Impact-resistant partitions containing solid electrolyte ceramics for electrolytic cells

Abstract

The present invention relates in a first aspect to a partition wall W suitable for use in an electrolytic cell E. The partition wall W is provided with an end element R R and the separation element R T The frame element R has two opposing portions R1 and R2 between which at least two alkali metal cation conductive solid electrolyte ceramics F A and F B The separation element R T is located between and separates the alkali metal cation conducting solid electrolyte ceramics contained in the partition wall W from each other. A feature of the invention is that the two parts R1 and R2 are connected to at least one fixing element B R Therefore, the end element R R and at least one fixed element B T Separation element R T are fixed relative to each other. In comparison with the prior art, where the partition wall W contains an integral solid electrolyte, this arrangement is firstly more flexible, since the individual ceramics have more freedom to react to temperature variations, for example by contraction or expansion. This improves the stability of the ceramics against mechanical stresses. At the same time, the parts R1 and R2 are more easily connected to the end elements R R and the separation element R T In both cases, at least one fixing element B R Or B T The fixed arrangement of the at least two solid electrolyte ceramics between the portions R1 and R2 improves the mechanical stability of the arrangement of the at least two solid electrolyte ceramics between the portions R1 and R2. In a second aspect, the present invention provides a cathode chamber K separated from an adjacent chamber by a partition wall W. K The adjacent chamber refers to the anode chamber K of the electrolytic cell E. A or intermediate chamber K M It is. In a third aspect, the present invention relates to a method for producing an alkali metal alkoxide solution in an electrolytic cell E according to the second aspect of the invention.

Description

[Technical field]

[0001] The present invention relates in a first aspect to a partition wall W suitable for use in an electrolytic cell E. The partition wall W is provided with an end element R R and the separation element R T The frame element R includes two opposing portions R1 and R2, between which are disposed at least two alkali metal cation conductive solid ceramics F A and F B The separation element R T are located between and separate the alkali metal cation conducting solid electrolyte ceramics contained in the partition wall W from each other. A feature of the present invention is that the two parts R1 and R2 are connected to at least one fixing element B R Therefore, the end element R R and at least one fixed element B T Separation element R T are fixed relative to each other.

[0002] In comparison with the prior art, where the partition wall W contains an integral solid electrolyte, this arrangement is firstly more flexible, since the individual ceramics have more freedom to react to temperature variations, for example by contraction or expansion. This improves the stability of the ceramics against mechanical stresses. At the same time, the parts R1 and R2 are more easily connected to the end elements R R and the separation element R T In both cases, at least one fixing element B R Or B T The fixed arrangement of the at least two solid electrolyte ceramics between the portions R1 and R2 improves the mechanical stability of the arrangement of the at least two solid electrolyte ceramics between the portions R1 and R2.

[0003] In a second aspect, the present invention provides a cathode chamber K separated from an adjacent chamber by a partition wall W. K The adjacent chamber refers to the anode chamber K of the electrolytic cell E. A or intermediate chamber K M It is.

[0004] In a third aspect, the present invention relates to a method for producing an alkali metal alkoxide solution in an electrolytic cell E according to the second aspect of the invention. [Background technology]

[0005] 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.

[0006] NaSICON solid electrolytes are also used in the electrochemical production of other compounds.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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.

[0012] The object of the present invention is therefore to provide an electrolytic cell which does not have these drawbacks.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] Such cells have also been proposed in the prior art for the production or purification of alkali metal alkoxides.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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]

[0022] [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]

[0023] 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]

[0024] 2. Brief description of the invention The problem addressed by the present invention is solved by a partition wall W according to a first aspect of the present invention. <16> is the surface KK <163> One side S has KK <161> And, side S KK <161> and the surface O, which is opposite A / MK <164> Side S with A / MK <162> It is equipped with:

[0025] Partition wall W <16> is made up of two opposing parts R1 <201> and R2 <202> Between them, there are at least two alkali metal cation conducting solid electrolyte ceramics F A <18> and F B <19> Frame element R in which <2> Also includes. At the same time, R1 <201> is the surface KK <163> Direct contact is possible from R2 <202> is the surface A / MK <164> can be contacted directly from Frame element R <2> is the frame element R R <20> and the separation element R T <17> and frame element R R <20> is the surface KK <163> and O A / MK<164> and preferably completely surrounds the frame element R T <17> Partition wall W <16> and separating the alkali metal cation conductive solid electrolyte ceramics contained in the <16> The alkali metal cation conductive solid electrolyte ceramics contained in KK <163> and surface O A / MK <164> Both can be contacted directly. Partition wall W <16> is R1 <201> and R2 <202> But the end element R R <20> At least one fixing element B R <91> are fixed together by R1 <201> and R2 <202> is the separation element R T <17> At least one fixing element B T <92> The present invention is characterized in that the two components are fixed to each other by

[0026] In a second aspect, the present invention provides a method for producing a pharmaceutical 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 KA <112> At least one anode chamber K having A <11> , - 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 KK <122> At least one cathode chamber K having K <12> , - If necessary, at least one inlet 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> Electrolyzer E containing <1> and I KA <112> and I KM<132> is the diffusion barrier D <14> are separated from each other by A KM <131> is the connection V AM <15> By Entrance Z KA <110> Connected to V AM <15> via I KM <132> From I KA <112> It is possible to deliver liquid to Electrolytic cell E <1> is the middle room K M <13> If you do not have I KA <112> and I KK <122> is a partition wall W according to the first aspect of the present invention. <16> are separated from each other by Electrolytic cell E <1> At least one intermediate chamber K M <13> If it has I KK <122> and I KM <132> is a partition wall W according to the first aspect of the present invention. <16> are separated from each other by Partition wall W <16> , in particular the separation element R T <17> The alkali metal cation conductive solid electrolyte ceramics contained in KK <163> Via S KK <166> Side internal structure I KK <122> In direct contact with Electrolytic cell E <1> is the middle room K M <13> If not equipped with a partition wall W <16> , in particular the separation element R T <17> The alkali metal cation conductive solid electrolyte ceramics contained in A / MK <164> Via S A / MK <162> Side internal structure I KA <112> Direct contact with Electrolytic cell E <1> At least one intermediate chamber K M <13> If equipped with a partition wall W <16> , in particular the separation element R T <17> The alkali metal cation conductive solid electrolyte ceramics contained in A / MK <164> Via S A / MK <162> Side internal structure I KM <132> In direct contact with the electrolytic cell E <1> Regarding.

[0027] In a third aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: A method for producing an alcoholic 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, (α) Solution L2 containing alcohol ROH is added to K K A neutral or alkaline aqueous solution L3 of salt S containing X as a cation is passed through K A The process of passing the A and E K and a step (α3) of applying a voltage between the intermediate chamber K M or in an electrolytic cell E according to the second aspect of the invention, which does not comprise (β) Solution L2 containing alcohol ROH is K K A neutral or alkaline aqueous solution L3 of salt S containing X as a cation is passed through K M Then through V AM Then pass it through K A (β2), E A and E K At the same time, a step (β3) of applying a voltage between the intermediate chamber K M In an electrolytic cell E according to the second aspect of the invention, This allows Exit A KK In L2 <22> A solution L1 with a higher XOR concentration than Exit A KA and obtaining an aqueous solution L4 having a lower S concentration than L3.

[0028] 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:

[0029] 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:

[0030] 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.

[0031] 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.

[0032] Sodium methoxide in methanol L2 <22> But the entrance Z KK <120> Via Internal Structure I KK <122> will be sent.

[0033] 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.

[0034] 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 in L3? <23> Reduced compared to aqueous solution L4 <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.

[0035] 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:

[0036] Internal structure I KA <112> is the connection V AM <15> Internal structure I KM <132> is connected to

[0037] 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.

[0038] 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).

[0039] 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 outer wall W of the electrolytic cell E A <80> Exit A through KM <131> Anode chamber K A <11> At the bottom of the outer wall W of the electrolytic cell E A <80> Entrance Z through KA <110> is connected to.

[0040] 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.

[0041] 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.

[0042] 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 in L3? <23> Reduced compared to aqueous solution L4 <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.

[0043] 3.2 Figures 2A and 2B FIG. 2A shows a partition wall W of the present invention. <16> Surface O KK <163> Side S with KK <161> is in the plane of the drawing and the surface O A / MK <164> Side S withA / MK <162> is not visible in FIG. 2A but is below the plane of the drawing.

[0044] Partition wall W <16> is the frame element R <2> Two NaSICON solid electrolyte ceramics F placed between A <18> and F B <19> Frame element R <2> is divided into two parts R1 <201> and R2 <202> Between them, ceramic F A <18> and F B <19> Frame element R is placed. <2> is the end element R R <20> and the separation element R T <17> The separating element R T <17> NaSICON solid electrolyte ceramic F A <18> and F B <19> and separate them from each other. T <17> is a frame element R shown shaded in Figs. 2A and 2B <2> It is a part of the end element R R <20> is a frame element R shown without shading in Figs. 2A and 2B <2> It is a part of the end element R R <20> Two frame parts R1 in the region <201> and R2 <202> are the eight fixed elements B R <91> and fixed to each other by the separating element R T <17> Two frame parts R1 in the region <201> and R2 <202> is one fixed element B T <92> The illustrated diagram is of the partition wall W which is described in detail in Figs. 3A to 3C. <16> Section Q RR <165> and Q RT <166> It shows that. Q RR <165> and Q RT <166> Two solid electrolyte ceramics F A <18> and F B <19> In one region of the surface O KK <163> It intersects with partition wall W at right angles to .

[0045] FIG. 2B shows the partition wall W of the present invention. <16> This shows another embodiment of the partition wall W <16> Four NaSICON solid electrolyte ceramic F A <18> , F B <19> , F C <28> , F D <29> F A <18> , F B <19> , F C <28> , F D <29> is the frame part R1 <201> and R2 <202> 2, except that the separating element R T <17> is a cross shape. End element R R <20> Two frame parts R1 within the region <201> and R2 <202> 12 fixed elements B R <91> and fixed to each other by the separating element R T <17> Two frame parts R1 within the region <201> and R2 <202> are three fixed elements B T <92> The surfaces are fixed together by KK <163> Side S with KK <161> is in the plane of the drawing and the surface O A / MK <164> Side S with A / MK <162> is not visible in FIG. 2B but is below the plane of the drawing.

[0046] 3.3 Figures 3A to 3C 3A to 3C show the partition wall W above the continuous dotted line. <16> End element R of R <20> The cross section Q shown in FIGS. 2A and 2B in the region RR <165> 3A and 3B also show, below the continuous dotted line, a detailed view of the partition wall W <16> Separation element R T <17> The cross section Q shown in FIGS. 2A and 2B in the region RT <166> A detailed view of the surface O KK <163> Side S with KK <161> is on the right side of Figure 3A. Surface O A / MK <164> Side S with A / MK <162> is on the left side of Figure 3A.

[0047] In FIG. 3A, the solid electrolyte ceramic F A <18> is the cross section Q RR <165> In the frame element, two frame parts R1 <201> and R2 <202> They may be in one piece or independent of each other, as shown by the dotted lines. Preferably, they are separated from each other. They are arranged between the fixing element B R <91> The solid electrolyte ceramic F is fixed to the substrate by screws. A <18> are clamped. The two frame parts R1 <201> and R2 <202> and solid electrolyte ceramics F A <18> Between the seal Di <40> is preferably provided.

[0048] Cross section Q RT <166> Now, the separation element R T <17> The two frame parts R1 <201> and R2 <202> Between them, two solid electrolyte ceramics F A <18> and F B <19> They are fixed elements B T <92> The solid electrolyte ceramic F is fixed to the plate by screws. A <18> and F B <19> is clamped, preferably with a seal Di <40> It is equipped with:

[0049] FIG. 3B shows two cross sections Q RR <165> and Q RT <166> A further embodiment of each is shown. This is a two-part fixing element B R <91> and B. T <92> Hook B H<93> These hooks correspond to the embodiment shown in FIG. 3A, except that they are formed by <201> or R2 <202> They may be integral with each other (as shown in the present specification) or may be joined to each other. <201> and R2 <202> can be fixed to each other.

[0050] FIG. 3C shows cross section Q RR <165> This shows a further embodiment of the end element R R <20> 3A, except that it forms rounded corners.

[0051] 3.4 Figures 4A and 4B 4A and 4B respectively show electrolytic cell E according to a second embodiment of the present invention. <1> These are the partition walls W <16> Cathode chamber K K <12> Internal Structure I KK <122> Anode chamber K A <11> Internal Structure I KA <112> 1A, except that it is separated from the separator 10. The separator 10 is the separator shown in FIG. 2A or FIG. 2B.

[0052] In this case, in the embodiment according to FIG. 4A, the fixing element B R <91> and B. T <92> Screws are used as the fasteners. Partition wall W <16> End element R of R <20> Section Q of the area RR <165> And partition wall W <16> Separation element R T <17> Section Q of the area RT <166> In each case, as illustrated in FIG. 3A.

[0053] In the embodiment according to FIG. 4B, the mutually engaging hooks B H <93> But fixed element B R <91> and B. T <92> It is used as a partition wall. <16> End element R of R <20> Section Q of the areaRR <165> And partition wall W <16> Separation element R T <17> Section Q of the area RT <166> In each case, as illustrated in FIG. 3B.

[0054] 3.5 Figures 5A and 5B FIG. 5A shows an electrolytic cell E1 according to a second embodiment of the invention. It is separated by a partition wall W <16> Cathode chamber K K <12> Internal Structure I KK <122> The intermediate chamber K M <13 Internal Structure I KM <132> 1B, except that it is separated from the partition wall W <16> is the partition wall shown in FIG. 2A or 2B. In this case, in the embodiment according to FIG. 4A, the screw is fixed to the fixing element B R <91> and B. T <92> It is used as a partition wall. <16> End element R of R <20> Section Q of the area RR <165> and the separating element R of the partition wall W T <17> Section Q of the area RT <166> In each case, as illustrated in FIG. 3A.

[0055] FIG 5B shows an electrolytic cell E1 according to a second embodiment of the invention. This is the same as the electrolytic cell E shown in FIG 5A. <1> It corresponds to, but there are two differences: Difference 1 Intermediate room K M <13> Internal Structure I KM <132> From anode chamber K A <11> Internal Structure I KA <112> Connection to V AM <15> Electrolyzer E <1> rather, the diffusion barrier D <14> This perforation is formed on the inside through the diffusion barrier D <14> or a diffusion barrier D <14> From the beginning of production, the diffusion barrier D <14> The polymer may already be present within the material (eg, in the case of fabrics such as filter fabrics or metal weaves). Difference 2 In the embodiment according to FIG. 5B, the mutually engaging hooks B H <93> is fixed element B R <91> and B. T <92> It is used as a partition wall. <16> End element R of R <20> Section Q of the area RR <165> And partition wall W <16> Separation element R T <17> Section Q of the area RT <166> In each case, as illustrated in FIG. 3B.

[0056] Separation element R T <17> is a frame element R shown shaded in Figs. 6A and 6B <2> is part of.

[0057] 3.6 Figures 6A and 6B FIG. 6A shows a partition wall W of the present invention. <16> Further embodiments of the present invention are shown (on the left) with surface O KK <163> Side S with KK <161> 1 is a top view of the curved clamp shown in FIG.

[0058] This consists of four NaSICON solid electrolyte ceramic F A <18> , F B <19> , F C <28> and F D <29> These are frame elements R <2> Both halves of R1 <201> and R2 <202> It is placed between frame element R. <2> is the end element R R <20> and the separation element R T <17> The separating element R T <17> is a cross-shaped ceramic with NaSICON solid electrolyte A <18> , F B <19> , F C <28> and F D <29> and separate them from each other. T <17> is a frame element R shown shaded in Figs. 6A and 6B <2> It is a part of the end element R R<20> is a frame element R shown without shading in Figs. 6A and 6B <2> It is a part of the end element R R <20> Two frame parts R1 in the region <201> and R2 <202> is the fixed element B R <91> and the separating element R T <17> Two frame parts R1 in the region <201> and R2 <202> is the fixed element B T <92> They are fixed together by hinges, if necessary. <50> In either case, the seal Di <40> As a rubber ring, each solid electrolyte ceramic F A <18> , F B <19> , F C <28> and F D <29> and two frame parts R1 <201> and R2 <202> It is preferable that the seal Di is provided between the <40> The ring functioning as the axial guide is shown in dotted outline in the front view on the left of FIG. 6A.

[0059] FIG. 6B 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> 6A, except that it further comprises a frame element R <2> Each has a hole <61> With four bulges <60> ("rabbit ears"), so that the partition wall can be appropriately designed to separate, for example, the cathode chamber K K <12> can be fixed to.

[0060] 4. Detailed Description of the Invention 4.1 Partition wall W The present invention relates in a first aspect to a partition wall W. It is particularly suitable as a partition wall of an electrolytic cell, in particular an electrolytic cell E.

[0061] Thus, in one aspect, the present invention also relates to an electrolytic cell comprising a partition wall W, in particular an electrolytic cell E comprising a partition wall W.

[0062] The partition wall W is the separating element R T At least two alkali metal cation conductive solid electrolyte ceramics (hereinafter abbreviated as "ASC") F are separated from each other by A and F B It is equipped with:

[0063] The partition wall W has two opposing sides S KK and S A / MK This is equipped with side S A / MK Side S KK (and vice versa). KK and S A / MK in particular have planes which are entirely parallel to one another. Otherwise, the geometric shape of the partition W is not subject to further constraints and can in particular be adapted to the cross-section of the electrolytic cell E in which it is used. For example, it may be cuboidal in shape and have a rectangular cross-section, or conical or cylindrical in shape and have a circular cross-section. If desired, the partition W may 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") by means of which the partition W can be fixed to the electrolytic cell or by means of which the two frame parts R1 and R2 of the partition W can be fixed to each other.

[0064] 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.

[0065] The partition wall W includes a frame element R. It is composed of two opposing parts, preferably halves R1 and R2, between which are disposed at least two alkali metal cation conducting solid ceramics F A and F B R1 is located on the surface O KK R2 is directly accessible from the surface O A / MK can be contacted directly from

[0066] Frame element R is frame element R R and the separation element R T and frame element R R is the surface O KK and O A / MK and preferably completely surrounds the frame element R T are located between the alkali metal cation conductive solid electrolyte ceramics included in the partition wall W and separate them from each other. Therefore, the alkali metal cation conductive solid electrolyte ceramics included in the partition wall W are KK and surface O A / MK Both can be contacted directly.

[0067] The feature "partition wall" means that the partition wall W is liquid-tight. This means that the ASC and the frame element R are adjacent to each other without any gaps. Therefore, there is no gap between the frame element R and the ASC contained in the partition wall, and aqueous solutions, alcohol solutions, alcohol or water can enter the S through the gap. KK S from the side A / MK It will not flow to one side or the other.

[0068] In the case where there are two or more pairs of sides where the alkali metal cation conductive solid electrolyte ceramics contained in the partition wall W and each part R1 or R2 face each other via a surface that can directly contact each other, this is referred to as S in the context of this specification. KK and S A / MK A pair of opposing sides, denoted as KK and O A / MK When the surface areas included in the two pairs of opposite sides are the same, a person skilled in the art can easily distinguish the surface O KK and OA / MK S with KK and S A / MK One pair can be selected as

[0069] Among the partition walls W having two or more pairs of opposing sides through a surface where the alkali metal cation conductive solid electrolyte ceramics contained in the partition walls W and each portion R1 or R2 can directly contact each other, it is preferable that the surface areas of the opposing pairs of 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 the O KK and O A / MK It includes.

[0070] The partition W according to the first aspect of the invention also includes embodiments in which the partition W comprises more than one ASC, for example 4, 9 or 12 ASC.

[0071] In the case of a partition wall W, all ASCs contained in the partition wall W are separated by the separation element R of the frame element R. T which means that no ASC is directly adjacent to another ASC, i.e. there is no frame element R between them.

[0072] The partition wall W has an ASC on the surface O KK and surface O A / MK It is further characterized in that it is directly accessible from both the

[0073] With respect to the ASC contained in the partition wall W, "direct contact" means that the surface O KK and O A / MK This means that a part of the ASC in the partition wall W is formed by the surface of the ASC in the partition wall W, and the ASC in the partition wall W is formed by the two surfaces O KK and O A / MK This means that the two surfaces are directly accessible from each other, for example, by aqueous solutions, alcohol solutions, alcohol or water. KK and O A / MK They can be wetted in

[0074] With respect to the arrangement of ASCs within a partition wall W, this means that for each ASC contained within the partition wall W, KK Surface of KK From there, each ASC is completely passed through to the side S A / MK Surface of A / MK This means that there is a route to

[0075] The two frame elements R1 and R2 are KK and O A / MK can be contacted directly from

[0076] Regarding the frame portion R1 included in the partition wall W, "direct contact is possible" means that the surface O KK This means that a part of the surface O is formed by the surface of the frame portion R1. KK Therefore, the surface O can be directly accessed by, for example, an aqueous solution, an alcohol solution, alcohol, or water. KK It can be wetted in

[0077] Regarding the frame portion R2 included in the partition wall W, "direct contact is possible" means that the surface O A / MK A part of the frame portion R2 is formed by the surface of the frame portion R2, and the frame portion R2 is formed by the surface O A / MK Therefore, the surface O can be directly accessed by, for example, an aqueous solution, an alcohol solution, alcohol, or water. A / MK It can be wetted in

[0078] In particular, with regard to the arrangement of frame elements R in partition walls W, this means that KK Surface of KK Then, it passes through the R1 portion, then through the R2 portion (possibly through the seal Di), and does not pass through the ASC, and enters the side S A / MK Surface of A / MK This means that there is a route to

[0079] In a preferred embodiment of the partition wall W in the first aspect of the invention, the surface OKK 50% to 95%, more preferably 60% to 90%, and even more preferably 70% to 85% of the surface O is formed by ASC contained in the partition wall W. KK The remaining part is even more preferably formed by the frame part R1.

[0080] In a preferred embodiment of the partition wall W in the first aspect of the 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 ASC contained in the partition wall W. A / MK The remaining part is even more preferably formed by the frame part R2.

[0081] In a preferred embodiment, the partitions W, in particular the partitions W between the frame elements R and the ASC, are provided with seals Di (for example as shown in Figures 3A, 3B and 3C), which ensure in a particularly efficient manner that the partitions W are liquid-tight. The seals Di can be selected for each ASC or each frame element R by the person skilled in the art.

[0082] The seal Di especially comprises a material selected from the group consisting of elastomers, adhesives, preferably elastomers.

[0083] Useful elastomers are especially rubbers, preferably ethylene-propylene-diene rubbers ("EPDM"), fluoropolymer rubbers ("FPM"), perfluoropolymer rubbers ("FFPM"), or acrylonitrile-butadiene rubbers ("NBR").

[0084] The seal Di is preferably selected such that it is compressed when the two frame parts R1 and R2 are secured together and the ASC is placed between them, thereby further enhancing the integrity of the partition wall W.

[0085] In a preferred embodiment, the partition wall W is made up of at least four ASCs F A , F B , F Cand F D and even more preferably, exactly four ASCs, F A , F B , F C and F D It is equipped with:

[0086] 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:

[0087] 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:

[0088] 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.

[0089] In contrast, the individual ASCs in the partition wall W in the first embodiment of the present invention are separated by separation elements R T Adjacent to the surface O KK and O A / MK In the case of an ASC at the edge of frame element R R This has beneficial effects, both of which increase the long-term stability of ASCs. Each ASC further has an available degree of freedom, i.e. an 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. This direction of expansion does not exist or is at least strongly limited 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. -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.

[0090] As a result, the tendency for breakage to occur is clearly reduced for the "split" ASC in the partition wall W compared to using a single sheet.

[0091] 4.1.1 Frame element R The frame element R comprises two opposing parts R1 and R2 between which are arranged two alkali metal cation conductive solid ceramics F contained in a partition wall W. A and F B is placed. This placement can be done in all ways well known to those skilled in the art. In a particular embodiment, the two parts R1 and R2 clamp the ASC between them, preferably using a seal Di that further stabilizes the ASC in the frame element R. In another preferred embodiment, the ASC is glued to the two frame parts R1 and R2. The adhesive KI used for this purpose can be all adhesives well known to those skilled in the art that are stable under electrolytic conditions. Preferred KI include at least one substance selected from epoxy resins, phenolic resins.

[0092] The partition wall W may be provided with a hinge that allows the two parts R1 and R2 of the frame element R to be opened and closed.

[0093] The frame element R comprises in particular a material selected from the group consisting of plastic, glass, wood, more preferably the frame element R comprises plastic. Even more preferably, the plastic is selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride.

[0094] In a preferred embodiment, the seal Di is provided between the frame element R and the ASC included in the partition W. This improves the liquid-tightness of the partition W.

[0095] Frame element R is end element R R and the separation element R T Form.

[0096] 4.1.1.1 Separation element R T Separation element R T refers to the area of ​​a frame element R that is located between at least two ASCs and separates them from each other. T is formed by two moieties R1 and R2.

[0097] A suitable separating element R formed by a frame element R T are all objects by which the respective ASCs can be arranged in isolation from one another. The ASCs are arranged so as not to impair the function of the partition wall W, which separates the cathode chamber from the adjacent intermediate or anode chambers in a liquid-tight manner in the electrolytic cell E, by separating elements R T are adjacent with no gaps.

[0098] Separation element R T The shape of the partition wall W may be selected by one skilled in the art, depending in particular on the number and shape of the ASCs to be included in the partition wall W.

[0099] For example, if the partition wall W comprises two or three ASCs, these are separated by a separation element R T The ASCs may be separated from each other by lands disposed between the ASCs as shown in FIG. 2A (e.g., see FIG. 2A).

[0100] If the partition wall W comprises four or more ASCs, they are separated by cross-shaped (see Fig. 2B and Fig. 6A) or lattice-shaped (see Fig. 6B) separating elements R T can be separated by

[0101] It is preferred that the partition wall W comprises at least four ASCs, and the separation element R T More preferably, the shape is a cross or a lattice.

[0102] Separation element R T are in particular designed in such a way that the respective ASC can be fitted or clamped into the separating element, which may already have been carried out in a corresponding manner in the production of the partition wall W.

[0103] Separation element R T Preferably, the separating element R comprises a material selected from the group consisting of plastic, glass and wood. More preferably, the separating element R T contains plastic. Even more preferably, the plastic is selected from the group consisting of polypropylene, polystyrene, and polyvinyl chloride ("PVC"), including post-chlorinated polyvinyl chloride ("PVC-C").

[0104] 4.1.1.2 End element R R The frame element R is a separation element R T In addition to forming the end element R R Also form the end element R as the area of ​​the frame element R. R is formed by two parts R1 and R2. The end element R R (separation element R T (different from) are regions of the frame element R that are not arranged between the alkali metal cation conductive solid electrolyte ceramics contained in the partition wall W, i.e., do not separate the alkali metal cation conductive solid electrolyte ceramics from one another.

[0105] End element R R is the surface O KK and O A / MK This means, more specifically, that the end element R R is the surface O KK and O A / MK at least partially, and preferably completely, surrounding the

[0106] End element R R is the surface O KK and O A / MK It may or may not be part of the end element R. R is the surface O KK and O A / MK It is preferable that the ion exchange resin is a part of the ion exchange resin.

[0107] End element R R In particular, surface O KK and O A / MK may or may not be directly accessible from

[0108] End element R Ris the surface O KK and O A / MK In this preferred embodiment, the end element R as part of R1 is directly accessible from R is the surface O KK is directly accessible from the end element R as part of R2 R is the surface O A / MK can be contacted directly from

[0109] End element R included in partition wall W R Regarding "not directly accessible" means that the end element R R However, only the side S of the partition wall W KK and S A / MK More specifically, the end element R in this case is formed as at least a part of the surface of the side that is not R is 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.

[0110] Frame element R included in partition wall W R "Directly accessible" means that the surface O KK Part of the frame element R R This means that the surface of the frame element R R Surface O KK This means that it is directly accessible from the surface O, for example by aqueous or alcoholic solutions, alcohol or water. KK It can be wetted with.

[0111] Frame element R included in partition wall W R "Directly accessible" means that the surface O A / MK Part of the frame element R R The surface of the frame element R R The surface O A / MK This means that it is directly accessible from the surface O, for example, by an aqueous solution, an alcohol solution, alcohol or water. A / MKThis is the end element R in the partition wall W. R Regarding the arrangement of the side S KK Surface of KK From the end element R R Completely through side S A / MK Surface of A / MK The key point is that there is a route to this.

[0112] This includes the following embodiments: -Surface O KK and O A / MK A part of the end of R It is formed by: - Surface O (as shown in Figs. 2A, 2B, 6A and 6B) KK and O A / MK The end of is the end element R R It is completely formed by

[0113] End element R R is the side S of the partition wall W KK and S A / MK More specifically, the end element R may be formed as at least a part of the surface of the side that is not R is 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.

[0114] For example, FIG. 2A and FIG. 2B show an end element R R But side S of partition wall W KK and S A / MK 13 shows an embodiment in which the surface on the non-contact side is completely formed.

[0115] End element R R Preferably, the end element R comprises a material selected from the group consisting of plastic, glass, and wood. More preferably, the end element R R Contains plastic. Even more preferably, the plastic is selected from the group consisting of polypropylene, polystyrene, and polyvinyl chloride ("PVC"), including post-chlorinated polyvinyl chloride ("PVC-C").

[0116] In a further preferred embodiment, the end element R R and the separation element R T It is even more preferred that they comprise the same material, both comprising a plastic, which is even more preferred selected from polypropylene, polystyrene, polyvinyl chloride, PVC-C.

[0117] In a preferred embodiment, the separation element R T At least a part of the frame element R R This more specifically means that the separating element R T At least a part of the end element R R This means that it is combined with

[0118] End element R R The embodiment of has the further advantage of acting as part of the outer wall of the electrolytic cell E. This part of the partition wall W is connected to each internal structure I KK , I KA or I KM The partition wall W does not come into contact with the solution inside the wall. It would therefore be wasteful to form this part of the partition wall W from solid electrolyte ceramic. Moreover, the parts of the partition wall W which are clamped between or form part of the outer walls would be subjected to forces which the brittle solid electrolyte ceramic would not be able to withstand. Therefore, instead, a fracture-resistant, cheaper material is chosen for the frame element R.

[0119] 4.1.2 Fixed element B R and B. T In the first embodiment of the present invention, the partition wall W is such that R1 and R2 are end elements R R At least one fixing element B R and R1 and R2 are fixed to each other by the separating element R TAt least one fixing element B T The present invention is characterized in that the two components are fixed to each other by

[0120] In this regard, the end element R R "In" means "end element R R It means "in the area of".

[0121] In this regard, the separation element R T "In" means "separation element R T It means "in the area of".

[0122] Suitable fixing element B R and B. T are all means well known to those skilled in the art for fastening the two frame portions R1 and R2 to each other.

[0123] These fixed elements B R and B. T is in particular selected from hinges, clamps, nails, screws and hooks, preferably selected from screws and hooks, and most preferably hooks.

[0124] Fixed element B R and B. T can be made from materials well known to those skilled in the art. They preferably comprise a material selected from the group consisting of plastic, glass, wood, with plastic being particularly preferred. Even more preferably, the plastic is selected from the group consisting of polypropylene, polystyrene, polyvinyl chloride, PVC-C.

[0125] Even more preferably, at least one fixing element B R and at least one fixed element B T are mutually engaging hooks B H In the mutually fixed state, these hooks in particular straddle the partition wall W.

[0126] For this purpose, B T As a pair of hooks B facing each other, H However, advantageously, the separating element R T on the mutually facing sides of the two frame parts R1 and R2, respectively, which preferably reversibly engage with each other depending on the arrangement of the ASC between the frame parts R1 and R2. R Surface O KK and O A / MK It is clear that the material must be directly accessible from the

[0127] For this purpose, B R As a pair of hooks B facing each other, H but advantageously, the end element R R are formed on the mutually facing sides of the two frame parts R1 and R2, respectively, which reversibly engage with each other depending on the arrangement of the ASC between the frame parts R1 and R2.

[0128] "The mutually facing sides of the two frame parts R1 and R2" means, in the case of R1, that face is face O KK In the case of R2, the side of the frame part that is not directly contactable from the surface O A / MK These are in particular the faces R1 and R2 which abut the ASC and / or the seal Di in the partition wall W.

[0129] Fixing means B R and B. T , and in particular the hook, is preferably integral with at least one of the parts R1 and R2 (FIG. 3B).

[0130] In another preferred embodiment, at least one fixing element B R and at least one fixed element B T are mutually engaging hooks B H It is in the form of:

[0131] In a preferred embodiment, hook B HThe separation element R is adapted to engage when the ASC is disposed between the frame portions R1 and R2, thereby securing the frame portions R1 and R2 to one another. T The domain and end element R R Even more preferably, this is reversible and the hook B H means that they can be detached from one another. This can be achieved, for example, by designing the hooks to be movable relative to one another.

[0132] Fixing means B R and B. T Let R be the end element R and the separation element R T Surprisingly, the stability of the partition wall W is improved by attaching it to both the end elements R. R Not only the area of ​​R but also the separation element R T By using fixing means in this area as well, it is possible to introduce compressive forces over the entire area of ​​the frame element R and not just at the outer corners.

[0133] 4.1.3 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.

[0134] 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+ , Ni 2+ 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.

[0135] The Roman numerals I, II, III, IV, and V indicate the oxidation numbers in which each metal cation exists.

[0136] 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.

[0137] 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.

[0138] In a preferred embodiment of the partition W according to the first aspect of the invention, the ASCs contained in the partition W have an identical structure.

[0139] 4.1.4 Manufacturing of Partition Wall W The partition wall W can be manufactured by methods known to those skilled in the art.

[0140] For example, the ASC contained in the partition wall W may be inserted into a suitable casting mould, optionally equipped with seals, and the frame element R may be cast with liquid plastic and then left to solidify (injection moulding method). During solidification, it surrounds the ASC. T and B. R may be provided as one casting with suitable shape on the frame element R (and form integral with the frame element R). In this embodiment, the interengaging hooks B H are particularly suitable as fastening means.

[0141] Alternatively, the frame element R, or the frame parts R1 and R2, are cast separately. T and B. R may be provided as one casting with suitable shape on the frame element R (and form integral with the frame element R). In this embodiment, the interengaging hooks B H are particularly suitable as fastening means.

[0142] Alternatively, an ASC, optionally equipped with a seal Di, can be placed between the frame parts R1 and R2, and then the fixing element B T and B. R Suitable examples for this purpose are screws or nails which are driven into suitable notches in the frame parts R1 and R2 and secure them to one another.

[0143] 4.2 Electrolyzer E The partition wall W of the first embodiment of the present invention is suitable as a partition wall of an electrolytic cell E. Thus, in a second aspect, the present invention provides a method for producing a medicament for the treatment of a cancer, comprising: - at least one entrance Z KAand at least one exit A KA and the anode electrode E A Internal structure I KA At least one anode chamber K having A , - at least one entrance Z KK and at least one exit A KK and the cathode electrode E K Internal structure I KK At least one cathode chamber K having K , and - If necessary, at least one inlet Z KM and at least one exit A KM and Internal Structure I KM At least one intermediate chamber K having M An electrolytic cell E comprising: I KA and I KM are separated from each other by a diffusion barrier D, and A KM is the connection V AM By Entrance Z KA Connected to V AM via I KM From I KA It is possible to deliver liquid to Electrolytic cell E is in intermediate chamber K M If you do not have I KA and I KK are separated from each other by a partition wall W according to the first aspect of the invention, The electrolytic cell E is provided with at least one intermediate chamber K M If it has I KK and I KM are separated from each other by a partition wall W according to the first aspect of the invention, Partition wall W <16> Alkali metal cation conducting solid electrolyte ceramics, especially the separating element R T is the surface KK Via S KK Side internal structure I KK In direct contact with Electrolytic cell E is in intermediate chamber K MIn the case where the partition wall W does not have a surface O A / MK Via S A / MK Side internal structure I KA Direct contact with The electrolytic cell E is provided with at least one intermediate chamber K M In the case where the partition wall W is provided with the above-mentioned, the alkali metal cation conductive solid electrolyte ceramics contained in the partition wall W, and in particular the frame element R, have a surface O A / MK Via S A / MK Side internal structure I KM In direct contact with the electrolytic cell E Regarding.

[0144] The electrolytic cell E in the second 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 in which the chambers are interconnected in the form of modules. Such electrolytic cells are described, for example, in DE-A 258143 and US-A 2006 / 0226022.

[0145] In a preferred embodiment, the electrolytic cell E in the second aspect of the present invention includes an anode chamber K A and cathode chamber K K And, if necessary, the intermediate room K M It is equipped with.

[0146] 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). AThe may be perforated, in particular for inlets and outlets. A At least one anode chamber K A and at least one cathode chamber K K and an intermediate chamber K with one electrolytic cell E. M In the embodiment, at least one intermediate chamber K M There is a saying.

[0147] 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

[0148] Electrolytic cell E is in intermediate chamber K M If the cathode chamber K K Internal Structure I KK The anode chamber K is separated from the anode chamber K by the partition wall W of the first embodiment of the present invention. A Internal Structure I KA The electrolytic cell E is separated from at least one intermediate chamber K M If equipped with a cathode chamber K K Internal Structure I KK The intermediate chamber K is separated by the partition wall W of the first embodiment of the present invention. M Internal Structure I KM Separated from.

[0149] 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 well known to the person skilled in the art that are stable under the conditions of the method according to the invention in the third 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 Kmay 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.

[0150] Intermediate room K M In an embodiment of the electrolytic cell E according to the second aspect of the invention, the intermediate chamber K M Anode chamber K A and cathode chamber K K It is between.

[0151] 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 As the liquid flows through the cathode electrode E K In 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 third aspect of the invention, KK This is a prerequisite for obtaining solution L1.

[0152] 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.

[0153] 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 has.

[0154] Electrolytic cell E is in intermediate chamber K M If equipped with 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 Separated from.

[0155] Electrolytic cell E is in intermediate chamber K M If the anode chamber K does not have an internal structure I KA The cathode chamber K is separated by a partition wall W. K Internal Structure I KK Separated from.

[0156] 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 A are all electrodes familiar to the skilled artisan that are stable under the conditions of the method according to the invention in the third aspect of the invention. They are in particular described in paragraph

[0024] of WO 2014 / 008410 A 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. Acomprises 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).

[0157] 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 KA In the implementation of the method according to the invention in the third aspect of the invention, KA This is a prerequisite for obtaining solution L4.

[0158] Entrance Z KA and Exit A KA The electrolytic cell E may be attached to the intermediate chamber K 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. M In certain embodiments, the inlet ZKA may also be present in the electrolytic cell, for example in the form of perforations in the diffusion barrier D.

[0159] 4.2.3 Optional intermediate chamber K M The electrolytic cell E in the second embodiment of the present invention has an intermediate chamber K M It is preferable to have an optional 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.

[0160] Electrolytic cell E is in intermediate chamber K M If equipped with 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

[0161] 4.2.3.1 Diffusion Barrier D Optional intermediate chamber 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. K Internal Structure I KK is separated from

[0162] The material used for the diffusion barrier D is stable under the conditions of the method of the present invention in the third aspect of the present invention and is suitable for use in the anode chamber K A Internal Structure I KA Protons from the liquid present in the optional intermediate chamber K M Internal Structure IKM The material may be any material that prevents or retards migration of the

[0163] 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.

[0164] 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").

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] "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. 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

[0170] 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.

[0171] The salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide. The halides are fluoride, chloride, bromide and iodide. The most preferred halide is chloride.

[0172] The anion-conducting membrane used is preferably a membrane selective for halides, preferably chloride.

[0173] 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.

[0174] 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,

[0175] 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.

[0176] 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.

[0177] 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:

[0178] 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.

[0179] 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 NAFIONIn 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.

[0180] [ka]

[0181] 4.2.3.2 Entrance Z KM and Exit A KM Optional intermediate chamber 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 will be possible to transfer the

[0182] 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.

[0183] 4.2.3.3 Connection V AM In the electrolytic cell E according to the second 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

[0184] 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.

[0185] (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 include the connection V AM The insulating layer 14 has perforations and gaps that function as a shield from the elements.

[0186] (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 K M 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 More preferably, it is at the upper end of the range.

[0187] "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.

[0188] "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.

[0189] "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.

[0190] "Anode chamber K A Exit AK at the top of A " 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.

[0191] 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

[0192] Connection V AM When is formed outside the electrolytic cell E, as shown in FIG. 5A, 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 KAand 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.

[0193] (3) Connection V AM is 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. 5B, 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

[0194] These embodiments allow the aqueous salt solution L3 to beA 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.

[0195] According to the present invention, the "bottom of the electrolytic cell E" refers to the solution (e.g., A KM 5A and 5B) 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 L2, A in Figs. 4A and 4B KA In the case of FIG. 1, L3) is the side of electrolytic cell E where water is supplied to electrolytic cell E against gravity. 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. 5A and FIG. 5B). KA In the case of L4, A KK The side of the electrolytic cell E where the solution (e.g., Z in Figures 5A and 5B) exits the electrolytic cell E against gravity, or KM In 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.

[0196] 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 frame element R, and the alkali metal cation conductive solid electrolyte ceramic contained in the partition wall W and the frame element R are preferably in contact with each other at the surface O. KK Through side S KK Internal Structure I KK The electrolytic cell E is disposed so as to be in direct contact with the

[0197] This is the side S KK Side internal structure I KK When the liquid is completely filled with the liquid L4, the liquid L4 flows to 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 via part R1 and preferably also with the frame element R via part R1. Therefore, ions (e.g. alkali metal ions such as sodium, lithium, etc.) from all the ASC contained in the partition W can enter the solution L4.

[0198] Furthermore, the partition wall W separates the electrolytic cell E from the intermediate chamber K M In the embodiment not including the above, the alkali metal cation conductive solid electrolyte ceramics contained in the partition wall W and preferably the frame element R are preferably 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

[0199] This means that the electrolytic cell E is connected to the intermediate chamber K M In an embodiment not including the anode chamber K, the partition wall W is A Internal Structure I KA 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 KA When the liquid is completely filled with the liquid L3, the liquid L3 flows over the surface O A / MK and preferably also through part R2, with respect to frame element R, so that ions from solution L3 (e.g., alkali metal ions such as sodium, lithium, etc.) can enter all the ASC contained in partition wall W.

[0200] Furthermore, the electrolytic cell E is provided with at least one intermediate chamber K M In the case where the partition wall W is provided with the above-mentioned, the alkali metal cation conductive solid electrolyte ceramics contained in the partition wall W and, in particular, the frame element R are in contact with each other at the surface O. A / MK Through side S A / MK Internal Structure I KM The electrolytic cell E is placed in direct contact with the

[0201] This means that the electrolytic cell E is connected to at least one intermediate chamber K M In the embodiment, the partition wall W is 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 OA / MK and preferably also through part R2, with respect to frame element R, so that ions from solution L3 (e.g., alkali metal ions such as sodium, lithium, etc.) can enter all the ASC contained in partition wall W.

[0202] In a preferred embodiment of the electrolytic cell E in the second 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.

[0203] In a preferred embodiment of the electrolytic cell E without an intermediate chamber according to the second 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 KA is in contact with.

[0204] In a preferred embodiment of the electrolytic cell E with at least one intermediate chamber according to the second 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.

[0205] 4.3 The method according to the invention In a third 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 third aspect of the present invention is carried out in an electrolytic cell E according to the second aspect of the present invention.

[0206] X is preferably Li + , K + , Na + More preferably, the group consisting of K + , Na+ Most preferably, X=Na + It is.

[0207] 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.

[0208] 4.3.1 Intermediate room K M The method according to the invention in an electrolytic cell E not provided with Electrolytic cell E is in intermediate chamber K M When the above-mentioned step (α1), step (α2), and step (α3) are performed simultaneously.

[0209] 4.3.1.1 Process (α1) In step (α1), 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 4.3.1.2 Process (α2) In step (α2), a neutral or alkaline aqueous solution L3 of a salt S containing X as a cation is added to K A is sent through.

[0214] The salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.

[0215] The halides are fluoride, chloride, bromide and iodide. The most preferred halide is chloride.

[0216] 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.

[0217] 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.

[0218] 4.3.1.3 Process (α3) Next, in step (α3), E A and E K A voltage is applied between the

[0219] 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.

[0220] 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 higher concentration of S than L3 is at outlet A. KA is obtained.

[0221] In step (α3) of the method according to the third aspect of the invention, in particular the current density (= anode chamber K A 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 anode chamber K such that a current flows such that A The 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.

[0222] Step (α3) of the method according to the third aspect of the invention is to align the partition wall W and the frame element R in the chamber K so that both L3 and L2 are in contact with the ASC contained in the partition wall W and in particular also in contact with the frame element R. 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.

[0223] In step (α3), E A and E K The fact that charge transfer occurs between K K and K. A L2 and L3 are simultaneously applied to the electrode E so that they complete a circuit. A and EK It means to cover.

[0224] This is especially true when the liquid flow of L3 is 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

[0225] In a further preferred embodiment, the method according to the third aspect of the invention is carried out continuously, i.e. steps (α1) and (α2) are carried out continuously whilst applying a voltage according to step (α3).

[0226] After step (α3) is performed, the solution L1 is discharged to the outlet A KK and 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%.

[0227] The aqueous solution L4 of S, whose S concentration is lower than L3, is at outlet A. KA is obtained.

[0228] 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.

[0229] More specifically, steps (α1) to (α3) of the method according to the third 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.

[0230] In the course of carrying out the steps (α1) to (α3) according to the third 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 KK may 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.

[0231] 4.3.2 Intermediate room K M The method according to the invention in an electrolytic cell E equipped with The electrolytic cell E is provided with at least one intermediate chamber K M In the case of the above, steps (β1), (β2), and (β3) are carried out simultaneously.

[0232] The electrolytic cell E has at least one intermediate chamber K M and then, it is preferable to carry out steps (β1), (β2), and (β3) which proceed simultaneously.

[0233] 4.3.2.1 Process (β1) In step (β1), a solution L2 containing an alcohol ROH, preferably an alkali metal alkoxide XOR and an alcohol ROH, is K is sent through.

[0234] 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.

[0235] 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.

[0236] If the solution L2 contains XOR, the mass ratio of XOR to alcohol ROH in the 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.

[0237] 4.3.2.2 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 through, then V AM Then through K A is sent through.

[0238] The salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.

[0239] The halides are fluoride, chloride, bromide and iodide, with the most preferred halide being chloride.

[0240] 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.

[0241] The mass proportion of salt S in solution L3 is preferably in the range of 0% to more than 20% by weight, more preferably 1% to 20% by weight, more preferably 5% to 20% by weight, even more preferably 10% to 20% by weight, and most preferably 20% by weight, relative to the entire solution L3.

[0242] 4.3.2.3 Process (β3) Next, in step (β3), E A and E K A voltage is applied between the

[0243] 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.

[0244] 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 higher concentration of S than L3 is at outlet A. KA is obtained.

[0245] In step (β3) of the method according to the third 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 thatM The 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.

[0246] Step (β3) of the method according to the third aspect of the invention is to separate the two chambers K so that L3 and L2 are both in contact with the solid electrolyte contained in the partition wall W and in particular also in contact with the frame element R. 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.

[0247] In step (β3), E A and E K The fact that charge transfer occurs between K K , K M and K. A L2 and L3 are simultaneously loaded to the electrode E so that the circuit is completed. A and E K It means to cover.

[0248] 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 of L3 passes through 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

[0249] In a further preferred embodiment, the method according to the third 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).

[0250] 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%.

[0251] The aqueous solution L4 of S, whose S concentration is lower than L3, is at outlet A. KA is obtained.

[0252] 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.

[0253] More specifically, steps (β1) to (β3) of the method according to the third 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.

[0254] In the course of carrying out the steps (β1) to (β3) according to the third 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.

[0255] 4.3.2.4 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]

[0256] [Figure 1] (A) shows an inventive electrolytic cell E. (B) shows another inventive electrolytic cell E. [Diagram 2] (A) Partition wall W of the present invention <16> (B) Partition wall W of the present invention <16> 1 shows another embodiment of the present invention. [Diagram 3] (A) Above the continuous dotted line, partition wall W <16> End element RR <20> The cross section QRR shown in FIG. 2A and FIG. 2B in the region <165> A detailed view of the partition wall W is shown below the continuous dotted line. <16> Separation element RT <17> The cross section QRT shown in Figures 2A and 2B in the region of <166> (B) A detailed view of the two cross sections QRR. <165> and Q.R.T. <166> (C) Cross section QRR. <165> 1 shows a further embodiment of the [Figure 4](A) Electrolytic cell E according to the second aspect of the invention <1> (B) Electrolytic cell E according to the second aspect of the present invention. <1> Shows. [Diagram 5] (A) Electrolytic cell E1 according to a second embodiment of the invention. (B) Electrolytic cell E1 according to a second embodiment of the invention. [Figure 6] (A) Partition wall W of the present invention <16> Further embodiments of the surface OKK (on the left) <163> Side with SKK <161> (B) A top view of the partition wall W of the present invention; and (C) a side view showing the details of the curved clamp as viewed in the direction of the arrow. <16> 1 shows a further embodiment of the EXAMPLES

[0257] 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 (water) 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.

[0258] 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.

[0259] 5.2 Comparative Example 2 Comparative Example 1 was reproduced in a two-compartment 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.

[0260] 5.3 Example 1 Comparative Example 1 was reproduced using an electrolytic cell according to FIG. 5A, in which a partition containing two NaSICON ceramics was inserted into a frame and fixed with screws.

[0261] 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.

[0262] 5.4 Comparative Example 3 Comparative Example 2 was carried out using an electrolytic cell according to FIG. 5B in which a partition containing four NaSICON ceramics was inserted into a frame and fixed with hooks as shown in FIG. 7A. However, the difference is that the fixed element B T <92> (Cross-section of Fig. 5B <166> ) has been omitted.

[0263] This arrangement reduced the extent of the expansion and contraction processes, which contributed to the service life of the ceramic, and also resulted in a cleaner product solution, since leakage was prevented. However, the frame R was not able to accommodate the separating element R. T It is observed that the partition wall W is easily sagging in this region, and therefore the stability of the partition wall W is low in this region.

[0264] 5.5 Example 2 Separation element R T Fixed element B in the area T <92> (interlocking hooks) were installed to replicate Comparative Example 3. This spread the compressive force across the entire surface of each side of the partition, improving the stability of the partition.

[0265] 5.6 Results During the expansion and contraction processes caused by repeated electrolysis cycles, the tension in the solid electrolyte ceramic is relieved, which leads to an increase in the life of the electrolysis chamber. The implementation of the present invention according to Examples 1 and 2 reduces these effects and increases the stability of the solid electrolyte. Furthermore, in comparison with Comparative Example 3, the separation element R T Fixed element B in the area T By providing this, the compressive force applied from the frame element to the ceramics within the partition wall is distributed evenly, thereby increasing the stability of the partition wall W. 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 according to the invention with at least one intermediate chamber and of the process carried out therein.

[0266] JPEG2024527770000002.jpg247170

Claims

1. Surface O ＫＫ One side S having <163> ＫＫ <161> and the side S ＫＫ The surface O, which is the side opposite to <161> Ａ／ＭＫ The side S having <164> Ａ／ＭＫ Including <162> Two opposing portions R １ <201> and R ２ It is composed of <202>, and at least two alkali metal cation-conductive solid electrolyte ceramics F Ａ <18> and F Ｂ Frame element R<2> in which <19> is arranged A partition wall W<16> including The aforesaid R １ <201> can be in direct contact with the aforesaid surface O ＫＫ <163> Said R ２ <202> can be in direct contact with said surface O Ａ／ＭＫ <164>, and The frame element R<2> is the end element R Ｒ <20> and the separation element R Ｔ <17> to form the end element R Ｒ <20> is the surface O ＫＫ <163> and O Ａ／ＭＫ <164> at least partially bounds, and The separation element R Ｔ <17> is located between the alkali metal cation conductive solid electrolyte ceramics included in the partition wall W<16> and separates them from each other, The alkali metal cation-conductive solid electrolyte ceramics contained in the partition wall W<16> are directly accessible from both the surface O ＫＫ <163> and the surface O Ａ／ＭＫ <164>. ＫＫ <163> and the surface O Ａ／ＭＫ <164> are both directly accessible, said R １ <201> and R ２ <202> is the end element R Ｒ <20> has at least one fixing element B Ｒ <91> are fixed to each other, and Said R １ <201> and R ２ <202> are the partition wall W<16> which are fixed to each other by at least one fixing element B Ｔ <17> in the separation element R Ｔ <92>.

2. the at least one fixing element B Ｒ <91> and the at least one fixing element B Ｔ <92> is the portion R １ <201> and R ２ The partition wall W<16> according to claim 1, which is integrally formed with at least one of <201> and <202>.

3. said at least one fixing element B Ｒ <91> and said at least one fixing element B Ｔ <92> each have hooks B engaging with each other Ｈ Partition wall W<16> according to claim 1, which has the shape of <93>.

4. At least four alkali metal cation-conductive solid electrolyte ceramics F Ａ <18>, F Ｂ <19>, F Ｃ <28> and F Ｄ The partition wall W<16> according to claim 1, comprising <29>.

5. the separation element R Ｔ The partition wall W<16> according to claim 4, <17> is in a cross shape or a lattice shape.

6. The partition wall W<16> according to claim 1, wherein the frame element R<2> includes a material selected from the group consisting of plastic, glass, and wood.

7. The alkali metal cation-conductive solid electrolyte ceramics contained 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 (wherein, M Ｉ is selected from Na ＋ and Li ＋ and is selected from M ＩＩ is a divalent metal cation, M ＩＩＩ is a trivalent metal cation, M Ｖ is a pentavalent metal cation, The Roman numeral indices I, II, III, IV, V indicate the oxidation number in which each of the metal cations is present. w, x, y, z are real numbers, where 0 ≦ x < 2, 0 ≦ y < 2, 0 ≦ w < 2, 0 ≦ z < 3. w, x, y, z are selected such that 1 + 2w + x - y + z ≧ 0 and 2 - w - x - y ≧ 0. ) The partition wall W<16> according to claim 1, having the structure of

8. - 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>, - At least one inlet Z ＫＫ <120>, and at least one outlet A ＫＫ <121>, and a cathode electrode E Ｋ <123>, an internal structure I including ＫＫ <122>, and having at least one cathode chamber K Ｋ <12>, and - At least one inlet Z as necessary 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> An electrolytic cell E<1> including the aforementioned I ＫＡ <112> and the aforementioned I ＫＭ <132> are separated from each other by a diffusion barrier D<14>, and the A ＫＭ <131> is a connection V ＡＭ <15> connects to the aforementioned inlet Z ＫＡ <110>, and the connection V ＡＭ <15> via which the I ＫＭ from <132> to the I ＫＡ <112> can send liquid, When the electrolytic cell E<1> does not include the intermediate chamber K<13>, the I<112> and the I<122> are separated from each other by the partition wall W<16> described in claim 1. Ｍ <13>, the I<112> and the I<122> are separated from each other by the partition wall W<16> described in claim 1. ＫＡ <112> and the I<122> are separated from each other by the partition wall W<16> described in claim 1. ＫＫ <122> are separated from each other by the partition wall W<16> described in claim 1. when the electrolytic cell E<1> includes at least one of the intermediate chambers K<13>, Ｍ <122> and <132> are separated from each other by the partition wall W<16> according to claim 1, ＫＫ <122> and <132> ＫＭ when the electrolytic cell E<1> includes at least one of the intermediate chambers K<13>, The alkali metal cation-conductive solid electrolyte ceramics contained in the partition wall W<16> are in direct contact with the internal structure I<122> on the S<166> side through the surface O<163> and ＫＫ <163> ＫＫ <166> ＫＫ <122> and The electrolytic cell E<1> is in the intermediate chamber K Ｍ When the partition wall W<13> is not provided, the alkali metal cation conductive solid electrolyte ceramics included in the partition wall W<16> has a surface O Ａ／ＭＫ <164> through the S Ａ／ＭＫ The inner structure I on the <162> side ＫＡ Direct contact with <112> When the electrolytic cell E<1> includes at least one of the intermediate chambers K<13>, the alkali metal cation-conductive solid electrolyte ceramics included in the partition wall W<16> are in direct contact with the internal structure I<132> on the S<162> side through the surface O<164>. Electrolytic cell E<1>. Ｍ <13>, when included, the alkali metal cation-conductive solid electrolyte ceramics included in the partition wall W<16> are the S Ａ／ＭＫ <164> via the Ａ／ＭＫ <162>-side internal structure I ＫＭ <132>, electrolytic cell E<1>.

9. the intermediate chamber K Ｍ The electrolytic cell E<1> according to claim 8, which does not include <13>.

10. At least one of said intermediate chambers K Ｍ The electrolytic cell E<1> according to claim 8, comprising <13>.

11. The connection V ＡＭ <15> is the electrolytic cell E<1> according to claim 10, which is formed inside the electrolytic cell E<1>.

12. An alcohol ROH solution L of an alkali metal alkoxide XOR １ A method for generating <21>, Wherein X is an alkali metal cation and R is an alkyl group having 1 to 4 carbon atoms. Solution L containing the alcohol ROH (α) ２ Pass <22> through the K Ｋ Step (α1) of passing through <12>, a neutral or alkaline aqueous solution L of a salt S containing X as a cation ３ Pass <23> through the K Ａ Step of passing through <11>, the E Ａ Between <113> and the E Ｋ Simultaneously carry out the step of applying a voltage (α3) between <123> and carry out them in the electrolytic cell E1 according to claim 9, or (β) Solution L containing the alcohol ROH ２ <22> is passed through the K Ｋ Step (β1) of passing through <12>, 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>, then passed through the V ＡＭ <15>, then passed through the K Ａ Step (β2) of passing through <11>, the E Ａ Between <113> and the E Ｋ Step (β3) of applying a voltage between <123> is carried out simultaneously, and they are carried out in the electrolytic cell E1 according to claim 10, As a result, the outlet A ＫＫ In <121>, the solution L ２ <21> with an XOR concentration higher than that of <22> is obtained, and １ <21> is obtained, and the said outlet A ＫＡ In <111>, the said L ３ aqueous solution L with an S concentration lower than <23> ４ <24> is obtained, method.

13. Wherein X is Li ＋ , Na ＋ , K ＋ The method according to claim 12, selected from the group consisting of

14. The method according to claim 12, wherein S is a halide, sulfate, sulfite, nitrate, bicarbonate, or carbonate of X.

15. The method according to claim 12, wherein R is selected from the group consisting of methyl and ethyl.

Images