entrance Z KA is also connected to

[0138] 4.2.3.1 Diffusion Barrier D Intermediate room K M Internal Structure I KM The diffusion barrier D separates the anode chamber K from the A Internal Structure I KA The cathode chamber K is separated from the cathode chamber K by a partition wall W. KInternal Structure I KK is separated from

[0139] The material used for the diffusion barrier D is stable under the conditions of the method of the present invention in the second aspect of the present invention and is suitable for use in the anode chamber K A Internal Structure I KA Protons from the liquid in the intermediate chamber K M Internal Structure I KM The material may be any material that prevents or retards migration of the

[0140] The diffusion barrier D used is in particular an ion-nonspecific partition or a membrane permeable to specific ions. The diffusion barrier D is preferably an ion-nonspecific partition.

[0141] The material of the non-ion specific partition is in particular selected from the group consisting of fabrics, in particular textile fabrics or metal weaves, glass, in particular sintered glass or glass frits, ceramics, in particular ceramic frits, membrane diaphragms, more preferably textile fabrics or metal weaves, particularly preferably textile fabrics. The textile fabrics preferably comprise plastics, more preferably plastics selected from PVC, PVC-C, polyvinyl ether ("PVE"), polytetrafluoroethylene ("PTFE").

[0142] If the diffusion barrier D is a "membrane permeable to specific ions", what is meant according to the invention is that the respective membrane promotes the diffusion of the specific ions through it more than other ions. More specifically, what is meant is a membrane that promotes the diffusion of ions of a specific charge type more than ions of the opposite charge. Even more preferably, the membrane permeable to specific ions also promotes the diffusion of specific ions of one charge type more than other ions of the same charge type.

[0143] If the diffusion barrier D is a "membrane permeable to certain ions", the diffusion barrier D is in particular an anion-conducting or cation-conducting membrane.

[0144] According to the invention, anion-conducting membranes are membranes that selectively conduct anions, preferably membranes that selectively conduct certain anions. In other words, they favor the diffusion of anions over that of cations, especially protons. Even more preferably, they favor the diffusion of certain anions over that of other anions.

[0145] According to the invention, cation-conducting membranes are membranes that selectively conduct cations, preferably membranes that selectively conduct certain cations. In other words, they favor the diffusion of cations over that of anions. Even more preferably, they favor the diffusion of certain cations over that of other cations, and more preferably, they favor the diffusion of non-proton cations, more preferably sodium cations, over protons.

[0146] "Enhancing the diffusion of a particular ion X over the diffusion of other ions Y" refers more specifically to the diffusion coefficient (unit: m 2 / sec) is 10 times, preferably 100 times, preferably 1000 times higher than the diffusion coefficient of the Y-type ion in the membrane.

[0147] When the diffusion barrier D is a "membrane permeable to a specific ion", it is preferably an anion-conducting membrane, because it is an anion-conducting membrane that is permeable to the protons in the anode chamber K A From intermediate room K M This is to particularly effectively prevent diffusion to the

[0148] The anion-conducting membrane used is in particular a membrane selective for the anions contained in the salt S. Such membranes are known to and can be used by those skilled in the art.

[0149] The salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.

[0150] The halides are fluoride, chloride, bromide and iodide. The most preferred halide is chloride.

[0151] The anion-conducting membrane used is preferably a membrane selective for halides, preferably chloride.

[0152] Anion-conducting membranes are described, for example, in Journal of Polymer Science Part B: Polymer Physics 2013, 51, 1727-1735 by MA Hickner, AM Herring, EB Coughlin, Electrochemical Society Interface 2010, 19, 31-35 by CGArges, V. Ramani, PNPintauro, WO 2007 / 048712, and in the textbook Electrochemical Engineering: Fundamentals, Reaction Techniques, Process Optimization, 1st edition (October 8, 2003) by Volkmar M. Schmidt, p. 181.

[0153] Even more preferably, the anion-conducting membrane used is therefore an organic polymer, in particular chosen from polyethylene, polybenzimidazole, polyetherketone, polystyrene, polypropylene and fluorinated membranes such as polyperfluoroethylene, preferably polystyrene. These are the anion-conducting membranes that react with -NH3 + , -NRH2 + , -NR3 + , =NR + , -PR3 + In the formula, R is preferably an alkyl group having 1 to 20 carbon atoms, or other cationic group. They are preferably -NH3 + , -NRH2 + and -NR3 + More preferably, selected from -NH3 + and -NR3 + and even more preferably selected from -NR3 + has a covalently attached functional group,

[0154] If the diffusion barrier D is a cation-conducting membrane, it is in particular a membrane selective for the cations contained in the salt S. Even more preferably, the diffusion barrier D is an alkali metal cation-conducting membrane, even more preferably a potassium and / or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.

[0155] Cation-conducting membranes are described, for example, on page 181 of the textbook Electrochemical Engineering: Fundamentals, Reaction Techniques, Process Optimization, 1st Edition (October 8, 2003) by Volkmar M. Schmidt. Even more preferably, the cation-conducting membranes used are therefore organic polymers, in particular selected from fluorinated membranes such as polyethylene, polybenzimidazole, polyetherketone, polystyrene, polypropylene and polyperfluoroethylene, preferably polystyrene and polyperfluoroethylene. These are (described in DE 102010062804 A1, U.S. Pat. No. 4,831,146) -SO3 - , -COO - , -PO3 2- and -POH - , preferably -SO3 - has a covalently attached functional group selected from:

[0156] This can be, for example, sulfonated polyperfluoroethylene (Nafion®, CAS number: 31175-20-9). These are known to the skilled artisan, for example from WO 2008 / 076327, US 2010 / 0044242, US 2016 / 0204459, and are commercially available under the trade names Nafion®, Aciplex® F, Flemion®, Neosepta®, Ultrex®, PC-SK®. Neosepta® membranes are described, for example, in Journal of Membrane Science 2018, 563, pp. 768-776 by SAMareev, D.Yu.Butylskii, NDPismenskaya, C.Larchet, L.Dammak, VVNikonenko.

[0157] If a cation-conducting membrane is used as the diffusion barrier D, this may be, for example, a polymer functionalized with sulfonic acid groups, in particular a polymer of the formula P NAFION In the formula, n and m are independently 1 to 10. 6 An integer of 10 to 10 5 an integer of 10 or more preferably 2 ~10 4 can be an integer.

[0158] [ka]

[0159] 4.2.3.2 Entrance Z KM and Exit A KM Intermediate room K M There is an entrance Z KM and Exit A KM This also includes the intermediate chamber K M Internal Structure I KM Addition of a liquid, e.g. solution L3, to the anode chamber K A It is possible to transfer the

[0160] Entrance Z KM and Exit A KM may be attached to the electrolytic cell E by methods known to those skilled in the art, for example by means of external wall holes and corresponding connections (valves) that simplify the introduction and discharge of liquids. KM may also be present in the electrolytic cell, for example in the form of perforations in the diffusion barrier D.

[0161] 4.2.3.3 Connection V AM In the electrolytic cell E according to the first aspect of the invention, the liquid is connected to the connection V AM Through I KM From I KA As directed by the exit A KM V is connected AM By Entrance Z KA is connected to Connection V AM may be formed within the electrolytic cell E and / or outside the electrolytic cell E, and is preferably formed within the electrolytic cell E.

[0162] (1) Connection V AM If is formed in the electrolytic cell E, then the connection V AM is preferably formed by at least one perforation of the diffusion barrier D. This embodiment is particularly preferred when the diffusion barrier D used is a non-ion specific partition wall, in particular a metal weave or a woven fabric, which acts as a diffusion barrier D and, due to the properties of the weave, does not allow the connection V AM The insulating layer 14 has perforations and gaps that function as a shield from the elements.

[0163] (2) The embodiment described below is particularly preferred when the diffusion barrier D used is a membrane permeable to certain ions. In this embodiment, the connection V AM is formed on the outside of the electrolytic cell E. In particular, the outer wall W A Exit A through KM The internal structure of the intermediate chamber I KM From the intermediate chamber K M At the bottom of the inlet Z KM More preferably, the intermediate chamber KM and at the top of the exterior wall W A Entrance Z through KA But, anode chamber K A Internal Structure I KA From the anode chamber K A At the point where the connection V AM is A operating outside the electrolytic cell E KM and Z KA These are connected by a conduit, for example a pipe or hose, preferably comprising a material selected from rubber and plastic. Then, outlet A KA Anode chamber K A It is more preferable that the temperature is at the upper end of the range.

[0164] "Intermediate room K M Bottom outlet A KM " means that the solution L3 is in the middle chamber K along the direction of gravity. M Exit A KM This means that the electrolytic cell E is attached to the electrolytic cell E.

[0165] "Anode chamber K A Inlet Z at the bottom of KA " means that the solution L3 flows against gravity into the anode chamber K A To enter, enter the entrance Z KA This means that the electrolytic cell E is attached to the electrolytic cell E.

[0166] "Intermediate room K M Entrance Z at the top of KM " means that the solution L3 is in the middle chamber K along the direction of gravity. M To enter, enter the entrance Z KM This means that the electrolytic cell E is attached to the electrolytic cell E.

[0167] "Anode chamber K A Exit A at the top of KA " means that the solution L4 flows against gravity into the anode chamber K A Exit A KA This means that the electrolytic cell E is attached to the electrolytic cell E.

[0168] In this embodiment, exit A KM But, the middle room K M The bottom outer wall W A The inlet Z is formed by KA Anode chamber K A The bottom outer wall W A This arrangement is particularly advantageous and therefore preferred when the anode chamber K A The gases generated in the anode chamber K are then separated in a particularly simple manner using L4 in order to separate them further. A It becomes possible to remove it from

[0169] Connection V AM When is formed outside the electrolytic cell E, as shown in FIG. 6A, Z KM and A KM In particular, the intermediate chamber K M Outer wall W A (i.e., for example, Z KM , A at the top KM , or vice versa), and Z KA and A KA Anode chamber K A Outer wall W A (i.e., Z is placed at the bottom of the electrolytic cell E) KA , A at the top KA , or vice versa). Due to this geometry, L3 must be a two-chambered M and K. A It flows through Z KA and Z KM can be formed on the same side of the electrolytic cell E, in which case A KM and A KA is also automatically formed on the same side of the electrolytic cell E. Alternatively, Z KA and Z KM may be formed on the opposite side of the electrolytic cell E, in which case A KM and A KA is also automatically formed on the opposite side of electrolytic cell E.

[0170] (3) Connection V AMis formed in the electrolytic cell E, this is particularly the case when one side of the electrolytic cell E ("side A"), which is the top end or bottom of the electrolytic cell E, preferably the top end shown in FIG. 6B, is connected to the inlet Z KM and Exit A KA This can be ensured by the fact that the diffusion barrier D extends from this side ("side A") towards the electrolytic cell E but does not reach completely to the side ("side B") of the electrolytic cell E opposite side A, side B being the bottom or top of the electrolytic cell E and at the same time covering more than 50% of the height of the three-compartment cell E, preferably 60% to 99% of the height of the three-compartment cell E, more preferably 70% to 95% of the height of the three-compartment cell E, even more preferably 80% to 90% of the height of the three-compartment cell E, and even more preferably 85% of the height of the three-compartment cell E. Since the diffusion barrier D does not touch side B of the three-compartment cell E, the diffusion barrier D and the outer wall W of side B of the three-compartment cell E are not in contact with each other. A In this case, the gap is between the connection V AM Due to this geometric shape, L3 must be a two-chambered K M and K. A Flows completely through the

[0171] These embodiments allow the aqueous salt solution L3 to be A It will most likely flow through an acid-sensitive solid electrolyte before coming into contact with the electrolyte, resulting in the formation of an acid.

[0172] According to the present invention, the "bottom of the electrolytic cell E" refers to the solution (e.g., A KM 6A and 6B) exits from the electrolytic cell E along the direction of gravity, or the side of the solution (e.g., Z KK In the case of FIG. 1, L2) is the side of electrolytic cell E where water is supplied to electrolytic cell E against gravity.

[0173] According to the present invention, the "upper end of the electrolytic cell E" refers to the upper end of the solution (e.g., A in FIG. 6A and FIG. 6B). KA In the case of L4, A KK The side of the electrolytic cell E where the solution (e.g., Z in Fig. 6A and Fig. 6B) exits the electrolytic cell E against gravity, or KMIn the case of FIG. 1, L3) is the side of electrolytic cell E where the water is supplied to electrolytic cell E along the direction of gravity.

[0174] 4.2.4 Arrangement of Partition Wall W in Electrolytic Cell E The partition wall W has an alkali metal cation conductive solid electrolyte ceramic contained in the partition wall W and preferably a separation element T, and the alkali metal cation conductive solid electrolyte ceramic contained in the partition wall W and the separation element T are preferably arranged on the surface O KK Through side S KK Internal Structure I KK It is placed in the electrolytic cell E so that it is in direct contact with the side S KK Side internal structure I KK When the liquid is completely filled with the liquid L2, the liquid L2 flows over the surface O KK This means that the partition W is arranged in the electrolytic cell E such that it is in contact with all the alkali metal cation conducting solid electrolyte ceramic contained in the partition W and preferably also with the separation element T via the separation element T. Thus, ions (e.g. alkali metal ions such as sodium, lithium, etc.) from all the ASC contained in the partition W can enter the solution L2.

[0175] Furthermore, the partition wall W has an alkali metal cation conductive solid electrolyte ceramic contained in the partition wall W and preferably the separation element T, which is formed on the surface O A / MK Through side S A / MK Internal Structure I KA The electrolytic cell E is placed in such a way that the electrolytic cell E is in direct contact with the

[0176] This means that the partition wall W separates the intermediate chamber K. M Internal Structure I KM In these embodiments, the partition wall W is disposed within the electrolytic cell E as follows: adjacent to the side S AM / K Internal Structure I KM When the liquid is completely filled with the liquid L3, the liquid L3 flows over the surface O A / MK via the separation element T, thereby allowing ions from the solution L3 (e.g., alkali metal ions such as sodium, lithium, etc.) to enter all the ASC contained in the partition wall W.

[0177] In a preferred embodiment of the electrolytic cell E in the first aspect of the present invention, the surface O formed by ASC KK At least 50%, in particular at least 70%, preferably at least 90%, most preferably 100% of the part has an internal structure I KK is in contact with.

[0178] In a preferred embodiment of the electrolytic cell E with at least one intermediate chamber according to the first aspect of the present invention, the surface O formed by the ASC A / MK At least 50%, in particular at least 70%, preferably at least 90%, most preferably 100% of the part has an internal structure I KM is in contact with.

[0179] 4.3 The method according to the invention In a second aspect, the present invention relates to a method for producing an alcohol ROH solution L1 of an alkali metal alkoxide XOR, where X is an alkali metal cation and R is an alkyl group having 1 to 4 carbon atoms. The method according to the second aspect of the present invention is carried out in an electrolytic cell E according to the first aspect of the present invention.

[0180] X is preferably Li + , K + , Na + More preferably, the group consisting of K + , Na + Most preferably, X=Na + It is.

[0181] R is preferably selected from the group consisting of n-propyl, iso-propyl, ethyl and methyl, more preferably from the group consisting of ethyl and methyl. R is most preferably methyl.

[0182] According to the invention, the electrolytic cell E comprises at least one intermediate chamber K M The process includes steps (β1), (β2), and (β3) which proceed simultaneously.

[0183] 4.3.1 Process (β1) In step (β1), a solution L2 containing an alcohol ROH, preferably an alkali metal alkoxide XOR and an alcohol ROH, is added to K K is sent through.

[0184] Preferably, solution L2 is water-free. According to the present invention, "water-free" means that the weight (mass ratio) of water in solution L2 based on the weight of alcohol ROH in solution L2 is 1:10 or less, more preferably 1:20 or less, even more preferably 1:100 or less, even more preferably 0.5:100 or less. When solution L2 contains XOR, the mass proportion of XOR in solution L2 is in particular from 0% to more than 30% by weight, preferably from 5% to 20% by weight, more preferably from 10% to 20% by weight, more preferably from 10% to 15% by weight, most preferably from 13% to 14% by weight, and very most preferably 13% by weight, relative to the entire solution L2.

[0185] When solution L2 contains XOR, the mass ratio of XOR to alcohol ROH in solution L2 is in particular in the range of 1:100 to 1:5, more preferably in the range of 1:25 to 3:20, even more preferably in the range of 1:12 to 1:8, and even more preferably 1:10.

[0186] 4.3.2 Process (β2) In step (β2), a neutral or alkaline aqueous solution L3 of a salt S containing X as a cation is added to K M Then through V AM Then through K A is sent through.

[0187] The salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.

[0188] The halides are fluoride, chloride, bromide and iodide. The most preferred halide is chloride.

[0189] The pH of the aqueous solution L3 is 7.0 or higher, preferably in the range of 7 to 12, more preferably in the range of 8 to 11, even more preferably 10 to 11, and most preferably 10.5.

[0190] The mass proportion of salt S in solution L3 is preferably from 0% to more than 20% by weight, more preferably from 1% to 20% by weight, more preferably from 5% to 20% by weight, even more preferably from 10% to 20% by weight, and most preferably 20% by weight, relative to the entire solution L3.

[0191] 4.3.3 Process (β3) In step (β3), E A and E K A voltage is applied between the

[0192] This causes current to move from the charging source to the anode, transfer charge through the ions to the cathode, and finally return the current to the charging source. Charging sources are known to those skilled in the art and are typically rectifiers that can convert AC to DC and generate a specific voltage via a transformer.

[0193] This results in the following: Solution L1, which has a higher concentration of XOR than L2, is at outlet A. KK is obtained. Aqueous solution L4 with a lower concentration of S than L3 is at outlet A. KA is obtained.

[0194] In step (β3) of the method according to the second aspect of the invention, in particular the current density (= intermediate chamber K M The ratio of the current supplied to the electrolytic cell to the area of ​​the solid electrolyte in contact with the anolyte present in the electrolytic cell is in the range of 10 to 8000 A / m2, more preferably 100 to 2000 A / m2. 2 and even more preferably in the range of 300 to 800 A / m 2 and even more preferably in the range of 494 A / m 2 A voltage is applied to the intermediate chamber K such that a current flows such that MThe area of ​​the solid electrolyte in contact with the anolyte present in the electrolyte is preferably in the range of 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , and even more preferably 2.83 cm 2 It is.

[0195] Step (β3) of the method according to the second aspect of the invention is to separate the two chambers K so that both L3 and L2 are in contact with the solid electrolyte contained in the partition W and in particular also with the separating element T. M and K. A is at least partially filled with L3, and K K It will be clear that this is implemented when is at least partially filled with L2.

[0196] In step (β3), A and E K The fact that charge transfer occurs between K K , K M and K. A L2 and L3 are simultaneously applied to the electrode E so that they complete a circuit. A and E K It means to cover.

[0197] This is especially true when the liquid flow of L3 is K M , V AM and K. A is continuously pumped through the L2 liquid flow, K The liquid flow at L3 is fed through the electrode E A The liquid flow of L2 covers the electrode E K This is the case when the coating at least partially, preferably completely, covers the

[0198] In a further preferred embodiment, the method according to the second aspect of the invention is carried out continuously, i.e. steps (β1) and (β2) are carried out continuously whilst applying a voltage according to step (β3).

[0199] After step (β3) is performed, solution L1 is discharged to outlet A KKand the concentration of XOR in L1 is higher than the concentration of XOR in L2. When L2 already contains XOR, the concentration of XOR in L1 is preferably 1.01 to 2.2 times, more preferably 1.04 to 1.8 times, even more preferably 1.077 to 1.4 times, even more preferably 1.077 to 1.08 times, and most preferably 1.077 times higher than that of L2, and the mass proportion of XOR in L1 and L2 is more preferably in the range of 10 wt% to 20 wt%, and even more preferably 13 wt% to 14 wt%.

[0200] The aqueous solution L4 of S, whose S concentration is lower than L3, is at outlet A. KA is obtained.

[0201] 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 the concentration of the aqueous solution L3 used in each case.

[0202] More specifically, steps (β1) to (β3) of the method according to the second aspect of the present invention are carried out at a temperature of 20° C. to 70° C., preferably 35° C. to 65° C., more preferably 35° C. to 60° C., and even more preferably 35° C. to 50° C., and at a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, and more preferably 1.0 bar.

[0203] In the course of carrying out the steps (β1) to (β3) according to the second embodiment of the method according to the present invention, hydrogen is usually introduced into the cathode chamber K K This is generated in Exit A KK The hydrogen and solution L1 may then be removed from the cell together with the solution L1 from the anode chamber K. In a particular embodiment of the invention, the mixture of hydrogen and solution L1 may then be separated by methods known to those skilled in the art. If the alkali metal compound used is a halide, in particular a chloride, then chlorine or other halogen gas may be removed from the anode chamber K. A This may be generated within the exit A KKmay be removed from the tank together with solution L4. In addition, oxygen and / or carbon dioxide may be produced, which may also be removed. In a particular embodiment of the invention, the mixture of chlorine, oxygen and / or CO2 with solution L4 may then be separated by methods known to those skilled in the art. It is then equally possible to separate the chlorine, oxygen and / or CO2 gases from solution L4, followed by their separation by methods known to those skilled in the art.

[0204] 4.3.4 Further advantages of steps (β1) to (β3) Carrying out steps (β1) to (β3) leads to further surprising advantages that were not anticipated in the light of the prior art: steps (β1) to (β3) of the method according to the invention protect the acid-labile solid electrolyte from corrosion without sacrificing alkoxide solution from the anode space as a buffer, as in the prior art. The method according to the invention is therefore more efficient than the method described in WO 2008 / 076327, which uses product solution in the intermediate chamber, reducing the overall conversion. [Brief description of the drawings]

[0205] [Figure 1] (A) shows an inventive electrolytic cell E. (B) shows another inventive electrolytic cell E. [Diagram 2] (A) Partition wall W <16> (B) Partition wall W <16> 1 shows another embodiment of the present invention. [Diagram 3] 2A and 2B, a detailed view of the portion highlighted by the dotted circle in FIG. 2B, and FIG. [Figure 4] (A) Partition wall W <16> (B) Partition wall W <16> (C) Partition wall W <16> (D) Partition wall W <16> 1 shows a further embodiment of the present invention. [Diagram 5] (A) shows an inventive electrolytic cell E. (B) shows an inventive electrolytic cell E. [Figure 6] (A) Electrolytic cell E according to the first aspect of the invention <1> (B) Electrolytic cell E according to the first aspect of the present invention. <1> Shows. [Figure 7] (A) Partition wall W of the present invention <16> (B) A further embodiment of the partition wall W of the present invention is shown. <16> 1 shows a further embodiment of the EXAMPLES

[0206] 5. Experimental Example 5.1 Comparative Example 1 Sodium methoxide (SM) was produced by the cathodic method, where the anode chamber was fed with a 20 wt. % NaCl (aqueous) solution and the cathode chamber was fed with a 10 wt. % methanolic SM solution. The electrolytic cell consisted of three compartments corresponding to that shown in Figure 1B. The connection between the intermediate and anode chambers was made by a hose attached to the bottom of the electrolytic cell. The anode and intermediate chambers were separated by a 2.83 cm 2 The cathode and intermediate chambers were separated by an anion exchange membrane (Tokuyama AMX, ammonium groups on the polymer). 2 The NaSICON type ceramics are classified according to the formula Na 3.4 Zr 2.0 S 2.4 P 0.6 O 12 The chemical composition was: The anolyte was transferred to the anode chamber through the intermediate chamber. The flow rate of the anolyte was 1 L / h, the flow rate of the catholyte was 90 mL / h, and a current of 0.14 A was applied. The temperature was 35°C. Electrolysis was carried out at a constant voltage of 5 V for 500 hours. It was observed that over a long period of time, a pH gradient develops in the intermediate chamber, which is due to the migration of ions to the electrodes during the electrolysis and the diffusion of protons produced by further reactions at the anode. This local increase in pH is undesirable, as it attacks the solid electrolyte and can cause corrosion and failure of the solid electrolyte, especially when operating for very long periods of time.

[0207] Furthermore, when the electrolytic cell is repeatedly started and stopped, the heating and cooling effects cause the NaSICON ceramic to expand and contract. Furthermore, the NaSICON membrane may become displaced within the cell. This is problematic because it increases the tendency of the ceramic to break, leading to leakage of electrolyte from the intermediate chamber to the cathode chamber, which may cause the electrolysis product to become waterlogged. Furthermore, this may cause leaks in the outer wall of the cell, allowing electrolyte to leak to the outside.

[0208] 5.2 Comparative Example 2 Comparative Example 1 was reproduced in a two-chamber cell (FIG. 1A) with only one anode chamber and only one cathode chamber, the latter separated from the cathode chamber by a NaSICON-type ceramic. This electrolytic cell therefore did not contain an intermediate chamber. Therefore, compared to Comparative Example 1, the corrosion of the ceramic was even faster, which resulted in a rapid rise in the voltage curve. If the initial voltage value was less than 5 V, it rose to more than 20 V within 100 hours.

[0209] 5.3 Example 1 Comparative Example 1 was reproduced using an electrolytic cell according to FIG. 6A in which a partition containing two NaSICON ceramics was inserted into the frame.

[0210] This arrangement reduced the extent of the expansion and contraction processes, which contributed to the useful life of the ceramic, and it prevented leakage, resulting in a cleaner product solution.

[0211] 5.4 Example 2 Comparative Example 2 was reproduced using an electrolytic cell according to FIG. 6A in which a partition wall containing four NaSICON ceramics was inserted into the frame and in which the frame element R and the separation element T were joined (FIG. 7A, but without hinges and locks).

[0212] This arrangement reduced the extent of the expansion and contraction processes, which contributed to the useful life of the ceramic, and it prevented leakage, resulting in a cleaner product solution.

[0213] 5.5 Results The expansion and contraction processes that occur during repeated electrolysis cycles relieve tensions within the ASC, which leads to an increased lifetime of the electrolysis chamber. Implementations of the present invention according to Examples 1 and 2 reduce these effects, increasing the stability of the solid electrolyte.

[0214] The use of the three-compartment cell according to the invention in the process according to the invention also prevents corrosion of the solid electrolyte, while at the same time the voltage remains constant without the need to sacrifice the alkali metal alkoxide product for the intermediate chamber. These advantages, which are already evident from the comparison of the two comparative examples 1 and 2, clearly show the surprising effectiveness of the electrolytic cell with an intermediate chamber and the corresponding process carried out therein.

[0215] TIFF2024527769000003.tif229170

Claims

1. At least one inlet Z KA <110> and at least one outlet A KA <111> and an anode electrode E A An internal structure I including <113> KA <112> and having at least one anode chamber K A <11> and At least one inlet Z KK <120>, and at least one outlet A KK <121>, and a cathode electrode E K An internal structure I including <123> KK <122> and having at least one cathode chamber K K <12>, and At least one inlet Z KM <130> and at least one outlet A KM <131> and an internal structure I KM <132> and having at least one intervening intermediate chamber K M <13> and comprising said I KA <112> and said I KM <132> are separated from each other by a diffusion barrier D<14>, The liquid is connected to V AM through <15> to the I KM from <132> to the I KA so that it can flow to <112>, the A KM <131> is the connection V AM <15> connects the inlet Z KA to <110>, the said I KK <122> and the said I KM <132> is the surface O KK <163> on one side S having KK <161> and the surface O A / MK <164> on the said side S having KK <161> on the side S opposite to A / MK <162> are separated from each other by a partition wall W including The partition wall W<16> includes at least two alkali metal cation-conductive solid electrolyte ceramics F separated from each other by at least one separation element T<17>. A <18> and F B <19>, and the alkali metal cation-conductive solid electrolyte ceramic included in the partition wall W<16> can be in direct contact with both the surface O KK <163> and the surface O A / MK <164>. The alkali metal cation-conductive solid electrolyte ceramic contained in the partition wall W<16> is in direct contact with the internal structure I<122> on the S<161> side through the surface O<163>, and the alkali metal cation-conductive solid electrolyte ceramic contained in the partition wall W<16> is in direct contact with the internal structure I<132> on the S<162> side through the surface O<164>. Electrolytic cell E<1>. KK <163> to the S KK Internal structure I on side <161> KK <163> to the S A / MK <164> to the S A / MK Internal structure I on the <162> side KM <132>. Electrolytic cell E<1>.

2. The partition wall W<16> is composed of at least four alkali metal cation-conductive solid electrolyte ceramics F A <18>, F B <19>, F C <28> and F D <29>, and the electrolytic cell E<1> according to claim 1.

3. The separation element T<17> is in a cross shape or a lattice shape, and the electrolytic cell E<1> according to Claim 2.

4. The separation element T<17> includes a material selected from the group consisting of plastic, glass, and wood, and the electrolytic cell E<1> according to Claim 1.

5. The partition wall W<16> includes a frame element R<20>, and the electrolytic cell E<1> according to Claim 1.

6. At least a part of the separation element T<17> is in an integrated shape with at least a part of the frame element R<20>, and the electrolytic cell E<1> according to Claim 5.

7. The alkali metal cation-conductive solid electrolyte ceramics included in the partition wall W<16> are independently Formula M I 1+2w+x-y+z M II w M III x Zr IV 2-w-x-y M V y (SiO 4 ) z (PO 4 ) 3-z (In the formula, M I is selected from Na + and Li + and M II is a divalent metal cation, M III is a trivalent metal cation, M V is a pentavalent metal cation, Roman numerals I, II, III, IV, V indicate the oxidation numbers at which the respective metal cations are present, w, x, y, z are real numbers, 0 ≦ x < 2, 0 ≦ y < 2, 0 ≦ w < 2, 0 ≦ z < 3, and are selected such that 1 + 2w + x - y + z ≧ 0 and 2 - w - x - y ≧ 0. ) having the structure of, and the electrolytic cell E1<1> according to Claim 1.

8. The said connection V AM <15> is the electrolytic cell E<1> formed within the said electrolytic cell E<1> as claimed in claim 1.

9. An alcohol ROH solution L of an alkali metal alkoxide XOR 1 It is a production method of <21>, X is an alkali metal cation, R is an alkyl group having 1 to 4 carbon atoms, simultaneously proceeding the following: Solution L containing the alcohol ROH 2 <22> to the K K Step (β1) of passing through <12> and sending it A neutral or alkaline aqueous solution L of a salt S containing X as a cation 3 <23> is passed through the K M <13>, and then the V AM <15> is passed through, and then the K A <11> is passed through (step (β2)). the said E A applying a voltage between A <113> and the said E K step (β3) of applying a voltage between K <123> is carried out in the electrolytic cell E<1> according to Claim 1, As a result, the L 2 solution L with a higher XOR concentration than <22> 1 <21> is obtained at the outlet A KK <121> The above-mentioned L 3 An aqueous solution L of S having an S concentration lower than <23> 4 <24> is at the outlet A KA A method obtained at <111>

10. Said X is Li + , Na + , K + The method according to claim 9, selected from the group consisting of

11. The S is a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of the X, and the method according to Claim 9.

12. The R is selected from the group consisting of methyl and ethyl, and the method according to Claim 9.

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