EP3622100A1 - Cathode couplée à une membrane destinée à la réduction de dioxyde de carbone dans un électrolyte à base acide dépourvu de cations mobiles - Google Patents

Cathode couplée à une membrane destinée à la réduction de dioxyde de carbone dans un électrolyte à base acide dépourvu de cations mobiles

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Publication number
EP3622100A1
EP3622100A1 EP18734473.4A EP18734473A EP3622100A1 EP 3622100 A1 EP3622100 A1 EP 3622100A1 EP 18734473 A EP18734473 A EP 18734473A EP 3622100 A1 EP3622100 A1 EP 3622100A1
Authority
EP
European Patent Office
Prior art keywords
cathode
anode
acid
membrane
salt bridge
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP18734473.4A
Other languages
German (de)
English (en)
Inventor
Bernhard Schmid
Christian Reller
Günter Schmid
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3622100A1 publication Critical patent/EP3622100A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/63—Holders for electrodes; Positioning of the electrodes

Definitions

  • the present invention relates to a method for electric ⁇ analysis of CO2, wherein the electrolytic cell comprises a salt bridges ⁇ space that can accommodate a liquid and / or dissolved acid environmentally, an electrolytic cell having a cathode compartment comprising a cathode, a first ion exchange membrane to an anion exchanger and / or anion contains and which is adjacent to the cathode compartment, said cathode contacting the first ion exchange membrane directly adjoins an anode compartment comprising an anode, and a diaphragm wel ⁇ ches to said anode compartment, wherein further a Salzbrü ⁇ ckenraum is present, which is between the first ion exchange membrane and the diaphragm is arranged, a
  • Electrolysis plant comprising the electrolytic cell and the use of the electrolytic cell of the plant or to the Electric ⁇ analysis of CO2.
  • Table 1 shows Faraday efficiencies FE (in [%]) of products resulting from carbon dioxide reduction on various metal electrodes. The specified Values are valid for a 0.1 M
  • polymers elekt ⁇ driven conductive catalyst particles for example, as ex- trudierter or calendered film be present, representing a
  • Full-catalyst gas diffusion electrode corresponds, or as a porous, catalytically inactive, but conductive electrode, eg in the form of carbon fiber gas diffusion layers impregnated with a small amount of active catalyst particles.
  • a catalyst to a solid electrolyte, which can also be used as a catalyst.
  • Coated membrane can be called.
  • a three-phase zone between the catalyst, the Festelekt ⁇ rolyten and the CO2 can form. With corresponding structures electrochemical re ⁇ production of CO2 to chemically usable products is possible.
  • US 2017/0037522 A1 discloses a process for producing formic acid in an electrochemical device.
  • acids in the anode compartment are also quite common, as for example in J. Shi, F. Shi, N. Song, J-X. Liu, X-K Yang, Y-J Jia, Z-W Xiao, P. Du Journal of Power Sources, 2014, 259, 50-53.
  • Electrolysis cells in which the CO2 / O2 mixtures are formed at the anode are known, for example, from US 2016 0251755 A1 and US Pat. No. 9,481,939.
  • Anion exchanger and / or anion transporter contains, for example, in a salt bridge space and / or in the anolyte, effectively CO 2 can be converted to economically reusable products and the formation of hydrogen can be überra ⁇ sarily suppressed.
  • the cathodically produced HCC> 3 ⁇ ions occur in this case not from the electrode into the electrolyte. Instead penetrate the more mobile M + ions in the electrode and form with the HCC> 3 ⁇ ion a salt. This salt can then emerge as a solution or permeate at the side of the electrode facing away from the electrolyte.
  • MHCO 3 Lö ⁇ sung respected, it can also lead to crystallization of these salts.
  • Solid electrolytes are in electrolysis cells, for example, membranes from polymers modified with charged functionalities.
  • AEM anion exchange membranes
  • an AEM may occur when, for example, the anionic portion is completely ⁇ occupied by HCC> 3, while the occupied cationic see part partly by M + ion and partly by the kationi ⁇ rule functional groups of the polymer a formal double salt system exist, and in the interior becomes.
  • HCC can> 3 ⁇ No act as counter-ion for the single in the electrolyte cations "H +".
  • a presence of "H +" ions in the AEM is therefore only possible if the acid anions (eg SC> 4 2 ⁇ ) of the electrolyte are present in the AEM. Are they produced by a sufficiently high ion current from the AEM? In spite of an acid electrolyte, a high pH can be established in the cathode AEM composite.
  • the only other charge transport pathway is the conduction of OH ⁇ via the Grotthuß mechanism by the membrane swollen in H 2 O, or a hopping transport of HCC> 3 ⁇ from localized polymer-bound cation to localized cation.
  • Figures 1 and 2 illustrate this difference in the use of different electrolytes 1, which abut the anion exchange membrane AEM, and which pass as ions to the cathode K. 1 shows the variant of this is with a salt M + X ⁇ shown as the electrolyte 1 by way of example, while shown as Elect ⁇ rolyt 1 ⁇ against the variant in Figure 2 with an acid H + X ⁇ .
  • the present invention relates to a method for the electrolysis of CO 2, wherein an electrolyzer comprising ⁇ sezelle
  • a cathode compartment comprising a cathode
  • Anion exchanger and / or Anionentransporter which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane, wherein the contact according to certain embodiments is also ionic in nature;
  • an anode compartment comprising an anode
  • the present invention relates to a process for the electrolysis of CO 2 , comprising an electrolytic cell
  • a cathode compartment comprising a cathode
  • Anion exchanger and / or Anionentransporter which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane, wherein the contact according to certain embodiments is also ionic in nature;
  • an anode compartment comprising an anode, the anode compartment adjoining the first ion exchange membrane;
  • CO 2 is reduced at the cathode, wherein the electrolyte in the anode compartment consists of a liquid acid and / or a solution of an acid.
  • an electrolytic cell comprising a cathode compartment including a cathode
  • AnionenSer and / or Anionentransporter contains and which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane;
  • an anode compartment comprising an anode
  • Diaphragm is arranged, wherein the diaphragm is not ion-conductive.
  • an electrolysis system which comprises OF INVENTION ⁇ dung modern electrolytic cell and the use of OF INVENTION ⁇ to the invention electrolysis cell or electrolysis system according to the invention for the electrolysis of CO2 disclosed.
  • FIGS. 1 and 2 show a graphic representation of the cathodic half-cell of the previously described transport models of ions of salts and acids in an AEM, which is applied to a cathode.
  • Figure 3 shows schematically an example of a Elektrolyseanla- ge with an electrolytic cell as it is used in a erfindungsge ⁇ MAESSEN method of application.
  • FIGS. 4 and 5 schematically show further examples of electrolysis cells with which the method according to the invention can be carried out.
  • FIGS. 6 and 7 schematically show a graphical representation of the different CC> 2 release in a a salt electrolyte ( Figure 6) and an acid electrolyte ( Figure 7).
  • FIG. 8 shows schematically an electrolysis plant according to the invention with an AEM diaphragm cell according to the invention in which the process according to the invention can be carried out.
  • FIG. 9 shows a schematic representation of an AEM bipolar double-membrane cell in which the method according to the invention can likewise be carried out.
  • Figure 10 schematically shows the experimental setup in fiction, modern ⁇ Example 1.
  • the figure 11 are experimental results of the invention
  • Example 1 where there is a plot of Faraday efficiency against the applied current density.
  • Figure 12 schematically shows the experimental setup in the present Comparative Example 1, and 13, the thus obtained test results ⁇ , again a plot of the Faraday efficiency is against the applied current density.
  • Figure 15 shows a schematic representation of the prisonerssauf ⁇ construction in Comparative Example 2, and Figure 16, the thus erhalte- NEN experimental results, again a plot of the Faraday efficiency is against the applied current density.
  • Example 1 of the invention solid lines
  • Example 1 comparative example ⁇ Game 2 (dotted lines) juxtaposed for comparison.
  • Figure 18 a comparison of Comparative Example 2 (solid; w / o AEM) and Example 1 (ge ⁇ dashed lines; w / AEM) shown at a current density of 150 mAcm -2 he preserved ⁇ gas chromatograms.
  • FIGS. 19 and 20 each schematically show the experimental setup in Reference Examples 1 and 2, and FIGS. 21 and 22 show the experimental results obtained therein. Detailed description of the invention
  • Gas diffusion electrodes in general are electrodes in which liquid, solid and gaseous phases are present, and where in particular a conductive catalyst catalyses an electrochemical reaction between the liquid and the gaseous phase.
  • the embodiments may be of different nature, for example as a porous "solid material catalyst", possibly with auxiliary ⁇ layers to adjust the hydrophobicity, in which case, for example, a membrane GDE composite, eg AEM GDE composite may be prepared, as a conductive porous support having in which a catalyst can be applied in a thin layer, in which case again a membrane-GDE composite, eg AEM-GDE composite, can be produced, or as a composite porous catalyst, optionally with an additive directly on a membrane, eg AEM, can be applied and then form a CCM in the composite.
  • hydrophobic is understood as meaning water-repellent. Hydrophobic pores and / or channels According to the invention, therefore, those which reject water.
  • hydrophobic properties are associated according to the invention with substances or molecules with nonpolar groups.
  • hydrophilic is understood as the ability to interact with water and other polar substances.
  • electro-osmosis an electrodynamic Phenom ⁇ nouns, in which, on the particles in solution with a positive zeta potential, a force towards the cathode and on all of the particles with a negative zeta potential, a force acts to the anode. If a conversion takes place at the electrodes, ie a galvanic current flows, then also a stream of the particles with positive Zeta potential comes to the cathode, independently of whether the species participates in the conversion or not. The same applies to a negative zeta potential and the anode. If the cathode is porous, the medium is also pumped through the electrode. It is also known as an electro-osmotic pump.
  • the material flows caused by electro-osmosis can also flow in opposite directions to concentration gradients. Diffusion induced currents that the concentration gradient ausglei ⁇ chen can thereby be compensated.
  • the present invention relates to a method for the electrolysis of CO 2, wherein an electrolyzer comprising ⁇ sezelle
  • a cathode compartment comprising a cathode; a first ion exchange membrane containing a
  • AnionenSer and / or Anionentransporter contains and which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane;
  • an anode compartment comprising an anode
  • salt bridge space wherein the salt bridge space is arranged between the first ion exchange membrane and the first separator membrane
  • the electrolyte in the salt bridge space consists of the liquid acid and / or the solution of an acid, for example solid or gaseous acid, for example in water, for example double-distilled or demineralized water.
  • the present invention relates to a process for the electrolysis of CO 2 , comprising an electrolyte cell
  • a cathode compartment comprising a cathode
  • AnionenSer and / or Anionentransporter contains and which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane;
  • an anode compartment comprising an anode, wherein the anode compartment adjoins the first ion exchange membrane;
  • the electrolyte in the anode chamber from the liquid acid and / or the solution of a - for example, solid or gaseous - acid, for example in water, for example double-distilled or deionized water.
  • FIG. 3 shows an example of a 2 membrane assembly for CO 2 - electric reduction with an acidic anode reaction.
  • a salt bridge space II is formed, which is separated from the cathode space I by a first ion exchange membrane, here as AEM, and the anode space III by a first separator.
  • AEM first ion exchange membrane
  • CEM cation and / or proton exchange membrane
  • cathodically generated HCC> 3 ⁇ can be neutralized at the interface between the anion exchange membrane (AEM) and the salt bridge electrolyte by the present method according to the first aspect , This can prevent that HCC> 3 ⁇ can move to the anode and is then lost as unbrauch ⁇ bares CO 2 / O 2 mixture. It will thus be according ⁇ voted embodiments salt bridge space nearly pure CO 2 with only minimal traces of cathodic products macge ⁇ sets that can be directly supplied to the cathode compartment I again.
  • AEM anion exchange membrane
  • Figures 4 and 5 show in addition, other structures of an electrolytic cell such as may be used in a method according to the two ⁇ th aspect of the present invention.
  • no salt bridge space is provided, so that the anode space III connects directly to the AEM, in which case the anode, as shown in Figures 4 and 5, may be located at any point in the anode compartment III.
  • Corresponding embodiments of the anode space are as shown in Figure 3 is possible in a method with a structure, that is where the anode A is not located on the CEM on ⁇ .
  • the electrolytic cell shown in Figures 4 and 5 may also be used in the embodiment shown in Figure 3 Elektrolyseanla ⁇ ge.
  • the various half-cells of Figures 3 to 5, as well as the corresponding arranged components of the electrolysis system, can be combined as desired, as well as with other (not shown) Elektrolyserenzzellen.
  • the methods according to the invention are distinguished by the fact that the cathode K contacts the first ion exchange membrane, which contains an anion exchanger and / or anion transporter, directly, in particular also ionically.
  • the processes according to the invention are distinguished, in particular, by the use of a liquid and / or dissolved acid in the salt bridge space or in the anode space, especially in comparison to strongly acidic ion exchanger packages or similar solid devices:
  • gas bubbles produced in the salt bridge space or anode space can be transported away unhindered by the fluid through the medium, which enables a simple mode of operation.
  • higher flow rates can be selected to ensure better cooling of the system.
  • liquid and / or dissolved acids even with the use of liquid and / or dissolved acids a simple and inexpensive operation is possible, especially in comparison to ion exchangers.
  • an accumulation of metal impurities in parts of the electrolysis cell can be prevented by washing them out with the liquid and / or dissolved acid. Accordingly, an external electrolyte treatment, eg with a cation exchanger, is also possible below.
  • the salt bridge space in the method of the first aspect or the anode compartment in the method of the second aspect are not particularly limited insofar as they connect respectively to the first Io ⁇ nentoolermembran.
  • the term salt bridge space is used here in terms of its function to act as a bridge between the anode assembly and cathode assembly and thereby have cations and anions, which, however, do not have to form salts in the present case. Since in the present case a liquid or dissolved acid is present in the salt bridge space, this could also be called an acid bridge space or ion bridge space.
  • the space is according to the invention as a salt bridge space be ⁇ draws, even if in the classic sense, no salt must be present.
  • the salt bridge space if present, there is an electrolyte in the process according to the invention which can ensure the electrolytic ionic bond between the cathode arrangement and the anode arrangement.
  • This electrolyte is also referred to as salt bridge and has a liquid and / or gelös ⁇ te acid.
  • the salt bridge thus serves as an electrolyte, preferably with high ionic conductivity, and serves to establish the contact between anode and cathode. According to certain embodiments , the salt bridge also enables the dissipation of lost heat. In addition, the salt bridge can serve as the reaction medium for anodically and cathodically generated ions such as proton, hydroxide or hydrogen carbonate ions.
  • the technical teaching is the construction and the Be ⁇ drove the cathodic half-cell.
  • This consists of a gas-permeable electrically connected catalyst layer, which is in direct contact with an AEM, on the opposite side, an acid-based electrolyte, preferably without Al ⁇ kalimetallkationen, in particular without metal cations, followed.
  • the acid is not particularly limited insofar as it is present as a liquid and / or in solution, so that the acid can flow through the salt bridge space and / or the anode space.
  • the acid is water-soluble and / or is present as a solution in a suitable solvent such as water, alcohols, aldehydes, esters, carbonates, etc. and / or mixtures, in particular water, eg bidistilled or demineralized water.
  • Electrolytes in the salt bridge space a pK s value of 6 or less, preferably 5 or less, more preferably 3 or less, even more preferably 1 or less, particularly preferably 0 or less, wherein preferably the liquid and / or dissolved acid is selected from dilute or un ⁇ diluted H 2 SO 4 , a solution of H 2 N-SO 2 -OH, dilute or undiluted HCIO 4 , a solution of H 3 PO 4 , dilute or undiluted CF 3 -COOH, dilute or undiluted CF 3 - S O 2 - OH, a solution of (CF 3 - S O 2) 2 _NH , a solution of HF, dilute or undiluted HCOOH, dilute or undiluted CH 3 -COOH, a solution of HCl, a solution of HBr, a solution of HI, and / or mixtures thereof.
  • the acid electrolyte is characterized in accordance with certain exporting ⁇ by the embodiments absence of mobile cations - such as hereinafter defined, in particular metal cations, au ⁇ SSER "H +" or "D +" of.
  • mobile cations - such as hereinafter defined, in particular metal cations, au ⁇ SSER "H +" or "D +" of.
  • H + or D + instead of H + or protons are used.
  • the electrolyte preferably contains no cations other than mobile "H +", especially metal cations.
  • sulfuric acid in particular diluted pivot ⁇ ric acid (H2 SO4) is used which, because of their low price and their high conductivity as Alternatively, other acids may also be used, as stated above, with strong acids having non-oxidizing anions being preferred, such as H 2 N-SO 2 -OH, HC 10 4 , H 3 PO 4 , CF 3 -COOH, CF 3 -SO 2 -OH, (CF 3 - SC> 2) 2-NH, etc.
  • weak acids can, preferably in higher concentrations, for example greater than 10 wt.% Or 20 wt.%, Eg greater than 30% by weight, or at their respective maximum conductivity, for example HF, HCOOH, CH 3 -COOH.
  • this acid is identical to the cathodic product of the CO 2 electrolysis, for example in the case of formic acid or acetic acid.
  • the acids may be present in a concentration up to 30 wt.%, Preferably to 50 wt.%, More preferably to 70 wt.%, And in particular ⁇ sondere to 100 wt.%, Are present.
  • other acids can be used, such as dissolved HCl, HBr, HI.
  • a salt electrolyte which is usually adjacent to the first ion exchange membrane is added.
  • the salt bridge space or in the anode space in particular replaced by an acid.
  • anolyte as well as for the salt bridge acids are used, it is also possible to select these with identical composition. Since no osmotic pressures occur in this case and the release of the CO2 S can take place in front of the salt bridge, in particular in the region of the first ion exchange membrane and thus away from the first separator membrane, if present, wherein the HCC> 3 ⁇ the first separator membrane according to In certain embodiments, it is no longer absolutely necessary to use an ion-selective membrane as the first separator membrane, and, for example, a diaphragm can be used to separate CO2 and O2. Accordingly, a diaphragm is also possible as the first separator membrane, as further explained below, and consequently a corresponding electrolysis cell according to the invention, for example an AEM sensor, can also be used.
  • Diaphragm cell - as further explained below - be used in he ⁇ inventive method.
  • the processes according to the invention are therefore preferably carried out at elevated temperatures in the range of 50-120 ° C., preferably between 60-90 ° C., in order to further minimize gas solubility.
  • the acid concentration is preferably selected such that it lies around the Leitdozenssma ⁇ ximum the acid.
  • Exemplary Conductive ⁇ possibilities are shown in Tables 3 and 4 for sulfuric acid and phos phoric acid ⁇ .
  • the cathode space, the anode space and the possibly existing salt bridge space according to the invention in the methods as well as in the electrolysis cell according to the invention discussed below are not particularly limited in terms of shape, Ma ⁇ material, dimensions, etc., insofar as they the cathode, the anode and the receive first ion exchange membrane and possibly the first separator membrane.
  • the two or three spaces may be, for example, within a common cell ge ⁇ forms, in which case they can be accordingly separated by the first Ionenaustau ⁇ exchange membrane and possibly correspond the first separator membrane.
  • the individual rooms in this case may be provided corresponding to ⁇ guiding and outlet devices for reactants and products, for example in the form of liquid, gas, solution, suspension, etc. to be carried out depending on the electrolysis, which possibly also each gurge- can be led.
  • the individual rooms can be flowed through in parallel streams or in countercurrent.
  • % Said still further CO contained th may, thus for example at least 20 volume CO 2 contains - - For example, in an electrolysis of CO 2.
  • the materials of the respective rooms or the electrolysis cell and / or the other constituents of the electrolysis plant can also be appropriately adapted to desired reactions, reactants, products, electrolytes, etc.
  • at least one power source per electrolytic cell is included.
  • Other device parts which occur in electrolysis cells or electrolysis systems can also be provided in the electrolysis plant or electrolysis cell according to the invention.
  • a stack comprising 2 - 1000, preferably 2 - 200 cells, and whose operating voltage is preferably in the range of 3 - 1500 V, particularly preferably 200 - 600 V, is constructed from these individual cells.
  • a reactant gas formed in the salt bridge space for example CO 2 , which may also contain H 2 and / or CO, is recycled again in the direction of the cathode space.
  • the cathode according to the invention is not particularly limited and may be adapted to a desired half-reaction in ⁇ play with respect to the reaction products, in that they contact with the first ion exchange membrane directly, at least one location is so with the first ion exchange membrane directly in contact, preferably the cathode in Essentially flat with the first ion exchange membrane is in direct contact.
  • the cathode is adjacent at ⁇ least in a region directly to the first ion exchange membrane to.
  • a cathode such as Cu, Ag, Au, Zn, Pb, Sn, Bi, Pt, Pd, Ir, Os, Fe, Ni, Co, W, Mo, etc. may be a cathode for reducing CO 2 and possibly CO. , or mixtures and / or alloys thereof, preferably Cu, Ag, Au, Zn, Pb, Sn, or mixtures and / or alloys thereof, and / or a salt thereof, wherein suitable materials can be adapted to a desired product.
  • the catalyst can thus be selected depending on the desired product.
  • the Katalysa ⁇ tor is preferably based on Ag, Au, Zn and / or their compounds such as Ag 2 T, AgO, AU 2 O, Au 2 O 3, ZnO.
  • Ag, Au, Zn and / or their compounds such as Ag 2 T, AgO, AU 2 O, Au 2 O 3, ZnO.
  • Cu or Cu-containing compounds such as CU 2 O, CuO and / or copper-containing mixed oxides with other metals, etc.
  • formic acid are in ⁇ game as catalysts based on Pb and / or Cu, in particular Cu possible.
  • the cathode is the electrode on which takes place the reductive Halbreak ⁇ tion. It may be one or more parts and, for example, as a gas diffusion electrode, porous Electrode or directly with the AEM in the composite, etc. be soldbil ⁇ det.
  • Anion exchange membrane e.g. can be ion-conducting and / or mechanically bonded;
  • Gas diffusion electrode or porous bound Kataly ⁇ sator Modell which according to certain embodiments may be partially pressed into the first ion exchange membrane, for example an AEM;
  • porous, conductive, catalytically inactive structure for example carbon paper GDL or carbon-paper-GDL (gas diffusion layer, gas diffusion layer), coal ⁇ fabric Cloth GDL or Carbon-Cloth-GDL, and / or polymer-bound film granular glassy carbon, which is impregnated with the catalyst of the cathode and optionally an ionomer, that the connection to the first ion exchange membrane, such as an AEM, enables ⁇ , wherein the electrode then mechanically to the first ion exchange membrane, such as an AEM pressed or previously compressed with the first ion exchange membrane, for example an AEM, to form a composite; particulate catalyst, which is applied by means of a suitable ionomer to a suitable support, for example a porous conductive support, and according to certain embodiments can abut the first ion exchange membrane, for example an AEM;
  • a conductive, porous electrode for example as a so-called CCM (catalyst-catalyzed membrane), wherein a catalytic activity of this electrode is basically not required and, for example, carbon-based GDI / s or lattice, for example, titanium, wherein it is not excluded that this electrode contains ionomers and / or contains the active catalyst or consists thereof in large parts;
  • non-closed sheet such as a net or an expanded metal, which consists for example of a catalyst or comprises this or is coated with this and according to certain embodiments ⁇ forms on the first ion exchange membrane, such as an AEM, is applied;
  • the electrode then me ⁇ chanically to the first ion exchange membrane, for example an AEM, pressed or previously compressed with the first ion exchange membrane, for example an AEM, to form a composite; porous, conductive carrier impregnated with a suitable catalyst and optionally an ionomer and, according to certain embodiments, being attached to the first ion exchange membrane, for example an AEM;
  • non-ionic gas diffusion electrode which has been subsequently impregnated with a suitable ionomer, for example an anionic ionomer ionomer and, according to certain embodiments, is attached to the first ion exchange membrane, for example an AEM, or is connected thereto, eg via an ionomer.
  • a suitable ionomer for example an anionic ionomer ionomer and, according to certain embodiments, is attached to the first ion exchange membrane, for example an AEM, or is connected thereto, eg via an ionomer.
  • a suitable ionomer for example an anionic ionomer ionomer and, according to certain embodiments, is attached to the first ion exchange membrane, for example an AEM, or is connected thereto, eg via an ionomer.
  • the cathode may in this case also contain materials customary in cathodes, such as binders, ionomers, for example ani
  • the cathode may comprise at least one ionomer, for example an anion-conducting or anion-transporting ionomer (eg anion exchange resin, anion transport resin), which may for example comprise different ion exchange functional groups, which may be the same or different, for example tertiary amine groups, alkylammonium groups and / or phosphonium groups), a, for example, conductive, substrate (eg, a metal such as titanium), and / or at least one non-metal such as carbon, Si, boron nitride (BN), boron ⁇ doped diamond, etc., and / or at least one conductive oxide such as indium tin oxide (ITO), aluminum zinc oxide (AZO) or fluorinated tin oxide (FTO) - for example, as used to produce photoelectrodes, and / or at least one polymer based on polyacetylene,
  • anion exchange resin anion transport resin
  • different ion exchange functional groups
  • binders e.g., hydrophilic and / or hydrophobic polymers, e.g., organic binders, e.g., selected from PTFE
  • PVDF polyvinylidene difluoride
  • Perfluoroalkoxy polymers FEP (fluorinated ethylene-propylene copolymers), PFSA (perfluorosulfonic acid polymers), and mixtures thereof, in particular PTFE), conductive fillers (eg carbon), non-conductive fillers (eg glass) and / or hydrophilic additives (eg Al 2 O 3, MVDC 2, hydrophilic Ma ⁇ terialien such as polysulfones, such as polyphenylsulfones, polyimides, polybenzoxazoles or polyether ketones, or generally in Elect ⁇ rolyten electrochemically stable polymers, polymerized "Io niche liquids ", and / or organic conductors such as
  • PEDOT PSS or PANI (champrose sulfonic acid sorted
  • Polyaniline which are not particularly limited.
  • the cathode in particular in the form of a gas diffusion electric ⁇ de, for example connected to the first ion exchange membrane, or in the form of a CCM includes, in accordance with certain embodiments, ion-conducting components, in particular a anionenleitfixede component.
  • the anode according to the invention is not particularly limited and may be adapted to a desired half-reaction in ⁇ play with respect to the reaction products.
  • the anode which is electrically connected to the cathode by means of a current source for the provision of the voltage for the electrolysis, the oxidation of a substance takes place in the anode space.
  • the material of the anode is not special ⁇ limited and it depends primarily on the desired reaction from. Exemplary electrode materials include platinum or platinum alloys, palladium or palladium alloys and glassy carbon, iron, nickel, etc. More anode Mate ⁇ rials are also conductive oxides such as doped or
  • ITO indium tin oxide
  • FTO fluorine-doped tin oxide ⁇
  • AZO aluminum-doped zinc oxide
  • iridium oxide etc.
  • these catalytically active compounds can also be superficially applied only in thin-film technology, for example on a titanium and / or carbon support.
  • the anode catalyst is not particularly limited. As Ka ⁇ talysator for 0 2 - or Cl 2 ⁇ generation for example, IrO get x (1.5 ⁇ x ⁇ 2) or 2 Ru0 used.
  • conductive carbon black in the form of conductive carbon black, activated carbon, graphite, etc.
  • a mixed oxide with other metals such as Ti0 2, vorlie ⁇ gene, and / or on a conductive material such as C.
  • catalysts based on Fe-Ni or Co-Ni can also be used for the generation of C.
  • the structure described below with bipolar membrane or bipolar membrane is suitable.
  • the anode is the electrode at which the oxidative half reaction takes place. It can also be designed as a gas diffusion electrode, porous electrode or solid electrode or solid electrode, etc.
  • Gas diffusion electrode or porous bound Kataly ⁇ sator Utilizing a suitable ionomer, for example ei ⁇ cationic ionomer, with the first separator membrane, if present, for example, a cation exchange membrane (CEM) or a diaphragm, eg ion conducting and / or can be mechanically bonded; Gas diffusion electrode or porous bound Kataly ⁇ sator Design, which may be partially pressed into certain embodiments, partially in the first separator membrane, for example, a CEM or a diaphragm ⁇ ;
  • a suitable ionomer for example ei ⁇ cationic ionomer
  • first separator membrane if present, for example, a cation exchange membrane (CEM) or a diaphragm, eg ion conducting and / or can be mechanically bonded
  • CEM cation exchange membrane
  • diaphragm eg ion conducting and / or can be mechanical
  • particulate catalyst which is applied by means of a suitable ionomer to a suitable support, for example a porous conductive support, and according to certain embodiments, can abut the first separator membrane, for example a CEM or a diaphragm;
  • particulate catalyst which is pressed into the first separator membrane for example a CEM or a diaphragm, and for example is connected in accordance with it lei ⁇ tend;
  • non-closed sheet such as a net or an expanded metal, for example, consists of a catalyst or comprises this or is coated with this and according to certain embodiments ⁇ forms on the first separator membrane, such as a CEM or a diaphragm abuts; solid electrode, in which case also a gap between the first separator membrane, such as a CEM or a diaphragm, and the anode can best ⁇ hen, but this is not preferred;
  • Catalyst and possibly an ionomer is impregnated and according to certain embodiments of the first separator membrane, for example a CEM or a diaphragm abuts;
  • non-ionically conductive gas diffusion electrode which has been subsequently impregnated with a suitable ionomer, for example a cation-conducting ionomer, and according to certain embodiments bears against the first separator membrane, for example a CEM or a diaphragm
  • the electrode e.g. contains an anodically stable anionic conductive material and is applied directly to the anion-conducting layer of a bipolar membrane.
  • the anode may be attached to the acid electrolyte or directly on the first ion exchange membrane, e.g. AEM, for example in the form of a sheet (e.g., a fine mesh coated mesh), if no salt bridge space is present, but the latter is not preferred.
  • AEM first ion exchange membrane
  • the cathode is contacted via the liquid acid, for example in the salt bridge space or in the anode space, e.g. in the salt bridge space, coupled to the anodic half-cell.
  • the corresponding anodes can also contain materials customary in anodes such as binders, ionomers, for example cation-conducting ionomers, for example containing sulfonic acid and / or phosphonic acid groups, fillers, hydrophilic additives, etc., which are not particularly limited For example, also described above with respect to the cathodes.
  • the electrodes mentioned above by way of example can be combined with one another as desired.
  • electrolytes may also be present in the anode space and / or cathode space, which are also referred to as anolyte or catholyte, but it is not excluded according to the invention that no electrolytes are present in the two spaces and correspondingly, for example, only gases for conversion into These are supplied, for example, only CO2, if necessary, as a mixture with, for example, CO and / or H2O, which may also be liquid, for example as an aerosol, but before ⁇ admits gaseous H2O to the cathode and / or water or HCl to the anode.
  • an anolyte is present, which extends from the salt bridge, so the electrolyte of the salt bridge chamber having a liquid and / or dissolved acid - etc. under failed ⁇ may or may correspond to this, for example in terms contained solvents, acids - as available If no salt bridge is present, the anolyte comprises a liquid and / or dissolved acid.
  • a catholyte in this case is the electrolyte flow around the cathode and, according to certain embodiments, serves to supply the cathode with substrate or educt.
  • the following exporting ⁇ insurance forms are possible, for example.
  • the catholyte may be, for example, as a solution of the substrate (C0 2) in a liquid Trä ⁇ gerphase (eg water) and / or as a mixture of the substrate with other gases (eg CO + CO2; steam + CO2) vorlie ⁇ gene also may be prepared by a. Return recycled Ga ⁇ se as CO and / or H2 may be present. Also, as described above, the substrate may be present as a pure phase, eg CO2.
  • An anolyte is an electrolyte flow around the anode or at the anode and, according to certain embodiments, serves to supply the anode with substrate or starting material and, if appropriate, the removal of anode products.
  • the following embodiments are possible, for example.
  • the anode compartment comprises an anolyte that includes a liquid and / or dissolved acid, preferably wherein the anolyte and / or the acid salt ⁇ bridge space and the electrolyte in the salt bridge space no mobile cations other than protons and / or deuterons in particular no metal cations.
  • the acid in the salt bridge space does not comprise any mobile cations other than protons and / or deuterons, in particular no metal cations.
  • the anolyte does not comprise mobile cations except protons and / or deuterons, especially no metal cations.
  • Mobile cations are here cations which are not bound by a chemical bond to a carrier, and / or in particular an ion mobility of more than
  • halogen-hydrogen acids HCl, HBr or HI wherein halide salts may not be suitable when using a diaphragm as a first separator membrane, but when using a bipolar membrane as first separator membrane can be used.
  • SO2 in the anolyte for the preparation of Schwefelching ⁇ acid, or for the production of H2O H2O2, etc. is possible.
  • the anolyte is an aqueous electrolyte, it being possible if appropriate for the corresponding anolyte to be added to the anolyte, which are reacted at the anode.
  • the educt addition is not particularly limited here.
  • the educt addition in the supply to the cathode space is not limited.
  • CO2 can be added outside the cathode compartment to water, or can also be added through a gas diffusion electrode, or can be supplied only as a gas to the cathode compartment.
  • the anode compartment depending on the starting material used, e.g. Water, HCl, etc., and desired product.
  • the first ion exchange membrane which has a
  • Anionentransportmaterial contains and which is adjacent to the cathode ⁇ space, the invention is not particularly be ⁇ limits. It separates the cathode from the salt bridge space in the process of the first aspect as well as in the electrolysis cell according to the invention or in the process of the second aspect separates the cathode from the anode space, so that from the direction of the cathode space comprising CO2 in the direction of the electrolyte the order cathode / first IonenSermemb ⁇ ran / salt bridge space (first aspect) or cathode / first ion exchange membrane / anode space result.
  • an anion exchanger or consists of this, which in the currentless state in the form of an acid-anion salt, preferably according to the acid the salt bridge, is present, and more preferably passes from a minimum current density in the bicarbonate / carbonate form.
  • the first ion exchange membrane is an anion exchange membrane and / or anion transporter membrane.
  • the first ion exchange membrane may be a hydrophobic one
  • Anion exchange membrane and / anion-transporter membrane also as cationic (though for example trace), especially proton, blocker.
  • Anion transporter with tightly bound cations can constitute a blockade for mobile cations due to Coulomb repulsion, which can additionally counteract salt precipitation, in particular within the cathode. The reason for this is probably the formation of
  • the accumulation of the electrolyte cations in the region of the interface is usually due to the electroosmosis.
  • a concentration gradient can not simply be broken down on the electrode side, since a catalyst-based cathode, which is designed as described above, eg a gas diffusion electrode or a CCM, usually has only a very poor anion conductivity.
  • the anion conductivity can be improved significantly here.
  • the electrolyte contains only protons.
  • ion transporters in particular anion transport resins, can be used as binder material or additive in the electrode itself
  • Aniontransfer resins HCC> 3 ⁇ conduct self.
  • an anion transport can be carried out by anion exchangers.
  • an integrated anion exchanger again provides a blockade for cations, eg also
  • Metallkationspuren which can additionally counteract salt precipitation and contamination of the electrode. In the case of protons, hydrogen formation can be suppressed.
  • the first ion exchange membrane for example from the cathode side adjacent to the salt bridge in the process of the first aspect, can thus contain, for example, an anion exchanger and / or anion and / or anion transporter in the form of an anion exchanger and / or transporter layer, in which case further layers such as hydrophobic layers Improvement of contact with a gas, such as CO 2 , may be included.
  • the first ion exchange membrane is an anion exchange membrane and / or
  • Anionentransportermembran so for example an ion-conductive membrane (or in a broader sense, a membrane with an anion exchange layer and / or
  • Anionentransport für) with positively chargedmetalsie ⁇ of the pump which is not particularly limited.
  • a Favor ⁇ ter charge transport takes place in the anion exchange and / or Anionentransporter Mrs or a
  • the first Ionenaus ⁇ exchange membrane and in particular serves
  • Anion transporter membrane for providing a
  • Anion transport along fixed fixed positive charges In particular, the penetration of an electrolyte, for example proton-containing electrolyte, into the cathode promoted by electro-osmotic forces can be reduced or completely avoided.
  • the ion exchanger contained in the membrane can, according to certain embodiments, be converted in particular into the carbonate / bicarbonate form during operation and thereby suppress the passage of protons through the membrane to the cathode.
  • a suitable first ion exchange membrane for example anion exchange membrane and / or anion transporter membrane, exhibits good performance according to certain embodiments
  • An exemplary AEM according to the present invention is the A201-CE membrane marketed by Tokuyama, the "Sustainion” marketed by Dioxide Materials, or an anion exchange membrane sold by Fumatech, such as Fumasep FAS-PET or Fumasep FAD-PET.
  • the first separator membrane is not particularly limited if it is present, that is, for example, in the method according to the first aspect of the present invention.
  • the first separator membrane (as viewed from the anode side adjacent to the Salzbrü ⁇ CKE) is selected from an ion exchange membrane which contains a cation exchanger, a bipolar membrane, WO is at at the bipolar membrane is preferably the cation layer toward the cathode and oriented towards the anions lei ⁇ tend layer towards the anode, and a diaphragm.
  • a suitable first separator membrane for example a cation exchange membrane or a bipolar membrane, contains, for example, a cation exchanger which can be in contact with the electrolyte in the salt bridge space. It may, for example, contain a cation exchanger in the form of a cation exchange layer, in which case further layers, such as hydrophobicizing layers, may be contained. It may also be designed as a bipolar membrane or as a cation exchange membrane (CEM).
  • the cation exchange membrane or cation exchange layer is, for example, an ion-conductive membrane or ion-conducting layer with negatively charged functionalizations. An exemplary charge transport into the salt bridge takes place in such a first separator membrane by cations.
  • Nafion® membranes are suitable as CEM, or the product marketed by Fumatech fumapem-F membranes vertiebene Aciplex by Asahi Kasei, or Vertrie AGC ⁇ surrounded Flemionmembranen.
  • CEM chemical e.g., boron trifluoride
  • Fumatech fumapem-F membranes vertiebene Aciplex by Asahi Kasei or Vertrie AGC ⁇ surrounded Flemionmembranen.
  • other with strongly acidic groups groups such as sulfonic acid
  • the first separator membrane prevents the passage of anions, in particular HCC> 3 ⁇ , into the anode space.
  • the first separator membrane rendering the cell less com plex ⁇ and can be made cheaper may be formed as a diaphragm.
  • the diaphragm essentially separates the anode space and the salt bridge space, for example more than 70%, 80% or 90%, based on the interface between anode space and salt bridge space, or separates the anode space and the salt bridge space, that is to say 100%, based on the interface between anode compartment and salt bridge space.
  • the diaphragm essentially separates the anode space and the salt bridge space, for example more than 70%, 80% or 90%, based on the interface between anode space and salt bridge space, or separates the anode space and the salt bridge space, that is to say 100%, based on the interface between anode compartment and salt bridge space.
  • liquid acid in the salt bridge space that HCC> 3 ⁇ ions reach the anode compartment.
  • the slide is phragma this is not particularly limited and may for example ⁇ game based on a ceramic (eg ZrÜ 2 or 3 Zr (PC> 4) 3) and / or a swellable functionalized polymer, such as PTFE, to be.
  • binders eg hydrophilic and / or hydrophobic polymers, eg organic binders, eg selected from PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PFA
  • Perfluoroalkoxy polymers FEP (fluorinated ethylene-propylene copolymers), PFSA (perfluorosulfonic acid polymers), and mixtures thereof, in particular PTFE), conductive fillers (eg carbon), non-conductive fillers (eg glass) and / or hydrophilic additives (eg Al 2 O 3, MVDC 2, hydrophilic Ma ⁇ terialien such as polysulfones, such as polyphenylsulfones (PPSU), polyimides, polybenzoxazoles or polyether ketones or general ⁇ my electrochemically stable in the electrolyte polymers may be present.
  • PPSU polyphenylsulfones
  • PPSU polyimides
  • polybenzoxazoles polyether ketones
  • general ⁇ my electrochemically stable in the electrolyte polymers may be present.
  • the diaphragm is porous and Since it is not itself ionic, it should preferably be able to swell in the acid electrolyte used, and it is a physical barrier to gases and can not be penetrated by gas bubbles a porous polymeric structure, wherein the Gundpolymer is hydro ⁇ phil (eg PPSU). In contrast to the CEM or bipolar membrane umrox the polymer does not have charged functionalities.
  • the diaphragm more preferably hydro ⁇ hydrophilic structure-imparting components such as metal oxides (eg, ZrC> 2) or ceramics as set forth above.
  • a suitable first separator membrane for example a cation exchange membrane, a bipolar membrane and / or a diaphragm, exhibits a high wettability by water and / or acids, according to certain embodiments
  • the first ion exchange membrane and / or the first separator membrane are hydrophobic if they form a CCM with the electrodes, at least on the side facing the electrodes, so that the reactants of the electrodes are gaseous.
  • the anode and / or cathode is at least partially ⁇ hydrophilic.
  • the first ion exchange membrane and / or the first separator membrane are wettable with water. In order to ensure good ionic conductivity of the ionomers, preference is given to swelling with water. The experiment has shown that poorly wettable membranes can lead to a significant deterioration of the ionic bonding of the electrodes.
  • the anode and / or cathode also have sufficient hydrophilicity. Possibly. This can be adjusted by hydrophilic additives such as T1O 2 , Al 2 O 3 , or other electrochemically inert metal oxides, etc.
  • Minim ⁇ least used one of the following first separator membranes.
  • a diaphragm is preferably used when the salt ⁇ bridge (of the electrolyte in the salt bridge space) and the anolyte ei ⁇ ne identical, preferably inert, have acid or consisting of, in which case then the diaphragm serves to keep them separated gases, so that Carbon dioxide does not pass into the anode compartment, and / or if at the anode O 2 is produ ⁇ ed, in particular to save costs.
  • a corresponding construction of an exemplary electrolysis system with diaphragm DF is shown in FIG. 8, with the other system components corresponding to those of FIG. 3 here.
  • a cation exchange membrane or a membrane having a cation exchange layer are particularly USAGE ⁇ det when the salt bridge and anolyte are not identical, and / or especially when the anolyte HCl, HBr and / or HI containing, and / or if a chlorine production at the anode he follows. Since the cation exchange membrane is the transfer of
  • the anode Prevents anions from the anolyte into the salt bridge and unlike the diaphragm has no open porosity, the anode can be made more free.
  • the anodic reaction is limited only in that it does not release mobile cations, except protons, that can cross into the salt bridge through the CEM.
  • a bipolar membrane preferably a
  • AnionenSerhus and / or Anionenentransporter für the bipolar membrane is directed towards the anode space and a cation exchange layer and / or cation transport layer of the bipolar membrane directed towards the salt bridge space, is particularly used when the salt bridge and the anolyte are not identical, and / or the anolyte includes in particular ⁇ sondere bases and or salts, and / or use of aqueous electrolytes.
  • the anode compartment can be designed independently of the salt bridge and the cathode compartment, which allows a large number of anode reactions with desired products, and in particular when using bases, cheaper anodes or anode catalysts can also be used. For example, nickel-based Anodenkatalysato ⁇ ren for an oxygen evolution, can be used.
  • FIG. 9 shows by way of example a 2-membrane structure for CC> 2 electro-reduction with AEM on the cathode side and bipolar membrane.
  • Larem membrane (CEM / AEM) on the anode side shows, here as well as in Figure 1 to 3, the supply of catholyte k, electrolyte s with liquid and / or dissolved acid (electrolyte for the salt bridge space) and anolyte a, as well as a return R of CO 2 , is shown and on the anode side example ei ⁇ ne oxidation of water.
  • the other reference numerals correspond to those in FIG. 3.
  • a bipolar membrane may, for example, be designed as a sandwich of a CEM and an AEM. In this case are übli ⁇ chate but not two superposed membranes from ⁇ handen, but is a membrane having at least two layers.
  • the illustration in FIG. 9 with AEM and CEM serves only to illustrate the preferred orientation of the layers.
  • Anion exchanger layer shows to the anode, the CEM or cation exchange layer to the cathode. These membranes are almost impassable for both anions and cations.
  • the conductivity of a bipolar membrane is therefore not based on the transportability of ions. Instead, ion transport usually occurs by acid-base dissociation of water in the middle of the membrane. As a result, two oppositely charged charge carriers are generated, which are transported away by the E field.
  • the generative OH ⁇ ions can be passed through the AEM part of the bipolar membrane to the anode, where they are oxidized
  • the conductivity of the bipolar membrane is based on the separation of charges in the membrane, however, is usually expected with a higher voltage drop.
  • the advantage of such a structure lies in the decoupling of the electrolyte circuits, since, as already mentioned, the bipolar membrane is almost impermeable to all ions.
  • the anode and / or cathode have sufficient hydrophilicity. Possibly. This can be adjusted by hydrophilic additives such as T1O 2 , Al 2 O 3 , or other electrochemically inert metal oxides, etc.
  • the cathode and / or the anode is a gas diffusion electrode, as a porous bonded Catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second ion exchange membrane, as a porous conductive support, in which a catalyst is impregnated, and / or as non-closed sheet ⁇ forms.
  • the cathode is a gas diffusion electrode as a porous tethered catalyst ⁇ structure as particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second ion exchange membrane as a porous conductive support, in which a catalyst is impregnated, and or formed as a non-closed sheet, which (r / s) an anion exchange material and / or
  • Anionentransportmaterial contains. Approximately forms according to certain execution is the anode gas diffusion electrode, as po ⁇ Rteil-bound catalyst structure as particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second Ionenaustau ⁇ exchange membrane, a porous conductive support, in which a Ka - talysator is impregnated and / or formed as a non closed sheets which (r / s) is a cation exchanger ⁇ shear material contains and / or gekop ⁇ pelt to a bipolar membrane and / or is bound.
  • the various embodiments of the cathode and anode can be combined with one another as desired.
  • the anode contacts the first separator membrane, as already described by way of example be ⁇ .
  • no charge transport through the anolyte is necessary in this case and the charge transport path is shortened.
  • electrical shading effects can be bypassed by supporting structures between the anode and the first separator membrane so.
  • the anode and / or the cathode are contacted with a conductive structure on the side facing away from the salt bridge space.
  • the conductive structure tur is not particularly limited here.
  • conductive structures are not particularly limited. These may, for example, be coal flows, metal foams, metal knits, expanded metals, graphite structures or metal structures.
  • the electrolysis is carried out at a current density of more than 50 mAcm -2 , preferably more than 100 mAcm -2 , more preferably 150 mAcm -2 or more, even more preferably 170 mAcm -2 or more or 200 mAcm -2 or more, in particular of 250 mAcm -2 or more, eg 300 mAcm -2 or more, 400 mAcm -2 or more, or 600 mAcm -2 or more.
  • the Faraday yield can be improved, contrary to expectation.
  • Another advantage of the method according to the invention is the comparatively low demands on the chemical stability of the first ion exchange membrane, eg an AEM.
  • the stability and applicability of particular AEM's is currently limited primarily by two Degradationsme ⁇ mechanisms, on the one hand by the frequent lack of stability ⁇ formality of the functional groups to concentrated Ba sen such as KOH (Hoffmann elimination of quaternary ammonium ions, on the other hand by the destruction of the polymer backbone by anodic oxidation. Since only acid electrolytes are used in the imported here electrolysis systems in contact with the ers ⁇ th ion exchange membrane, the first ion exchange membrane, for example, is exposed to an AEM never concentrated bases.
  • the anode is preferably not directly attached to the first ion exchange membrane, eg an AEM, which also precludes the anodic damage of this membrane.
  • C0 2 electrolyte has limited to formic acid.
  • Ver ⁇ simplification can for example also in the salt bridge formic ⁇ sensäure such as dilute formic acid, as an electrolyte USAGE ⁇ be det, which can be concentrated by the electrolysis, which through an appropriate electrical conductivity
  • 25 of the formic acid is favored, as shown in Table 5 ersicht ⁇ lich.
  • anions are then, for example, also transported away by the first Ionenaustau ⁇ shear membrane, eg AEM, in the salt bridge (first aspect) or the anolyte (second aspect) and re-protonated by the local acid.
  • the latter is regenerated by the protons which pass from the anodic half-cell or are present in the anolyte.
  • a leakage of formic acid on the side facing away from the salt bridge space of the electrode, if any, is not expected.
  • a first ion exchange membrane for example AEM diaphragm cell ⁇ advantageous, since the components are cheaper and the electrical resistance of the cell is lower.
  • An acid-salt bridge double membrane cell is also advantageous for those applications where there is an exchange of anions between salt bridge and anolyte should be avoided, eg
  • CO2 is electrolyzed, is however not excluded that a further reactant such as CO is on the cathode side in addition to CO2 still present, wel ⁇ ches can be electrolyzed also, so a mixture is present which comprises CO2, and for example, CO.
  • ⁇ game as a starting material on the cathode side contains at least 20 vol.% CO2, for example at least 50 or at least 70 vol.% CO2, and in particular, the starting material is on the cathode side to 100 vol.% C0. 2
  • the present invention relates to an electrolytic cell comprising
  • a cathode compartment comprising a cathode
  • AnionenSer and / or Anionentransporter contains and which adjoins the cathode compartment, wherein the cathode, the first ion exchange membrane directly, preferably also ionically contacted;
  • an anode compartment comprising an anode
  • electrolysis cell of the invention or the electrolysis system according to the invention are used in particular in the novel process for the electrolysis of CO 2 application, which is why aspects that in to ⁇ connexion discussed with these in advance and subsequently ⁇ to, the electrolysis cell of the invention or the electrolysis system according to the invention affect. According Kings ⁇ nen also in conjunction with the electrolysis cell of the invention and / or electrolysis system concerning inventive procedural ⁇ ren that. Also described is an electrolytic cell comprising
  • a cathode compartment comprising a cathode
  • AnionenSer and / or Anionentransporter contains and which adjoins the cathode compartment, wherein the cathode directly contacts the first ion exchange membrane;
  • an anode compartment comprising an anode
  • the anode contacts the diaphragm.
  • the anode and / or the cathode are contacted with a conductive structure on the side facing away from the salt bridge space.
  • the cathode and / or the anode are impregnated as a gas diffusion electrode, as a porous bound catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second ion exchange membrane, as a porous conductive support into which a catalyst is impregnated is, and / or forms as non-closed sheet ⁇ forms.
  • the cathode gas ⁇ diffusion electrode as a porous tethered catalyst structural ⁇ tur, as particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second ion exchange membrane as a porous conductibility higer carrier in which a catalyst is impregnated, and / or formed as a non-closed sheet, which (r / s) an anion exchange material and / or
  • Anionentransportmaterial contains, and / or is the anode as a gas diffusion electrode, as a porous bound catalyst structure, as a particulate catalyst on a support, as a coating of a particulate catalyst on the first and / or second ion exchange membrane, as a porous conductive support in which a catalyst impregnated is, and / or formed as a non-closed sheet containing (r / s) a cation exchange material.
  • the first ion exchange membrane and / or the diaphragm are hydrophilic.
  • the salt bridge space comprises a liquid and / or dissolved acid, wherein preferably an acid of the liquid and / or dissolved acid in the salt bridge space has a pK s value of 6 or less, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, particularly preferably 0 or less, which is whereby further preferably selected the liquid and / or Geloes ⁇ te acid from diluted or undiluted H2 SO4, a solution of H 2 N- S O2-OH, dilute or undiluted HCIO 4 , a solution of H 3 PO 4 , dilute or undiluted CF 3 -COOH, dilute or undiluted CF 3 - S O 2 -OH, a solution of (CF 3 - S O 2 ) 2- NH, a solution of HF, dilute or undiluted HCOOH, dilute or neat CH 3 -CO
  • anode compartment contains an acid which is preferably identical with the electrolyte in the Salzbrü ⁇ blocks, in particular if the second membrane is designed as a diaphragm.
  • an electrolysis installation comprising the inventive Elect ⁇ rolysezelle.
  • the respective embodiments of the electrolysis cell as well as other exemplary components of an electrolysis system according to the invention have already been dis ⁇ cussed above and are therefore also applicable to the inventive electric ⁇ lysestrom.
  • an electrolysis plant according to the invention comprises a multiplicity of electrolysis cells according to the invention, although it is not excluded that there are also other electrolysis cells in addition.
  • the erfindungsge ⁇ Permitted electrolysis system further comprises a feedback device which is connected to a discharge of the salt bridge chamber and a supply of the cathode compartment, which is adapted to a starting material of the cathode reaction, which can be formed again in the salt bridge chamber, in particular a gaseous or with the electrolyte immiscible starting material, to lead back into the cathode space, such as CO 2 , which may also contain CO and / or H 2 .
  • the erfindungsge ⁇ Permitted electrolysis plant further comprises an external device for electrolyte treatment in particular a device for removing dissolved gases from an acid, with which in particular the anolyte and / or the electrolyte are treated in the salt bridge space, for example to remove gases such as CO 2 or O 2 , and thus a return of anolyte and / or the To allow electrolyte in the salt bridge space.
  • an external device for electrolyte treatment in particular a device for removing dissolved gases from an acid, with which in particular the anolyte and / or the electrolyte are treated in the salt bridge space, for example to remove gases such as CO 2 or O 2 , and thus a return of anolyte and / or the To allow electrolyte in the salt bridge space.
  • Anolyte / electrolyte for salt bridge space reservoir is present, al ⁇ so the anolyte and the electrolyte in the salt bridge space are identical.
  • the erfindungsge- Permitted electrolysis plant comprising two separate circuits for anolyte and the electrolyte in the salt bridge space, which may optionally separate a ⁇ directions for electrolytic treatment, may comprise particular devices for removing dissolved gases from an acid, or with only the circuit for the elec- rolyt in the salt bridge space a corresponding device on ⁇ has.
  • the present OF INVENTION ⁇ dung relates to the use of an electrolytic cell of the invention or an electrolysis system according to the invention for the electrolyzer ⁇ se of CO 2, which may also comprise a plurality of electrolytic cells according to the invention.
  • Example 1 The structure of the electrolyzer in Example 1 is similar to the structure shown in FIG. 3 and is shown schematically in FIG.
  • a three-compartment cell was used.
  • the cathode used was a carbon-GDL coated with silver particles: Freundenberg HL 23.
  • the particles were precipitated by means of NaBH 4 from AgNC> 3 in ethanol as follows. AGNC> 3 (3.4g, 20 mmol) was dissolved in ethanol ge ⁇ (250ml). NaBH 4 (3g, 80mmol) was dissolved in NaOH saturated methanol (100ml) and this solution added dropwise. After all silver was precipitated (no blackening at the drop in site), the addition was stopped. The precipitate was transferred to a frit (P4) and washed 4x with 50 ml of ethanol each time and 1 ⁇ with 50 ml of diethyl ether. Subsequently, the powder was dried in vacuo. Yield: 2.88 g of borate stabilized particles. From the particles (90 mg) was a dispersion with the
  • Ionomer AS-4 anion exchanger, Tokuyama
  • n-PrOH n-propanol
  • n-PrOH n-PrOH
  • a 10cm 2 piece of this cathode was mechanically pressed on an AEM A201-CE (Tokuyama) and the cathode contacted by a Ti ⁇ tan frame.
  • the anode used was an IrÜ 2- coated Ti expanded metal with a mesh size of 1x2 mm.
  • CEM a Nafion N115 membrane was used which was pressed directly onto the plug metal.
  • the cell was run at 4V for 20 min. Subsequently, the cell was retracted for 30 minutes at 10 mAcm -2 . Subsequently, at 10, 50, 100 and 150mAcm ⁇ 2 both the amount and the composition of the gases in slit I and slit 2 were determined.
  • Example 1 The test results of Example 1 are shown in FIG. 11, in which the Faraday efficiency FE is plotted against the applied current density J.
  • Fig. 12 The experimental setup used in Comparative Example 1 is shown in Fig. 12 and corresponds substantially to that of the case ⁇ Game 1 and is identical in terms of device components, except that the acid was replaced in the salt bridge chamber II through a KHCO3 salt electrolyte.
  • IM KHCO 3 was used as the electrolyte in the salt bridge space.
  • 150mAcm ⁇ 2 it had to be changed to a 2M KHCO 3 for technical reasons (maximum voltage of the potentiostat).
  • FIG. 15 A schematic representation of the experimental setup in Comparative Example 2 is shown in FIG. 15.
  • the same Ver ⁇ AEM was allowed ⁇ away in comparison to Example 1, to show that this is essential, the further experimental setup corresponds to that of Example. 1
  • the cathode still contains an anion exchange ionomer corresponding to the polymer base of the AEM.
  • Comparative Example 2 The test results of Comparative Example 2 are shown in FIG. 16, in which again the Faraday efficiency FE is shown. the applied current density J is applied. This shows the preferred production of hydrogen.
  • Electrode salt solutions can corrode due to the strong negative potential. As a consequence, the permeate turns blue (Ti3 + ). The titanium corrosion is confirmed here as the cause of the blue coloration by means of chromotropic acid, and the cathodic corrosion detected in control experiments.
  • the permeate liquids are not or little electrically conductive in the inventive arrangement presented here or in the inventive method. Although the contacts are still exposed to a strong negative potential, but not contacted ionic. Consequently, such corrosion phenomena do not occur or severely limited. As it may be at one The liquid occurring at the back of the electrode is water, this contains no ions, which must be recycled to the electrolyte ⁇ . This liquid can therefore be a ⁇ times discarded. Possibly occurring Korrosionspro- products of the contacts are not in accordance with the electric ⁇ LYTEN washed.
  • Reference Examples 1 and 2 In Reference Examples 1 and 2, the effects of low anode pH on cell voltage were examined.
  • the potential of oxidation of water to oxygen depends on the pH of the electrolyte.
  • the electrolyte in the salt bridge is identical in both cases All changes of the voltage are therefore due to the different pH of the anolyte, and then a UI characteristic was recorded again.
  • the structure in Fig. 19 represents an adaptation of an alkaline electrolysis cell for CO 2 electrolysis
  • the ion exchange membrane in a diaphragm was omitted for reasons of comparability.
  • the anolyte in the structure of FIG. 20 does not contain anions of stable acids. Therefore, the expression of a locally low pH values, as for example in the case of Na 2 SC would be possible> 4, here also be ⁇ closed.
  • FIGS. 21 and 22 show the comparison of the UI characteristics with the measurements with the structure of FIG. 19 with filled squares and the measurements with the structure of FIG. 20 with open circles, FIG. 21 showing the "onset" region of the characteristic - line (in particular the left and FIG. 22, the full line shows characteristic ⁇ to 200 mAcm -2.
  • the present invention is characterized by liquid and / or dissolved acids, in particular pure acids as
  • CO 2 is released in a separate chamber and can be recycled.
  • a diaphragm is sufficient to separate anode gas and CO2. Also applicable to the preparation of other CO 2 Redukti ⁇ modulation products (for example, formic acid)

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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé d'électrolyse de CO2, la cellule électrolytique présentant un espace formant pont salin qui comporte un acide liquide et/ou dissous, une cellule électrolytique dotée d'un espace cathode comportant une cathode, une première membrane échangeuse d'ions qui contient un échangeur d'anions et/ou un transporteur d'anions et qui est adjacent à l'espace cathode, la cathode est en contact direct avec la première membrane échangeuse d'ions, un espace anode comportant une anode, et un diaphragme qui est adjacent à l'espace anode, un espace formant pont salin également prévu est disposé entre la membrane échange d'ions et le diaphragme, une installation d'électrolyte comprenant la cellule électrolytique, ainsi que l'utilisation de la cellule électrolytique ou l'installation destinée à l'électrolyse de CO2.
EP18734473.4A 2017-07-12 2018-06-14 Cathode couplée à une membrane destinée à la réduction de dioxyde de carbone dans un électrolyte à base acide dépourvu de cations mobiles Withdrawn EP3622100A1 (fr)

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DE102017211930.6A DE102017211930A1 (de) 2017-07-12 2017-07-12 Membran gekoppelte Kathode zur Reduktion von Kohlendioxid in säurebasierten Elektrolyten ohne mobile Kationen
PCT/EP2018/065854 WO2019011577A1 (fr) 2017-07-12 2018-06-14 Cathode couplée à une membrane destinée à la réduction de dioxyde de carbone dans un électrolyte à base acide dépourvu de cations mobiles

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JP2018090838A (ja) * 2016-11-30 2018-06-14 昭和シェル石油株式会社 二酸化炭素還元装置
DE102017208610A1 (de) * 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
DE102018212409A1 (de) 2017-11-16 2019-05-16 Siemens Aktiengesellschaft Kohlenwasserstoff-selektive Elektrode
DE102017223521A1 (de) 2017-12-21 2019-06-27 Siemens Aktiengesellschaft Durchströmbare Anionentauscher-Füllungen für Elektrolytspalte in der CO2-Elektrolyse zur besseren räumlichen Verteilung der Gasentwicklung
WO2019200115A1 (fr) * 2018-04-11 2019-10-17 University Of Delaware Génération électrochimique de produits contenant du carbone à partir de dioxyde de carbone et de monoxyde de carbone
DE102018210303A1 (de) 2018-06-25 2020-01-02 Siemens Aktiengesellschaft Elektrochemische Niedertemperatur Reverse-Watergas-Shift Reaktion
DE102019201153A1 (de) * 2019-01-30 2020-07-30 Siemens Aktiengesellschaft Verfahren zur energieeffizienten Herstellung von CO
EP3725914A1 (fr) * 2019-04-18 2020-10-21 Siemens Aktiengesellschaft Procédé et dispositif d'usage électrochimique du dioxyde de carbone
US20240133057A1 (en) * 2019-10-24 2024-04-25 Siemens Energy Global GmbH & Co. KG Electrolyser device and method for carbon dioxide reduction
DE102020204224A1 (de) * 2020-04-01 2021-10-07 Siemens Aktiengesellschaft Vorrichtung und Verfahren zur Kohlenstoffdioxid- oder Kohlenstoffmonoxid-Elektrolyse
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DE102021214631A1 (de) * 2021-12-17 2023-06-22 Siemens Energy Global GmbH & Co. KG Zellkonzept zur Nutzung nicht-ionisch leitfähiger Extraktionsmedien
CN114645290B (zh) * 2022-02-25 2023-06-30 东南大学 一种co2捕集与电再生同步转化系统及方法
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DE102017211930A1 (de) 2019-01-17

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