WO2023274796A1 - Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins - Google Patents

Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins Download PDF

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Publication number
WO2023274796A1
WO2023274796A1 PCT/EP2022/066943 EP2022066943W WO2023274796A1 WO 2023274796 A1 WO2023274796 A1 WO 2023274796A1 EP 2022066943 W EP2022066943 W EP 2022066943W WO 2023274796 A1 WO2023274796 A1 WO 2023274796A1
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Prior art keywords
chamber
electrolytic cell
solution
internals
cation
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PCT/EP2022/066943
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German (de)
English (en)
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Philip Heinrich REINSBERG
Michael Horn
Jörn Klaus Erich WOLF
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Evonik Functional Solutions Gmbh
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Priority to KR1020237045183A priority Critical patent/KR20240023533A/ko
Priority to CN202280046253.5A priority patent/CN117580977A/zh
Priority to EP22735407.3A priority patent/EP4363639A1/fr
Publication of WO2023274796A1 publication Critical patent/WO2023274796A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
    • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/13—Single electrolytic cells with circulation of an electrolyte
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms

Definitions

  • the present invention relates to an electrolytic cell which has three chambers, the middle chamber being separated from the cathode chamber by a solid electrolyte which is permeable to cations, for example NaSICON, and from the anode chamber by a diffusion barrier.
  • the invention is characterized in that the middle chamber comprises internals.
  • the electrolytic cell according to the invention solves the problem that a concentration gradient forms in the middle chamber of the electrolytic cell during electrolysis, which leads to locally reduced pH values and thus to damage to the solid electrolyte.
  • the internals cause the electrolyte solution to be swirled as it flows through the central chamber during the electrolysis, which prevents the formation of a pH gradient.
  • the present invention relates to a method for producing an alkali metal alkoxide solution in the electrolytic cell according to the invention.
  • the electrochemical production of alkali metal alkoxide solutions is an important industrial process which is described, for example, in DE 10360758 A1, US 2006/0226022 A1 and WO 2005/059205 A1.
  • the principle of this process is reflected in an electrolytic cell, in the anode chamber of which there is a solution of an alkali salt, for example common salt or NaOH, and in the cathode chamber of which the alcohol in question or a low-concentration alcoholic solution of the alkali metal alcoholate in question, for example sodium methoxide or sodium ethoxide, is located.
  • the cathode compartment and the anode compartment are separated by a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
  • a ceramic which conducts the alkali metal ion used, for example NaSICON or an analog for potassium or lithium.
  • chlorine is formed at the anode - if a chloride salt of the alkali metal is used - and hydrogen and alcohol ions are formed at the cathode.
  • the charge is equalized by the alkali metal ions migrating from the middle chamber into the cathode chamber via the ceramic that is selective for them.
  • the charge equalization between the middle chamber and the anode chamber takes place through the migration of cations when using cation exchange membranes or the migration of anions when using anion exchange membranes or through the migration of both types of ions when using non-specific diffusion barriers.
  • WO 2014/008410 A1 describes an electrolytic process for the production of elemental titanium or rare earths. This process is based on the fact that titanium chloride is formed from TiO2 and the corresponding acid, this reacts with sodium alcoholate to form titanium alcoholate and NaCl and is finally electrolytically converted to elementary titanium and sodium alcoholate.
  • WO 2007/082092 A2 and WO 2009/059315 A1 describe processes for the production of biodiesel in which triglycerides are first converted into the corresponding alkali metal triglycerides with the aid of alcoholates electrolytically produced via NaSICON and in a second step with electrolytically produced protons to form glycerol and the respective alkali metal hydroxide be implemented. Accordingly, methods are described in the prior art which are carried out in electrolytic cells with an ion-permeable layer, such as, for example, NaSiCON solid electrolytes. However, these solid electrolytes typically have the disadvantage that they are not long-term stable to aqueous acids.
  • the cathode chamber and the middle chamber of the cell are separated by a cation-permeable solid electrolyte such as NaSICON.
  • the middle chamber is supplied with solution from the cathode chamber, for example.
  • US 2010/0044242 A1 also describes in Figure 6 that solution from the middle chamber can be mixed with solution from the anode chamber outside the chamber in order to obtain sodium hypochlorite.
  • Such cells have also been proposed in the prior art for the production or purification of alkali metal alkoxides.
  • 5,389,211 A describes a process for purifying alkoxide solutions in which a three-chamber cell is used, in which the chambers are separated from one another by cation-selective solid electrolytes or non-ionic partitions. The middle chamber is used as a buffer chamber to prevent the cleaned Alkoxide or hydroxide solution from the cathode compartment mixes with the contaminated solution from the anode compartment.
  • DE 4233191 A1 describes the electrolytic production of alkoxides from salts and alkoxides in multi-chamber cells and stacks of several cells.
  • WO 2008/076327 A1 describes a process for preparing alkali metal alkoxides.
  • a three-chamber cell is used, the middle chamber of which is filled with alkali metal alkoxide (see, for example, paragraphs [0008] and [0067] of WO 2008/076327 A1).
  • WO 2009/073062 A1 A similar arrangement is described in WO 2009/073062 A1. However, this arrangement has the disadvantage that the alkali metal alkoxide solution is the desired product, but this is consumed as a buffer solution and is continuously contaminated.
  • the drop in pH is particularly critical in the middle chamber, as this is bounded by the ion-conducting ceramic. Gases are usually formed at the anode and the cathode, so that there is at least a certain degree of mixing in these chambers. On the other hand, such mixing does not take place in the middle chamber, so that the pH gradient develops in it. This undesirable effect is amplified by the fact that the brine is generally pumped relatively slowly through the electrolytic cell.
  • the object of the present invention was therefore to provide an improved process for the electrolytic production of alkali metal alkoxide and an electrolysis chamber which is particularly suitable for such a process.
  • the electrolytic cell E ⁇ 100> comprises at least one anode chamber K A ⁇ 101>, at least one cathode chamber K K ⁇ 102> and at least one intermediate chamber K M ⁇ 103>, where K A ⁇ 101> is an anodic Electrode E A ⁇ 104> and an outlet A KA ⁇ 106>, where K K ⁇ 102> comprises a cathodic electrode EK ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>, where K M ⁇ 103> comprises an inlet Z KM ⁇ 108>, is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and is separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>, where K M ⁇ 103> and K A ⁇ 101> are connected to each other by a connection V AM ⁇ 112>, through which liquid can be conducted from K M ⁇ 103> to K A ⁇ 101
  • the present invention relates to a method for producing a solution L 1 ⁇ 115> of an alkali metal alcoholate XOR in the alcohol ROH in an electrolytic cell E ⁇ 100> according to the first aspect of the invention, the method comprising the following steps (a ), (b) and (c) comprises: (a) a solution L 2 ⁇ 113> comprising the alcohol ROH is passed through K K ⁇ 102>, (b) a neutral or alkaline aqueous solution L 3 ⁇ 114> of a Salt S comprising X as cation is passed through K M , then through V AM , then through K A ⁇ 101>, (c) voltage is applied between E A ⁇ 104> and E K ⁇ 105>, resulting in A KK ⁇ 109> the solution L 1 ⁇ 115> is obtained, the concentration of XOR in L 1 ⁇ 115> being higher than that in L 2 ⁇ 113>, and whereby at the outlet A KA ⁇ 106> an aqueous solution L 4 ⁇
  • FIG. 1 shows a preferred embodiment of an electrolytic cell ⁇ 100> according to the invention and of the method according to the invention.
  • the three-chamber cell E ⁇ 100> comprises a cathode chamber K K ⁇ 102>, an anode chamber K A ⁇ 101> and a middle chamber K M ⁇ 103> lying between them.
  • the cathode chamber K K ⁇ 102> comprises a cathodic electrode EK ⁇ 105>, an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>.
  • Anode chamber K A ⁇ 101> comprises an anodic electrode E A ⁇ 104> and drain A KA ⁇ 106> and is connected to middle chamber K M ⁇ 103> via connection V AM ⁇ 112>.
  • the middle chamber K M ⁇ 103> includes an inlet Z KM ⁇ 108>.
  • the three chambers are delimited by an outer wall ⁇ 117> of the three-chamber cell E ⁇ 100>.
  • the cathode chamber K K ⁇ 102> is also separated from the middle chamber K M ⁇ 103> by a NaSICON solid electrolyte F K ⁇ 111> that is selectively permeable for sodium ions.
  • the middle chamber K M ⁇ 103> is additionally in turn separated from the anode chamber K A ⁇ 101> by a diffusion barrier D ⁇ 110>.
  • the NaSICON solid electrolyte F K ⁇ 111> and the diffusion barrier D ⁇ 110> extend over the entire depth and height of the three-chamber cell E ⁇ 100>.
  • the diffusion barrier D ⁇ 110> is made of glass.
  • the connection V AM ⁇ 112> is formed outside the electrolytic cell E ⁇ 100>, in particular by a tube or hose, the material of which can be selected from rubber, metal or plastic.
  • liquid can be conducted from the central chamber K M ⁇ 103> into the anode chamber K A ⁇ 101> outside the outer wall WA ⁇ 117> of the three-chamber cell E ⁇ 100>.
  • connection V AM ⁇ 112> connects an outlet A KM ⁇ 118>, which breaks through the outer wall WA ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the central chamber K M ⁇ 103>, with an inlet Z KA ⁇ 119>, which breaks through the outer wall W A ⁇ 117> of the electrolytic cell E ⁇ 100> at the bottom of the anode chamber K A ⁇ 101>.
  • An aqueous solution of sodium chloride L 3 ⁇ 114> with a pH of 10.5 is added via the inlet Z KM ⁇ 108> in the same direction as gravity into the middle chamber KM ⁇ 103>.
  • connection V AM ⁇ 112> which is formed between an outlet A KM ⁇ 118> of the middle chamber K M ⁇ 103> and an inlet Z KA ⁇ 119> of the anode chamber KA ⁇ 101>, forms the middle chamber K M ⁇ 103 > connected to the anode chamber K A ⁇ 101>.
  • Sodium chloride solution L 3 ⁇ 114> is conducted through this connection V AM ⁇ 112> from the middle chamber KM ⁇ 103> into the anode chamber KA ⁇ 101>.
  • a solution of sodium methoxide in methanol L2 ⁇ 113> is fed into the cathode chamber K K ⁇ 102> via the inlet Z KK ⁇ 107>.
  • a voltage is applied between the cathodic electrode E K ⁇ 105> and the anodic electrode EA ⁇ 104>.
  • methanol im Electrolyte L2 ⁇ 113> reduced to methoxide and H2 (CH 3 OH + e- ⁇ CH 3 O- + 1 ⁇ 2 H2).
  • Sodium ions diffuse from the middle chamber K M ⁇ 103> through the NaSICON solid electrolyte F K ⁇ 111> into the cathode chamber K K ⁇ 102>.
  • Chlorine gas Cl2 forms hypochlorous acid and hydrochloric acid in water according to the reaction Cl2 + H2O ⁇ HOCl + HCl, which react acidically with other water molecules.
  • the acidity damages the NaSICON solid electrolyte ⁇ 111>, but is limited by the arrangement according to the invention in the anode chamber K A ⁇ 101> and is thus kept away from the NaSICON solid electrolyte F K ⁇ 111> in the electrolytic cell E ⁇ 100>. This increases its lifespan considerably.
  • the middle chamber K M ⁇ 103> there are also fixtures ⁇ 120> in the form of a net-like wire basket ⁇ 122> which contains glass or plastic balls ⁇ 121>.
  • the wire basket ⁇ 122> is placed loosely in the middle chamber ⁇ 103 >, but can also be attached to the inside of the outer wall of ⁇ 117>.
  • the aqueous solution L 3 ⁇ 114> fed in through the inlet Z KM ⁇ 108> is guided through these internals ⁇ 120>, as a result of which turbulence and turbulence occur.
  • These turbulences in the solution L 3 ⁇ 114> prevent a pH gradient building up in the central chamber K M ⁇ 103> as the electrolysis progresses and thus prevent the formation of a low pH value in the area immediately adjacent to the NaSICON solid electrolyte ⁇ 111> Solution. This further increases the durability of the NaSICON solid electrolyte ⁇ 111>.
  • connection V AM ⁇ 112> from the central chamber K M ⁇ 103> to the anode chamber K A ⁇ 101> is formed by a perforation in the diffusion barrier D ⁇ 110>.
  • wire basket ⁇ 122> loosely located in the middle chamber K M ⁇ 103> several pins made of glass or plastic ⁇ 123-2> are attached to the NaSICON solid electrolyte FK ⁇ 111> as internals ⁇ 120>, which can be inserted into the middle chamber K M ⁇ 103> protrude.
  • Electrolytic cell E The first aspect of the invention relates to an electrolytic cell E ⁇ 100>.
  • the electrolytic cell E ⁇ 100> comprises at least one anode chamber KA ⁇ 101>, at least one cathode chamber KK ⁇ 102> and at least one intermediate chamber KM ⁇ 103>.
  • This also includes electrolytic cells E ⁇ 100>, which have more than one anode chamber KA ⁇ 101> and/or cathode chamber KK ⁇ 102> and/or middle chamber KM ⁇ 103>.
  • electrolytic cells in which these chambers are joined together in a modular manner, are described, for example, in DD 258143 A3 and US 2006/0226022 A1.
  • the anode chamber K A ⁇ 101> includes an anodic electrode E A ⁇ 104>.
  • anodic electrode E A ⁇ 104> Any electrode familiar to a person skilled in the art that is stable under the conditions of the method according to the second aspect of the invention can be used as such an anodic electrode E A ⁇ 104>. Such are described in particular in WO 2014/008410 A1, paragraph [024] or DE 10360758 A1, paragraph [031].
  • This electrode E A ⁇ 104> can consist of one layer or of several planar layers parallel to one another, each of which can be perforated or expanded.
  • the anodic electrode E A ⁇ 104> comprises in particular a material selected from the group consisting of ruthenium oxide, iridium oxide, nickel, cobalt, nickel tungstate, nickel titanate, noble metals such as platinum in particular, which is deposited on a carrier such as titanium or Kovar ® (an iron /nickel/cobalt alloy, in which the individual proportions are preferably as follows: 54% by mass iron, 29% by mass nickel, 17% by mass cobalt).
  • Other possible anode materials are, in particular, stainless steel, lead, graphite, tungsten carbide, titanium diboride.
  • the anodic electrode E A ⁇ 104> preferably comprises a titanium anode (RuO2+IrO2/Ti) coated with ruthenium oxide/iridium oxide.
  • the cathode chamber K K ⁇ 102> includes a cathodic electrode E K ⁇ 105>. Any electrode familiar to a person skilled in the art that is stable under the conditions can be used as such a cathodic electrode E K ⁇ 105>. Such are described in particular in WO 2014/008410 A1, paragraph [025] or DE 10360758 A1, paragraph [030].
  • This electrode EK ⁇ 105> can be selected from the group consisting of mesh wool, three-dimensional matrix structure or "spheres".
  • the cathodic electrode E K ⁇ 105> comprises in particular a material selected from the group consisting of steel, nickel, copper, platinum, platinized metals, palladium, palladium supported on carbon, titanium.
  • EK ⁇ 105> preferably comprises nickel.
  • the at least one middle chamber K M ⁇ 103> is located between the anode chamber K A ⁇ 101> and the cathode chamber K K ⁇ 102>.
  • the electrolytic cell E ⁇ 100> usually has an outer wall W A ⁇ 117>.
  • the outer wall W A ⁇ 117> is in particular made of a material which is selected from the group consisting of steel, preferably rubberized steel, plastic, which is in particular made of Telene ® (thermosetting polydicyclopentadiene), PVC (polyvinyl chloride), PVC-C (post-chlorinated polyvinyl chloride), PVDF (polyvinylidene fluoride) is selected.
  • W A ⁇ 117> can be perforated in particular for inlets and outlets.
  • the at least one anode chamber K A ⁇ 101>, the at least one cathode chamber K K ⁇ 102> and the at least one intermediate chamber K M ⁇ 103> are then located within W A ⁇ 117>.
  • K M ⁇ 103> is separated from K A ⁇ 101> by a diffusion barrier D ⁇ 110> and separated from K K ⁇ 102> by an alkali cation-conducting solid electrolyte F K ⁇ 111>.
  • Any material which is stable under the conditions of the method according to the second aspect of the invention and which prevents the transfer of protons from the liquid in the anode chamber K A ⁇ 101> into the middle chamber K M can be used for the diffusion barrier D ⁇ 110> ⁇ 103> prevented or slowed down.
  • a non-ion-specific dividing wall or a membrane permeable to specific ions is used as the diffusion barrier D ⁇ 110>.
  • the diffusion barrier D ⁇ 110> is preferably a non-ion-specific partition.
  • the material of the non-ion-specific partition wall is in particular selected from the group consisting of fabric, in particular textile fabric or metal fabric, glass, in particular sintered glass or glass frits, ceramic, in particular ceramic frits, membrane diaphragms, and is selected particularly preferably glass.
  • the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”, this means according to the invention that the respective membrane favors the diffusion of certain ions through it compared to other ions.
  • membranes are meant that favor the diffusion through them of ions of a certain type of charge compared to oppositely charged ions. More preferably, specific ion permeable membranes also favor the diffusion of certain ions having one charge type through them over other ions of the same charge type.
  • the diffusion barrier D ⁇ 110> is a “membrane permeable to specific ions”
  • the diffusion barrier D ⁇ 110> is in particular an anion-conducting membrane or a cation-conducting membrane.
  • anion-conducting membranes are those which selectively conduct anions, preferably selectively specific anions. In other words, they favor the diffusion of anions through them over that of cations, especially protons, more preferably they additionally favor the diffusion of certain anions through them over the diffusion of other anions through them.
  • cation-conducting membranes are those which selectively conduct cations, preferably selectively specific cations.
  • “Favour the diffusion of certain ions X compared to the diffusion of other ions Y” means in particular that the diffusion coefficient (unit m 2 /s) of the ion species X at a given temperature for the membrane in question is higher by a factor of 10, preferably 100, preferably 1000 as the diffusion coefficient of the ionic species Y for the membrane in question.
  • the diffusion barrier D ⁇ 110> is a "membrane that is permeable to specific ions" it is preferably an anion-conducting membrane, because this is particularly good at preventing the diffusion of protons from the anode chamber KA ⁇ 101> into the middle chamber KM ⁇ 103>.
  • a membrane which is selective for the anions comprised by the salt S is used as the anion-conducting membrane.
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • a membrane selective for halides, more preferably chloride, is preferably used as the anion-conducting membrane.
  • Anion-conducting membranes are, for example, by MA Hickner, AM Herring, EB Coughlin, Journal of Polymer Science, Part B: Polymer Physics 2013, 51, 1727-1735, by CG Arges, V. Ramani, PN Pintauro, Electrochemical Society Interface 2010, 19, 31-35, in WO 2007/048712 A2 and on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003).
  • the diffusion barrier D ⁇ 110> is a cation-conducting membrane, it is in particular a membrane that is selective for the cations comprised by the salt S. Even more preferably, the diffusion barrier D ⁇ 110> is an alkali cation-conducting membrane, even more preferably a potassium and/or sodium ion-conducting membrane, most preferably a sodium ion-conducting membrane.
  • Cation-conducting membranes are described, for example, on page 181 of the textbook by Volkmar M. Schmidt Electrochemical Process Engineering: Fundamentals, Reaction Engineering, Process Optimization, 1st edition (October 8, 2003). Accordingly, organic polymers, which are selected in particular from polyethylene, polybenzimidazoles, polyetherketones, polystyrene, polypropylene or fluorinated membranes such as polyperfluoroethylene, preferably polystyrene, polyperfluoroethylene, are even more preferably used as the cation-conducting membrane, with these covalently bonded functional groups selected from -SO 3 - , -COO-, -PO 3 2- , -PO 2 H-, preferably -SO 3 -, (described in DE 102010062804 A1, US Pat.
  • Neosepta® membranes are described, for example, by SA Mareev, D.Yu.
  • a cation-conducting membrane is used as the diffusion barrier D ⁇ 110>, this can be, for example, a polymer functionalized with sulfonic acid groups, in particular of the following formula PNAFION, where n and m are independently an integer from 1 to 10 6 , more preferably an integer from 10 to 10 5 , more preferably an integer from 10 2 to 10 4 .
  • any solid electrolyte which can transport cations, in particular alkali cations, more preferably sodium cations, from the central chamber K M ⁇ 103> into the cathode chamber K K ⁇ 102> can be used as the alkali cation-conducting solid electrolyte F K ⁇ 111>.
  • Such solid electrolytes are known to the person skilled in the art and are known, for example, in DE 102015013155 A1, in WO 2012/048032 A2, paragraphs [0035], [0039], [0040], in US 2010/0044242 A1, paragraphs [0040], [0041 ], in DE 10360758 A1, paragraphs [014] to [025].
  • NaSICON preferably has a structure of the formula M I 1+2w+x-y+z M II w M III x Zr IV 2-wxy M V y (SiO 4 )z (PO 4 )3-z.
  • M I is selected from Na + , Li + , preferably Na + .
  • M II is a divalent metal cation preferably selected from Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Co 2+ , Ni 2+ , more preferably selected from Co 2+ , Ni 2+ .
  • M III is a trivalent metal cation, preferably selected from Al 3+ , Ga 3+ , Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , Lu 3+ , Fe 3+ , Cr 3+ , more preferably selected from Sc 3+ , La 3+ , Y 3+ , Gd 3+ , Sm 3+ , particularly preferably selected from Sc 3+ , Y 3+ , La 3+ .
  • M V is a pentavalent metal cation, preferably selected from V 5+ , Nb 5+ , Ta 5+ .
  • the Roman indices I, II, III, IV, V indicate the oxidation numbers in which the respective metal cations are present.
  • NaSICON more preferably has a structure of the formula Na(1 + v)Zr2SivP(3-v)O12, where v is a real number such that 0 ⁇ v ⁇ 3.
  • the cathode chamber K K ⁇ 102> also comprises an inlet Z KK ⁇ 107> and an outlet A KK ⁇ 109>, which allows liquid, such as the solution L 2 ⁇ 113>, to flow into the cathode chamber K K ⁇ 102>. to add and liquid contained therein, such as the solution L 1 ⁇ 115> to remove.
  • the inlet Z KK ⁇ 107> and the outlet A KK ⁇ 109> are attached to the cathode chamber K K ⁇ 102> in such a way that the liquid makes contact with the cathodic electrode E K ⁇ 105> as it flows through the cathode chamber K K ⁇ 102>.
  • the anode chamber K A ⁇ 101> also includes an outlet A KA ⁇ 106>, which makes it possible to remove liquid located in the anode chamber K A ⁇ 101>, for example the aqueous solution L 4 ⁇ 116>.
  • the middle chamber K M ⁇ 103> includes an inlet Z KM ⁇ 108>, while K A ⁇ 101> and K M ⁇ 103> are connected to one another by a connection V AM ⁇ 112>, through which liquid from K M ⁇ 103> can be directed into K A ⁇ 101>.
  • a solution L 3 ⁇ 114> can be added to K M ⁇ 103> via the inlet Z KM ⁇ 108> and this can be conducted through K M ⁇ 103>, then via V AM ⁇ 112> into the anode chamber KA ⁇ 101> , and finally through the anode chamber K A ⁇ 101>.
  • V AM ⁇ 112> and the drain A KA ⁇ 106> are attached to the anode chamber K A ⁇ 101> in such a way that the solution L 3 ⁇ 114> when flowing through the anode chamber K A ⁇ 101> touches the anodic electrode EA ⁇ 104> contacted.
  • This is the prerequisite for the aqueous solution L 4 ⁇ 116> being obtained when the method according to the invention is carried out according to the second aspect of the invention at the outflow A KA ⁇ 106> if the solution L 3 ⁇ 114> is first divided by K M ⁇ 103>, then V AM ⁇ 112>, then K A ⁇ 101>.
  • connection V AM ⁇ 112> can be formed inside the electrolytic cell E ⁇ 100> and/or outside, preferably inside, the electrolytic cell E ⁇ 100>. If the connection V AM ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, it is preferably formed by at least one perforation in the diffusion barrier D ⁇ 110>.
  • connection V AM ⁇ 112> is formed outside of the electrolytic cell E ⁇ 100>, it is preferably formed by a connection of K M ⁇ 103> and K A ⁇ 101> running outside of the electrolytic cell E ⁇ 100>, in particular by the fact that in the middle chamber K M ⁇ 103> an outlet A KM ⁇ 118> through the outer wall W A ⁇ 117>, preferably at the bottom of the middle chamber K M ⁇ 103>, with the inlet Z KM ⁇ 108> even more preferably at the top of the middle chamber K M ⁇ 103> is formed, and in the anode chamber K A ⁇ 101> an inlet Z KA ⁇ 119> through the outer wall W A ⁇ 117>, preferably at the bottom of the anode chamber K A ⁇ 101>, and these are connected by a line, for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic.
  • a line for example a pipe or a hose, which preferably comprises a material selected from rubber, plastic
  • the drain A KA ⁇ 106> is then even more preferably at the top of the anode chamber KA ⁇ 101>.
  • "Outflow A KM ⁇ 118> at the bottom of the middle chamber K M ⁇ 103>” means that the outflow A KM ⁇ 118> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> fills the middle chamber K M ⁇ 103> leaves in the same direction as gravity.
  • Inlet Z KA ⁇ 119> at the bottom of the anode chamber K A ⁇ 101> means that the inlet Z KA ⁇ 119> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> flows into the anode chamber K A ⁇ 101> occurs against gravity.
  • Inlet Z KM ⁇ 108> at the top of the middle chamber K M ⁇ 103> means that the inlet Z KM ⁇ 108> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 3 ⁇ 114> enters the middle chamber K M ⁇ 103> in the same direction as gravity.
  • Outflow A KA ⁇ 106> at the top of the anode chamber K A ⁇ 101> means that the outflow A KA ⁇ 106> is attached to the electrolytic cell E ⁇ 100> in such a way that the solution L 4 ⁇ 116> fills the anode chamber K A ⁇ 101> leaves against gravity.
  • This embodiment is particularly advantageous and therefore preferred if the outlet A KM ⁇ 118> through the outer wall WA ⁇ 117> at the bottom of the middle chamber KM ⁇ 103>, and the inlet Z KA ⁇ 119> through the outer wall WA ⁇ 117> at the bottom of the anode chamber K A ⁇ 101>.
  • This arrangement makes it particularly easy to discharge gases with L 4 ⁇ 116> formed in the anode chamber K A from the anode chamber K A ⁇ 101> in order to then separate them further.
  • Z KM ⁇ 108> and A KM ⁇ 118> are arranged on opposite sides of the outer wall W A ⁇ 117> of the central chamber K M ⁇ 103> ( eg Z KM ⁇ 108> at the bottom and A KM ⁇ 118> at the top of the electrolytic cell E ⁇ 100> or vice versa) and Z KA ⁇ 119> and A KA ⁇ 106> on opposite sides of the outer wall W A ⁇ 117> of the Anode chamber K A ⁇ 101> arranged (i.e.
  • Z KA ⁇ 119> at the bottom and A KA ⁇ 106> at the top of the electrolytic cell E ⁇ 100> or vice versa as shown in particular in Figure 1.
  • L 3 ⁇ 114> must flow through the two chambers KM ⁇ 103> and KA ⁇ 101> through this geometry.
  • Z KA ⁇ 119> and Z KM ⁇ 108> can be formed on the same side of the electrolytic cell E ⁇ 100>, with A KM ⁇ 118> and A KA ⁇ 106> then automatically also being formed on the same side of the electrolytic cell E ⁇ 100> are.
  • Z KA ⁇ 119> and Z KM ⁇ 108> may be formed on opposite sides of the electrolytic cell E ⁇ 100>, in which case A KM ⁇ 118> and A KA ⁇ 106> are automatically also formed on opposite sides of the electrolytic cell E ⁇ 100>.
  • connection V AM ⁇ 112> is formed within the electrolytic cell E ⁇ 100>, this can be ensured in that one side ("side A") of the electrolytic cell E ⁇ 100>, which is the top or the
  • the bottom of the electrolytic cell E ⁇ 100> is preferably the top, as shown in Figure 2, includes the inlet Z KM ⁇ 108> and the outlet A KA ⁇ 106> and the diffusion barrier D ⁇ 110> starting from this side ("side A”) extends into the E ⁇ 100> electrolytic cell, but not all the way to the opposite side (“side B”) of the E ⁇ 100> electrolytic cell from side A, which is then the bottom or top of the Electrolytic cell E ⁇ 100> is sufficient and 50% or more of the height of the three-chamber cell E ⁇ 100>, more preferably 60% to 99% of the height of the three-chamber cell E ⁇ 100>, even more preferably 70% to 95% of the height of the three-chamber cell E ⁇ 100>, more preferably 80% to 90% of the height of the
  • bottom of the electrolytic cell E ⁇ 100> is the side of the electrolytic cell E ⁇ 100> through which a solution (e.g. L 3 ⁇ 114> at A KM ⁇ 118> in Figure 1) exits the electrolytic cell E in the same direction as gravity or the side of the electrolytic cell E through which a solution (e.g. L2 ⁇ 113> at Z KK ⁇ 107> in Figures 1 and 2 and L 3 ⁇ 114> at A KA ⁇ 119> in Figure 1) of the electrolytic cell E against the Gravity is supplied.
  • “top side of the electrolytic cell E” is the side of the electrolytic cell E through which a solution (e.g.
  • the central chamber K M includes built-in components ⁇ 120>.
  • internals ⁇ 120> are in the solid state of aggregation. Any objects or structures known to those skilled in the art that are sufficiently inert to the electrolysis conditions are suitable as such internals.
  • the internals ⁇ 120> include, in particular, at least one material selected from rubber; Plastic chosen in particular from polystyrene, polypropylene, PVC, PVC-C; Glass; Porcelain; Metal.
  • the metal is in particular a metal or an alloy of several metals selected from titanium, iron, molybdenum, chromium, nickel, preferably an alloy comprising at least two metals selected from titanium, iron, molybdenum, chromium, nickel, even more preferably a steel alloy comprising, in addition to iron, at least one other metal selected from titanium, molybdenum, chromium, nickel, and most preferably it is stainless steel.
  • the internals ⁇ 120> are selected in particular from structured packings, unstructured packings (filling bodies) and trays, for example bubble-cap trays, valve trays, tunnel trays, Thormann trays, Phillips bell-bottom trays or sieve trays.
  • Unstructured packings are generally random packings. Raschig rings, Pall rings, Berl saddles or Intalox® saddles are usually used as packing. Structured packings are sold, for example, under the trade name Mellapack® from Sulzer.
  • the internals ⁇ 120> can be loose in the central chamber K M ⁇ 103>, for example balls ⁇ 121>, for example made of glass, in a basket made of wire frame ⁇ 122>, as shown in Figure 1.
  • the internals ⁇ 120> can also be attached, for example to the solid electrolyte F K ⁇ 111>, to the diffusion barrier D ⁇ 110> or to the outer wall ⁇ 117> delimiting the inside of the central chamber K M ⁇ 103>.
  • the attachment can be done by methods known to those skilled in the art, for example by screwing, clamping, gluing (plastic adhesive, PVC adhesive).
  • the pins ⁇ 123-2> shown in Figure 2 are attached to the solid electrolyte FK ⁇ 111>, and the pins ⁇ 123-1> to the diffusion barrier D ⁇ 110>.
  • Corresponding pegs can also be attached to the outer wall ⁇ 117> delimiting the inside of the central chamber K M ⁇ 103>, and then form stalactite or stalactite-like structures in the central chamber.
  • the fixtures ⁇ 120> can be attached to the alkali cation-conducting solid electrolyte FK ⁇ 111> or to the diffusion barrier D ⁇ 110>, for example by being attached to a wire frame on the relevant wall.
  • the internals ⁇ 120> make up a proportion ⁇ of 1 to 99%, more preferably 10 to 99%, even more preferably 40 to 90%, even more preferably 50 to 90% , more preferably 60 to 90%, most preferably 80 to 90% of the volume comprised by the central chamber K M .
  • VO is the maximum volume of liquid, for example the electrolyte L 3 ⁇ 114>, which the central chamber K M ⁇ 103> can hold if it does not include any internals ⁇ 120>.
  • V M is the maximum volume of liquid, for example the electrolyte L 3 ⁇ 114>, which the middle chamber K M ⁇ 103> can hold if it includes internals ⁇ 120>. It was surprisingly found that the internals ⁇ 120> in the central chamber K M ⁇ 103> lead to turbulence and turbulence in the electrolyte L 3 ⁇ 114> flowing through the central chamber K M ⁇ 103> during the method according to the invention. This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte FK ⁇ 111> and thus enables the electrolysis to run longer or prolongs the life of the electrolysis cell.
  • the internals ⁇ 120> are fitted in the middle chamber K M ⁇ 103> in such a way that they prevent the flow of the electrolyte L 3 ⁇ 114> through the middle chamber K M ⁇ 103> and the anode chamber K A ⁇ 101 > enable to a sufficient extent or not completely block.
  • the internals ⁇ 120> interrupt the direct path in the middle chamber K M between inlet Z KM ⁇ 108> and connection V AM ⁇ 112>.
  • the following "thread test" is used to determine whether the direct route between inlet Z KM ⁇ 108> and connection V AM ⁇ 112> in the middle chamber KM is interrupted: 1.
  • a thread is fed through the opening through which inlet Z KM ⁇ 108> opens into the middle chamber K M , and guided out of the opening through which the connection V AM ⁇ 112> opens into the middle chamber K M.
  • the thread is so long that its ends lie outside the central chamber K M .
  • a force is applied in the opposite direction to the respective end of the thread so that the thread tightens without breaking. 3. If there is at least one thread that touches the internals when it is introduced into the middle chamber and tightened according to steps 1. and 2., then the feature is that the direct path between inlet Z KM ⁇ 108> and connection V AM ⁇ 112> in the middle chamber K M is interrupted. 4. If no thread touches the internals when it is introduced into the middle chamber and tightened according to steps 1.
  • the thread is selected in particular from sewing thread (eg from the Schrmann company), fishing line, twine.
  • the method according to the second aspect of the invention comprises the following steps (a), (b) and (c) occurring simultaneously.
  • step (a) a solution L 2 ⁇ 113> comprising the alcohol ROH, preferably comprising an alkali metal alkoxide XOR and alcohol ROH, is passed through K K ⁇ 102>.
  • X is an alkali metal cation and R is an alkyl group of 1 to 4 carbon atoms.
  • X is selected from the group consisting of Li + , K + , Na + , more preferably from the group consisting of K + , Na + .
  • Most X Na + .
  • R is preferably selected from the group consisting of n-propyl, iso-propyl, ethyl, methyl, more preferably selected from the group consisting of ethyl, methyl. Most preferably R is methyl.
  • the solution L2 ⁇ 113> is preferably free of water. "Free of water” means according to the invention that the weight of the water in the solution L 2 ⁇ 113> based on the weight of the alcohol ROH in the solution L 2 ⁇ 113> (mass ratio) ⁇ 1:10, more preferably ⁇ 1:20, more preferably ⁇ 1:100, even more preferably ⁇ 0.5:100.
  • the mass fraction of XOR in the solution L 2 ⁇ 113> is in particular >0 to 30% by weight, preferably 5 to 20% by weight, more preferably at 10 to 20% by weight, even more preferably at 10 to 15% by weight, most preferably at 13 to 14% by weight, most preferably at 13% by weight.
  • the solution L 2 ⁇ 113> comprises XOR
  • the mass ratio of XOR to alcohol ROH is still in the range from 1:100 to 1:5, more preferably in the range from 1:25 to 3:20 more preferably in the range 1:12 to 1:8, even more preferably at 1:10.
  • a neutral or alkaline aqueous solution L 3 ⁇ 114> of a salt S comprising X as a cation is substituted by K M ⁇ 103>, then passed through V AM ⁇ 112>, then through K A ⁇ 101>.
  • the salt S is preferably a halide, sulfate, sulfite, nitrate, bicarbonate or carbonate of X, more preferably a halide.
  • Halides are fluorides, chlorides, bromides, iodides. The most preferred halide is chloride.
  • the pH of the aqueous solution L 3 ⁇ 114> is ⁇ 7.0, preferably in the range from 7 to 12, more preferably in the range from 8 to 11, even more preferably from 10 to 11, most preferably at 10.5.
  • the mass fraction of the salt S in the solution L 3 ⁇ 113> is preferably in the range >0 to 20% by weight, preferably 1 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 10 to 20% by weight, most preferably at 20% by weight, based on the total solution L 3 ⁇ 113>.
  • step (b) the internals ⁇ 120> in the central chamber K M ⁇ 103> result in turbulence and turbulence in the electrolyte L 3 ⁇ 114> flowing through the central chamber K M ⁇ 103> during the method according to the invention .
  • This slows down or completely prevents the build-up of a pH gradient during the electrolysis, which protects the acid-sensitive solid electrolyte FK ⁇ 111> and thus enables the electrolysis to run longer or prolongs the life of the electrolysis cell.
  • step (c) a voltage is then applied between EA ⁇ 104> and EK ⁇ 105>.
  • the charge source is known to those skilled in the art and is typically a rectifier that converts alternating current into direct current and can generate certain voltages via voltage converters.
  • This in turn has the following consequences: the solution L 1 ⁇ 115> is obtained at the outlet A KK ⁇ 109>, with the concentration of XOR in L 1 ⁇ 115> being higher than in L 2 ⁇ 113>, at outlet A KA ⁇ 106> an aqueous solution L 4 ⁇ 116> of S is obtained, the concentration of S in L 4 ⁇ 116> being lower than in L 3 ⁇ 114>.
  • the area of the solid electrolyte that contacts the anolyte located in the middle chamber K M ⁇ 103> is in particular 0.00001 to 10 m 2 , preferably 0.0001 to 2.5 m 2 , more preferably 0.0002 to 0.15 m 2 , even more preferably 2.83 cm 2 . It goes without saying that step (c) of the method according to the second aspect of the invention is carried out when both chambers K M ⁇ 103> and K A ⁇ 101> are at least partially loaded with L 3 ⁇ 114> and K K ⁇ 102> is at least partially loaded with L2 ⁇ 113>.
  • step (c) charge transport takes place between E A ⁇ 104> and E K ⁇ 105> implies that K K ⁇ 102>, K M ⁇ 103> and K A ⁇ 101> simultaneously with L 2 ⁇ 113> or L 3 ⁇ 114> are loaded in such a way that they cover the electrodes EA ⁇ 104> and EK ⁇ 105> to such an extent that the current circuit is closed.
  • step (a) and step (b) are carried out continuously and voltage is applied in accordance with step (c).
  • step (c) After step (c) has been carried out, solution L 1 ⁇ 115> is obtained at outlet A KK ⁇ 109>, the concentration of XOR in L 1 ⁇ 115> being higher than in L 2 ⁇ 113>.
  • the concentration of XOR in L 1 ⁇ 115> is preferably 1.01 to 2.2 fold, more preferably 1.04 to 1.8 fold, still more preferably 1.077 to 1.4 fold more preferably 1077 to 1.08 times higher than in L2 ⁇ 113>, most preferably 1077 times higher than in L 2 ⁇ 113>, more preferably the mass fraction of XOR in L 1 ⁇ 115> and in L 2 ⁇ 113> is in the range of 10 to 20% by weight, more preferably 13 to 14% by weight.
  • an aqueous solution L 4 ⁇ 116> of S is obtained, the concentration of S in L 4 ⁇ 116> being lower than that in L 3 ⁇ 114>.
  • the concentration of the cation X in the aqueous solution L 3 ⁇ 114> is preferably in the range of 3.5 to 5 mol/l, more preferably 4 mol/l.
  • the concentration of the cation X in the aqueous solution L 4 ⁇ 116> is more preferably 0.5 mol/l lower than that of the aqueous solution L 3 ⁇ 114> used in each case.
  • the method according to the second aspect of the invention is carried out at a temperature of 20°C to 70°C, preferably 35°C to 65°C, more preferably 35°C to 60°C, even more preferably 35°C to 50°C and a pressure of 0.5 bar to 1.5 bar, preferably 0.9 bar to 1.1 bar, more preferably 1.0 bar.
  • hydrogen is typically produced in the cathode chamber K K ⁇ 102>, which hydrogen can be discharged from the cell together with the solution L 1 ⁇ 115> via the outlet A KK ⁇ 109>.
  • the mixture of hydrogen and solution L 1 ⁇ 115> can then be separated by methods known to those skilled in the art.
  • the alkali metal compound used is a halide, in particular chloride, chlorine or another halogen gas can be produced, which can escape from the cell via the outlet A KK ⁇ 106> together with the solution L 4 ⁇ 116> can be discharged.
  • oxygen and/or carbon dioxide can also be formed, which can also be removed.
  • the mixture of chlorine, oxygen and/or CO2 and solution L 4 ⁇ 116> can then be separated by methods known to those skilled in the art.
  • the gases chlorine, oxygen and/or CO 2 have been separated from the solution L 4 ⁇ 116>, these can be separated from one another by methods known to those skilled in the art.
  • the method according to the invention is therefore more efficient than the procedure described in WO 2008/076327 A1, in which the product solution is used for the middle chamber, which reduces the overall turnover.
  • the acid-labile solid electrolyte is stabilized by preventing the formation of a pH gradient due to the built-in components ⁇ 120>.
  • NM Sodium methoxide
  • the electrolytic cell consisted of three chambers, which corresponded to those shown in Figure 1, except that the electrolytic cell had no installations in the middle chamber, ie it did not include the wire basket ⁇ 122> with the glass balls ⁇ 121> shown in Figure 1.
  • the connection between the middle and anode chamber was made by a hose that was attached to the bottom of the electrolytic cell.
  • the anode compartment and middle compartment were separated by a 2.83 cm2 anion exchange membrane (Tokuyama AMX, ammonium groups on polymer).
  • the cathode and middle chamber were separated by a NaSICON type ceramic with an area of 2.83 cm2.
  • the ceramic had a chemical composition of the formula Na3.4Zr2.0Si2.4P0.6O12.
  • the anolyte was transferred to the anode compartment through the middle compartment.
  • the flow rate of the anolyte was 1 l/h, that of the catholyte was 90 ml/h and a current of 0.14 A was applied.
  • the temperature was 35°C.
  • the electrolysis was carried out for 500 hours with the voltage remaining constant at 5V.
  • Comparative example 2 Comparative example 1 was repeated with a two-chamber cell comprising only an anode and a cathode chamber, the anode chamber being separated from the cathode chamber by the ceramic of the NaSICON type. Thus, this electrolytic cell did not contain a center chamber.
  • This gradient can make electrolysis even more difficult, especially in the case of very long running times, and can lead to corrosion and ultimately fracture of the solid electrolyte.
  • this pH gradient is destroyed, which, in addition to the stated advantages that a three-chamber cell has over a two-chamber cell, further increases the stability of the solid electrolyte.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Dans un premier aspect, la présente invention concerne une cellule d'électrolyse qui présente trois chambres, la chambre centrale étant séparée de la chambre cathodique par un électrolyte solide perméable aux cations, par exemple du NaSICON, et séparée de la chambre anodique par une barrière de diffusion. L'invention est caractérisée en ce que la chambre centrale comprend des éléments intégrés. La cellule d'électrolyse selon l'invention résout le problème selon lequel, pendant l'électrolyse, un gradient de concentration apparait dans la chambre centrale de la cellule d'électrolyse, lequel gradient mène à des valeurs de pH réduites localement et donc à une détérioration de l'électrolyte solide. Les éléments intégrés permettent de créer un tourbillonnement de la solution électrolytique lors de son passage à travers la chambre centrale pendant l'électrolyse, ce qui empêche la formation d'un gradient de pH. Dans un deuxième aspect, la présente invention concerne un procédé de production d'une solution d'alcoolate de métal alcalin dans la cellule d'électrolyse selon l'invention.
PCT/EP2022/066943 2021-06-29 2022-06-22 Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins WO2023274796A1 (fr)

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CN202280046253.5A CN117580977A (zh) 2021-06-29 2022-06-22 用于生产碱金属醇盐的三室电解池
EP22735407.3A EP4363639A1 (fr) 2021-06-29 2022-06-22 Cellule d'électrolyse à trois chambres pour la production d'alcoolates de métaux alcalins

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