EP3414362A1 - Device and method for the electrochemical utilisation of carbon dioxide - Google Patents
Device and method for the electrochemical utilisation of carbon dioxideInfo
- Publication number
- EP3414362A1 EP3414362A1 EP17724515.6A EP17724515A EP3414362A1 EP 3414362 A1 EP3414362 A1 EP 3414362A1 EP 17724515 A EP17724515 A EP 17724515A EP 3414362 A1 EP3414362 A1 EP 3414362A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- cathode
- carbon dioxide
- anode
- electrolyzer
- 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.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 52
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 108
- 150000001450 anions Chemical class 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005868 electrolysis reaction Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- -1 hydrogen ions Chemical class 0.000 claims description 16
- 125000006850 spacer group Chemical group 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
- C25B3/25—Reduction
-
- 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
Definitions
- the invention relates to a method and an electrolyzer for the electrochemical use of carbon dioxide.
- One of the currently envisaged solutions is the conversion of electrical energy into value products, which can serve, in particular, as platform chemicals or synthesis gas comprising carbon monoxide and hydrogen.
- One possible technique for converting electrical energy into value products is electrolysis.
- a further optimization of the electrolytic cell to Unterbin ⁇ tion of the formation of hydrogen may be the choice of a geeig ⁇ Neten cathode material, which must then demonstrate the highest possible overvoltage for the formation of hydrogen.
- metals are disadvantageously often toxic or lead to negative environmental influences.
- the metals in question include cadmium,
- the object of the invention is therefore to provide an electrolysis cell and a method for operating an electrolysis cell, in which the hydrogen formation is suppressed and the
- Electrolysis cell can be operated energy efficient.
- An electrolyser according to the invention for the electrochemical use of carbon dioxide least comprises an electric ⁇ lysezelle, wherein the electrolytic cell comprises an anode compartment having an anode and a cathode chamber with a cathode. Between the anode compartment and the cathode compartment, a first cation-permeable membrane is arranged. The anode is directly adjacent to the first membrane in the anode compartment. Between the first th membrane and the cathode according to the invention a second anion-selective membrane is arranged and the second membrane is at least partially, but not completely immediacy immediacy ⁇ bar to the first membrane.
- Electrolysers for the electrochemical use of carbon dioxide the following steps are performed. First, it ⁇ follows the provision of an electrolyzer with an anode space with an anode and a cathode space with a cathode.
- a first cation-permeable membrane is arranged between the anode compartment and the cathode compartment.
- the anode directly adjoins the first membrane and a second anode-selective membrane is disposed between the first membrane and the cathode.
- the decomposing carbon dioxide to a product at the cathode in the cathode chamber takes place subsequent ⁇ chd.
- Unreacted carbon dioxide is transported simultaneously as carbonate or hydrogen carbonate from the cathode, through the second membrane.
- hydrogen ions are transported from the anode through the first membrane.
- the hydrogen ions and the carbonate or bicarbonate react to form carbon dioxide and water.
- the released carbon dioxide can then be released via Flusskanä ⁇ le or pores between the first and second membrane.
- the anion-selective membrane advantageously reduces the evolution of hydrogen at the cathode.
- the anion-selective membrane typically comprises covalently bonded quaternary amines (NR 4 + ) such that hydrogen ions can not traverse the anion-selective membrane.
- the inventive method and the electrolyzer according to the invention advantageously allows the release of unreacted carbon dioxide and thus prevents the entry of the carbon dioxide into the anode space and thus also a mixing of the resulting oxygen in the anode space with the carbon dioxide.
- the electrolyzer In the electrolyzer according to the invention only water and carbon dioxide is used.
- the use of a conductive salt or a base can be advantageously avoided.
- water is broken down into protons and oxygen.
- the protons can migrate from the anode through the cation-selective membrane into the space between the first and the second membrane, in particular permeate via the cation-selective membrane.
- the carbon dioxide is converted to a product at the cathode, in particular carbon monoxide, formic acid or ethylene.
- Unreacted carbon dioxide with the hydroxide ions may migrate from the klassri- gen phase through the anion selective membrane as hydrogen carbonate or carbonate in the ⁇ or permeate.
- the first and second membranes are saturated with water.
- the hydrogen carbonate or carbonate and the hydrogen ions can react to form carbon dioxide and water.
- the carbon dioxide is then advantageously passed through flow channels or porous structures from the gap from the electrolyzer.
- further Ent ⁇ lastungsötechnischen between the flow channels and / or the interior of the porous structure and the outer surface of the cathode may be provided to ensure a return of the carbon dioxide and water.
- anion-selective membranes commercially avai ⁇ che membranes can be used.
- these include the Selemiom AMV from AGC Chemicals, the Neosepta from Tokuyama or the Fumasep FAß from Fuma GmbH.
- positive charges in particular quaternary amines NR 4 + immobili ⁇ Siert.
- the total charge of the membrane is counterbalanced by mobile counterions dissolved in the aqueous phase, in particular by hydroxide ions.
- These anion-selective membrane advantageously prevents hydrogen ions are transported to the Ka ⁇ Thode.
- the choice of Ka ⁇ method material can then be very flexible.
- the cathode materials can then be selected depending on the desired product of value.
- the second membrane is at least partially directly adjacent to the cathode.
- the cathode is connected to the anion-selective membrane via macropores to utilize the inner surface of the cathode.
- the macropores typically have a diameter of at least one micrometer.
- the binding of the cathode to the anion-selective membrane laboration may take more advantageous before ⁇ manner over an anion-selective polymer.
- Preferably carried out the connection by means of a solution of the same polymer which penetrates in the preparation in a portion of the diaphragm side cathode pores.
- the surface of the cathode is wetted with a solution of the membrane ⁇ material and then pressed onto the second membrane.
- the liquid phase includes ionic components, in particular hydroxide ions and hydrogen carbonate which are ge at the cathode forms ⁇ and are mobile in the anion-selective membrane so that the membrane sievorteilhaft can be trans- ported.
- ionic components in particular hydroxide ions and hydrogen carbonate which are ge at the cathode forms ⁇ and are mobile in the anion-selective membrane so that the membrane sievorteilhaft can be trans- ported.
- This allows the connection of the Ka ⁇ method with the anion-selective membrane and thus the reduction of the carbon dioxide. It is important that in the cathode the same ion as in the anion-selective membrane is mobile, in the case of the water in particular
- the connection of the anion-conducting membrane to the cathode is typically carried out by impregnating the membrane side of the cathode with an anion-conducting polymer.
- the anion-selective second membrane at least partially adjoins the cathode directly.
- the applied polymer becomes part of the membrane due to the polymerization.
- a common contact surface is arranged between the first and the second membrane, wherein the size of the contact surface is in the range of at least 80% to 98% of the membrane area of the first membrane.
- first and the second diaphragm touch a large area in order to maintain a high conductivity as possible within the electrolytic cell, and thus the energy requirement of the electrolytic cell as possible nied ⁇ rig, that is, to improve its efficiency.
- the cathode and / or the second membrane comprises relief openings in order to guide the carbon dioxide and the water from the spacer device into the gas-side cathode space.
- the gas-side cathode compartment is located on the anode side facing away from the cathode. From this gas-side cathode space, the starting material carbon dioxide is supplied. Guiding the resulting in the spacer device water and carbon dioxide in the gas-side cathode space advantageously allows a higher conversion of carbon dioxide ⁇ and thus a higher efficiency.
- a spacer device is arranged between the first and second membrane. This spacer ⁇ holding device may comprise mesh, grid or a porous structure.
- the cathode comprises at least one of the elements silver, copper, lead, indium, tin or zinc.
- the choice of the cathode material depends especially on the ge ⁇ desired value of the product Kohlenstoffdioxidzerlegung.
- the use of a silver cathode produces carbon monoxide.
- ethylene is produced and with the use of a lead cathode, formic acid is produced.
- Electrolysis cell the free choice of the cathode material suc ⁇ conditions and simultaneously the production of unwanted hydrogen are prevented at the cathode.
- the cathode is then ⁇ at typically as a gas diffusion electrode trained det.
- a gas diffusion electrode is understood as meaning a well-electronically conductive, porous catalyst structure which is partially wetted by the adjacent membrane material, remaining pore spaces being open towards the gas side.
- the unreacted and therefore released again ⁇ carbon dioxide is fed as educt back into the electroly- se.
- the efficiency of the electrolysis is increased because as much carbon dioxide is reacted.
- the electrolyzer is operated with pure water.
- pure water in this case water is called, which has a conductivity of less than 1 mS / cm. , Is avoided by advantageous that salts, in particular hydrogen carbonates, precipitated in the electrolytic cell and so ⁇ with a shortened lifetime of the electrolysis cell administrat ⁇ ren.
- Fig. 1 is an electrolytic cell with an anion-selective
- Fig. 2 shows a spacer for the electrolysis cell with an anion-selective membrane.
- the electrolytic cell 1 comprises a cathode chamber 14 and egg ⁇ nen anode compartment 13.
- the cathode compartment 14 is separated from the anode compartment 13 via a spacer device 11.
- a cation-selective membrane 3 is arranged in the anode compartment 13 .
- An anode 4 directly adjoins this.
- An anion-selective membrane 2 is arranged in the cathode space 14.
- the cathode 5 adjoins.
- the cathode 5 is connected to the on ⁇ ion-selective membrane 2 through an anion-selective polymer.
- a spacer 11 is arranged between the anion-selective membrane 2 and the cation-selective membrane.
- the membranes touch 90% over the contact surfaces.
- the electrolytic cell 1 is supplied with voltage, so that electrolysis can take place.
- carbon dioxide is reduced to carbon monoxide. This typically happens at a silver cathode ⁇ .
- the anion-selective membrane 2 and in the cation-selective membrane 3 water is present.
- positive charge in particular a proton, can move. This is due to the concentration profile of the hydrogen ion 7 in the anode compartment 13 shown.
- Quaternary amines NR 4 + are typically immobilized on the anion-selective membrane 2 on the other hand, resulting in egg ⁇ ner surface charge with a positive charge.
- negatively charged hydroxide ions in particular can move through this membrane. This is illustrated by the concentration profile of the hydroxide 6.
- Negative charges may be present within the Anio ⁇ NEN-selective membrane 2 in the form of bicarbonate or carbonate and transported (in concentration profile not shown).
- the carbon dioxide is reduced to carbon monoxide at the cathode 5, which comprises silver.
- water is decomposed into protons and oxygen in the anode compartment 13.
- the oxygen can leave the anode compartment.
- the protons can migrate via the cation-selective membrane 3 into the gap between bars 8 of the grid of the spacer 11. Unreacted carbon dioxide can with
- Hydroxide ions react to carbonate or bicarbonate and migrate through the anion-selective membrane.
- the bicarbonate or carbonate and the hydrogen ions may then react in the space within the lattice structure 8 to carbon dioxide and water.
- the carbon dioxide can thus be released from the electrolytic cell again, currency ⁇ rend the water can diffuse back into the two membranes.
- the formation of hydrogen at the cathode is advantageously avoided, since the proton can not cross the anion-selective membrane due to its positive charge.
- anion-selective membranes that are commercially available are used.
- the anion-selec tive membrane ⁇ 2 fixedly connected to the cathode 5 the anion-selective membrane 2 and the cathode 5 are fixedly connected to each other through an anion-selective polymer 12th This anion-selective polymer 12 not completely wetted the cathode 5, so that the gas space through openings or pores remain through which the carbon dioxide can dif ⁇ substantiate. From the cathode 5 are using the inner surface of the cathode 5 through the macropores
- the cathode 5 is typically designed as a gas diffusion electrode.
- the spacer device 10 is shown in sections as a lattice structure 8.
- the hatched spots on describe the contact surfaces of the anion-selective membrane 2 and the cation selective membrane 3.
- the white area between the contact surface and the grating structural ⁇ tur 8 denotes flow channels 10 through which the resulting in the intermediate ⁇ space carbon dioxide, the electrolytic cell ver - can let. It is advantageously possible by means of the spacer holder 11 to separate the carbon dioxide and the carbon monoxide from the anode gas oxygen. Furthermore, it is mög ⁇ Lich to use only water to operate the electrolysis cell.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to a method and an electrolyser for the electrochemical utilisation of carbon dioxide. The electrolyser for the electrochemical utilisation of carbon dioxide comprises at least one electrolytic cell, wherein the electrolytic cell has an anode chamber with an anode and a cathode chamber with a cathode, a first cation-permeable membrane is arranged between the anode chamber and the cathode chamber, and the anode is directly adjacent to the first membrane in the anode chamber, and a second anion-selective membrane is arranged in the cathode chamber between the first membrane and the cathode, and the second membrane is at least partially but not completely directly adjacent to the first membrane.
Description
Beschreibung description
Vorrichtung und Verfahren zur elektrochemischen Nutzung von Kohlenstoffdioxid Apparatus and method for the electrochemical use of carbon dioxide
Die Erfindung betrifft ein Verfahren und einen Elektrolyseur zur elektrochemischen Nutzung von Kohlenstoffdioxid . The invention relates to a method and an electrolyzer for the electrochemical use of carbon dioxide.
Die Nachfrage nach Strom schwankt im tagezeitlichen Verlauf stark. Auch die Stromerzeugung schwankt mit zunehmendem Anteil an Strom aus erneuerbaren Energien während des Tagesverlaufs. Um ein Überangebot an Strom in Zeiten mit viel Sonne und starkem Wind bei niedriger Nachfrage nach Strom ausglei¬ chen zu können, benötigt man regelbare Kraftwerke oder Spei- eher, um diese Energie zu speichern. The demand for electricity fluctuates strongly in the course of the day. Electricity generation also fluctuates with increasing share of electricity from renewable energies during the course of the day. To an oversupply of power at times with a lot of sun and strong winds at low demand for electricity to ausglei ¬ chen, you need controlled power plants or storage rather to store this energy.
Eine der derzeitig angedachten Lösungen ist das Umwandeln von elektrischer Energie in Wertprodukte, die insbesondere als Plattformchemikalien oder Synthesegas, welches Kohlenstoffmo- noxid und Wasserstoff umfasst, dienen können. Eine mögliche Technik zur Umwandlung der elektrischen Energie in Wertprodukte stellt die Elektrolyse dar. One of the currently envisaged solutions is the conversion of electrical energy into value products, which can serve, in particular, as platform chemicals or synthesis gas comprising carbon monoxide and hydrogen. One possible technique for converting electrical energy into value products is electrolysis.
Die Elektrolyse von Wasser zu Wasserstoff und Sauerstoff stellt eine im Stand der Technik bekannte Methode dar. Aber auch die Elektrolyse von Kohlenstoffdioxid zu Wertprodukten, wie insbesondere Kohlenstoffmonoxid, Ethylen oder Ameisensäu¬ re wird seit einigen Jahren erforscht und es gibt Bemühungen, ein elektrochemisches System zu entwickeln, das einen Kohlen- stoffdioxidstrom entsprechend des wirtschaftlichen Interesses umwandeln kann. The electrolysis of water into hydrogen and oxygen is a well-known in the prior art method. But the electrolysis of carbon dioxide into valuable products, such as in particular carbon monoxide, ethylene or formic ¬ re being researched for several years and there is an effort to provide an electrochemical system which can convert a carbon dioxide stream according to the economic interest.
Eine vorteilhafte Bauform einer Elektrolyseeinheit ist ein Niedertemperatur-Elektrolyseur bei dem als Eduktgas Kohlen- stoffdioxid mit Hilfe einer Gasdiffusionselektrode in einenAn advantageous design of an electrolysis unit is a low-temperature electrolyzer in which carbon dioxide as educt gas by means of a gas diffusion electrode in a
Kathodenraum umgesetzt wird. An einer Kathode der elektroche¬ mischen Zelle wird das Kohlenstoffdioxid zu Wertprodukten re¬ duziert und an einer Anode wird Wasser zu Sauerstoff oxi-
diert. Aufgrund von Diffusionslimitierungen an der Kathode kann es beim Einsatz eines wässrigen Elektrolyten neben der Bildung von Kohlenstoffmonoxid auch nachteilig zur Bildung von Wasserstoff kommen, da das Wasser des wässrigen Elektro- lyten ebenfalls elektrolysiert wird. Cathode space is implemented. The carbon dioxide is to value-added products ¬ re duced to a cathode of the electrochemical cell and ¬ mix at an anode water is oxy to oxygen diert. Due to diffusion limitations at the cathode, in addition to the formation of carbon monoxide, the use of an aqueous electrolyte can also disadvantageously lead to the formation of hydrogen, since the water of the aqueous electrolyte is also electrolyzed.
Verfahren oder Vorrichtung, die diese unerwünschte Bildung von Wasserstoff an der Kathode unterdrücken, führen oft zu weiteren Beschränkungen. Insbesondere sollte nachteiliger- weise bei der Verwendung einer Protonen-leitenden Membran die Kathode nicht direkt an die Protonen-leitende Membran anlie¬ gen, da wegen der relativ hohen Protonenkonzentration an der Kathode in diesem Fall die Bildung von Wasserstoff begünstigt ist. Um dies zu verhindern, ist daher ein mit einem Elektro- lyten gefüllter Spalt zwischen Protonen-leitender Membran und der Kathode vorhanden. Als Elektrolyt kann jedoch nachteiligerweise kein reines Wasser verwendet werden, da die Leitfähigkeit des reinen Wassers zu gering wäre und ein dra¬ matischer Spannungsabfall im Spalt resultieren würde. Das Verwenden einer Mineralsäure als Elektrolyt, insbesondere verdünnte Schwefelsäure, würde eine unerwünschte Wasserstoff¬ bildung begünstigen, da dies die Protonenkonzentration an der Kathode erhöhen würde. Im Stand der Technik wird daher die Leitfähigkeit innerhalb des Spaltes zwischen der Kathode und der Protonen-leitenden Membran erhöht, indem man eine Base oder ein Leitsalz zum Wasser hinzugibt. Nachteiligerweise werden in nicht saurem Milieu allerdings Hydroxidionen bei der Reduktion von Kohlen- stoffdioxid an der Kathode gebildet. Diese bilden wiederum mit weiterem Kohlestoffdioxid Hydrogencarbonat oder Carbonat. Zusammen mit den Kationen der Base oder den Kationen des Leitsalzes führt dies häufig zu schwer löslichen Substanzen, die als Feststoff innerhalb der Elektrolysezelle ausfallen können und daher den Betrieb der Elektrolysezelle nachteilig stören .
Die Verwendung eines Spalts im Kathodenraum führt bei Kohlenstoffdioxid-Elektrolyseuren zu weiteren Nachteilen: Insbesondere der Spannungsabfall über den Spalt erhöht den Energiebe¬ darf der Elektrolysezelle deutlich, so dass die Effizienz der Elektrolysezelle abnimmt. Methods or apparatus that suppress this undesirable formation of hydrogen at the cathode often lead to further limitations. In particular nachteiliger- should, when using a proton conducting membrane, the cathode is not directly connected to the proton conducting membrane anlie ¬ gene, as is favored the formation of hydrogen due to the relatively high concentration of protons at the cathode in this case. In order to prevent this, therefore, there is a gap between the proton-conducting membrane and the cathode filled with an electrolyte. As electrolyte, however, disadvantageously no pure water can be used, since the conductivity of the pure water would be too low and a dra ¬ matischer voltage drop in the gap would result. The use of a mineral acid as an electrolyte, especially dilute sulfuric acid, would favor undesired hydrogen ¬ education, as this would increase the concentration of protons at the cathode. In the prior art, therefore, the conductivity within the gap between the cathode and the proton-conducting membrane is increased by adding a base or a conducting salt to the water. Disadvantageously, however, hydroxide ions are formed in the reduction of carbon dioxide at the cathode in a non-acidic medium. These in turn form with further carbon dioxide hydrogen carbonate or carbonate. Together with the cations of the base or the cations of the conductive salt, this often leads to poorly soluble substances, which can precipitate as a solid within the electrolysis cell and therefore adversely affect the operation of the electrolysis cell. The use of a gap in the cathode space leads to carbon dioxide electrolyzers to further disadvantages: In particular, the voltage drop across the gap increases the Energiebe ¬ may the electrolytic cell significantly, so that the efficiency of the electrolysis cell decreases.
Eine weitere Optimierung der Elektrolysezelle zur Unterbin¬ dung der Bildung von Wasserstoff, kann die Wahl eines geeig¬ neten Kathodenmaterials sein, welches dann eine möglichst ho- he Überspannung für die Bildung von Wasserstoff vorweisen muss. Solche Metalle sind allerdings nachteiligerweise häufig toxisch oder führen zu negativen Umwelteinflüssen. Insbesondere zählen zu den in Frage kommenden Metallen Cadmium, A further optimization of the electrolytic cell to Unterbin ¬ tion of the formation of hydrogen, may be the choice of a geeig ¬ Neten cathode material, which must then demonstrate the highest possible overvoltage for the formation of hydrogen. However, such metals are disadvantageously often toxic or lead to negative environmental influences. In particular, the metals in question include cadmium,
Quecksilber und Thallium. Der Einsatz dieser Metalle als Ka- thodenmaterialien führt dabei häufig zu einer Einschränkung der Produkte, die in der Elektrolysezelle hergestellt werden können, da das Produkt maßgeblich vom Reaktionsmechanismus an der Kathode abhängt. Nachteilig sind die genannten Metalle allerdings nicht für die Produktion der gewünschten Wertmate- rialien, insbesondere Kohlenstoffmonoxid, Ameisensäure oder Ethylen geeignet. Mercury and thallium. The use of these metals as cathode materials often leads to a restriction of the products that can be produced in the electrolytic cell, since the product depends significantly on the reaction mechanism at the cathode. However, the metals mentioned are not disadvantageous for the production of the desired valuable materials, in particular carbon monoxide, formic acid or ethylene.
Aufgabe der Erfindung ist es daher, eine Elektrolysezelle und ein Verfahren zum Betrieb einer Elektrolysezelle anzugeben, bei der die Wasserstoffbildung unterdrückt wird und die The object of the invention is therefore to provide an electrolysis cell and a method for operating an electrolysis cell, in which the hydrogen formation is suppressed and the
Elektrolysezelle energieeffizient betrieben werden kann. Electrolysis cell can be operated energy efficient.
Die Aufgabe wird mit einen Elektrolyseur gemäß Anspruch 1 und einem Verfahren zum Betreiben eines Elektrolyseurs gemäß An- spruch 10 gelöst. The object is achieved with an electrolyzer according to claim 1 and a method for operating an electrolyzer according to claim 10.
Ein erfindungsgemäßer Elektrolyseur zur elektrochemischen Nutzung von Kohlenstoffdioxid umfasst wenigsten eine Elektro¬ lysezelle, wobei die Elektrolysezelle einen Anodenraum mit einer Anode und einen Kathodenraum mit einer Kathode umfasst. Zwischen dem Anodenraum und dem Kathodenraum ist eine erste Kationen-permeable Membran angeordnet. Die Anode grenzt dabei direkt an die erste Membran im Anodenraum. Zwischen der ers-
ten Membran und der Kathode ist erfindungsgemäß eine zweite Anionen-selektive Membran angeordnet und die zweite Membran grenzt wenigsten teilweise, aber nicht vollständig unmittel¬ bar an die erste Membran. An electrolyser according to the invention for the electrochemical use of carbon dioxide least comprises an electric ¬ lysezelle, wherein the electrolytic cell comprises an anode compartment having an anode and a cathode chamber with a cathode. Between the anode compartment and the cathode compartment, a first cation-permeable membrane is arranged. The anode is directly adjacent to the first membrane in the anode compartment. Between the first th membrane and the cathode according to the invention a second anion-selective membrane is arranged and the second membrane is at least partially, but not completely immediacy immediacy ¬ bar to the first membrane.
Bei dem erfindungsgemäßen Verfahren zum Betreiben eines In the inventive method for operating a
Elektrolyseurs zur elektrochemischen Nutzung von Kohlenstoffdioxid werden folgende Schritte durchgeführt. Zunächst er¬ folgt das Bereitstellen eines Elektrolyseurs mit einem Ano- denraum mit einer Anode und einem Kathodenraum mit einer Kathode. Dabei ist zwischen dem Anodenraum und dem Kathodenraum eine erste Kationen-permeable Membran angeordnet. Die Anode grenzt direkt an die erste Membran und zwischen der ersten Membran und der Kathode ist eine zweite Anoden-selektive Membran angeordnet. Die zweite Membran grenzt dabei wenigs¬ tens teilweise, aber nicht vollständig unmittelbar an die erste Membran an. In der Elektrolysezelle erfolgt anschlie¬ ßend das Zerlegen von Kohlenstoffdioxid zu einem Produkt an der Kathode in dem Kathodenraum. Nicht umgesetztes Kohlen- stoffdioxid wird zeitgleich als Carbonat oder Hydrogencarbo- nat von der Kathode weg, durch die zweite Membran, transportiert. Zeitgleich werden Wasserstoffionen von der Anode durch die erste Membran transportiert. Zwischen der ersten und der zweiten Membran reagieren die Wasserstoffionen und das Carbo- nat oder Hydrogencarbonat zu Kohlenstoffdioxid und Wasser.Electrolysers for the electrochemical use of carbon dioxide, the following steps are performed. First, it ¬ follows the provision of an electrolyzer with an anode space with an anode and a cathode space with a cathode. In this case, a first cation-permeable membrane is arranged between the anode compartment and the cathode compartment. The anode directly adjoins the first membrane and a second anode-selective membrane is disposed between the first membrane and the cathode. The second membrane bordering it Wenig ¬ least partially, but not completely directly on the first diaphragm to. In the electrolytic cell the decomposing carbon dioxide to a product at the cathode in the cathode chamber takes place subsequent ¬ ßend. Unreacted carbon dioxide is transported simultaneously as carbonate or hydrogen carbonate from the cathode, through the second membrane. At the same time, hydrogen ions are transported from the anode through the first membrane. Between the first and second membranes, the hydrogen ions and the carbonate or bicarbonate react to form carbon dioxide and water.
Das frei werdende Kohlenstoffdioxid kann dann über Flusskanä¬ le oder Poren zwischen der ersten und zweiten Membran frei gesetzt werden. Mit dem erfindungsgemäßen Verfahren und dem erfindungsgemäßen Elektrolyseur ist es möglich, eine Elektrolysezelle ohne ei¬ nen Spalt und ohne ein Leitsalz darin einzusetzen. Durch die Anionen-selektive Membran wird die Wasserstoffentwicklung an der Kathode vorteilhaft vermindert. Die Anionen-selektive Membran umfasst typischerweise kovalent gebundene quartäre Amine (NR4 +) , so dass Wasserstoffionen die Anionen-selektive Membran nicht durchqueren können.
Weiterhin ermöglicht das erfindungsgemäße Verfahren und der erfindungsgemäße Elektrolyseur vorteilhaft das Freisetzen von nicht umgesetztem Kohlenstoffdioxid und verhindert so den Eintritt des Kohlenstoffdioxids in den Anodenraum und somit auch eine Vermischung des im Anodenraum entstehenden Sauerstoffs mit dem Kohlenstoffdioxid . The released carbon dioxide can then be released via Flusskanä ¬ le or pores between the first and second membrane. With the method and the electrolyzer according to the invention, it is possible to use an electrolytic cell without ei ¬ nen gap and without a conductive salt in it. The anion-selective membrane advantageously reduces the evolution of hydrogen at the cathode. The anion-selective membrane typically comprises covalently bonded quaternary amines (NR 4 + ) such that hydrogen ions can not traverse the anion-selective membrane. Furthermore, the inventive method and the electrolyzer according to the invention advantageously allows the release of unreacted carbon dioxide and thus prevents the entry of the carbon dioxide into the anode space and thus also a mixing of the resulting oxygen in the anode space with the carbon dioxide.
In dem erfindungsgemäßen Elektrolyseur wird ausschließlich Wasser und Kohlenstoffdioxid verwendet. Der Einsatz eines Leitsalzes oder einer Base kann vorteilhaft vermieden werden. An der Anode wird Wasser zu Protonen und Sauerstoff zerlegt. Die Protonen können von der Anode durch die Kationen-selektive Membran in den Zwischenraum zwischen der ersten und der zweiten Membran migrieren, insbesondere über die Kationenselektive Membran permeieren. Das Kohlenstoffdioxid wird an der Kathode zu einem Produkt, insbesondere Kohlenstoffmono- xid, Ameisensäure oder Ethylen umgewandelt. Nicht umgesetztes Kohlenstoffdioxid kann mit den Hydroxidionen aus der wässri- gen Phase durch die Anionen-selektive Membran als Hydrogen¬ carbonat oder Carbonat in den migrieren, bzw. permeieren. Die erste und die zweite Membran sind mit Wasser gesättigt. In dem Zwischenraum können das Hydrogencarbonat oder Carbonat und die Wasserstoffionen zu Kohlenstoffdioxid und Wasser rea¬ gieren. Das Kohlenstoffdioxid wird dann vorteilhaft über Flusskanäle oder poröse Strukturen aus dem Zwischenraum aus dem Elektrolyseur geführt. Insbesondere können weitere Ent¬ lastungsöffnungen zwischen den Flusskanälen und/oder dem Innenraum der porösen Struktur und der äußeren Oberfläche der Kathode vorhanden sein, um eine Rückführung des Kohlendioxids und des Wassers zu gewährleisten. In the electrolyzer according to the invention only water and carbon dioxide is used. The use of a conductive salt or a base can be advantageously avoided. At the anode, water is broken down into protons and oxygen. The protons can migrate from the anode through the cation-selective membrane into the space between the first and the second membrane, in particular permeate via the cation-selective membrane. The carbon dioxide is converted to a product at the cathode, in particular carbon monoxide, formic acid or ethylene. Unreacted carbon dioxide with the hydroxide ions may migrate from the wässri- gen phase through the anion selective membrane as hydrogen carbonate or carbonate in the ¬ or permeate. The first and second membranes are saturated with water. In the intermediate space, the hydrogen carbonate or carbonate and the hydrogen ions can react to form carbon dioxide and water. The carbon dioxide is then advantageously passed through flow channels or porous structures from the gap from the electrolyzer. In particular, further Ent ¬ lastungsöffnungen between the flow channels and / or the interior of the porous structure and the outer surface of the cathode may be provided to ensure a return of the carbon dioxide and water.
Als Anionen-selektive Membranen können kommerziell erhältli¬ che Membranen verwendet werden. Insbesondere zählen dazu die Selemiom AMV von AGC Chemicals, die Neosepta von Tokuyama oder die Fumasep FAß der Fuma GmbH. In diesen Membranen sind positive Ladungen, insbesondere quartäre Amine NR4 + immobili¬ siert. Die Gesamtladung der Membran wird durch mobile Gegenionen ausgeglichen, die in der wässrigen Phase gelöst sind,
insbesondere durch Hydroxidionen. Diese Anionen-selektive Membran verhindert vorteilhaft, dass Wasserstoffionen zur Ka¬ thode transportiert werden. Vorteilhaft kann die Wahl des Ka¬ thodenmaterials dann sehr flexibel erfolgen. Die Kathodenma- terialien können dann also in Abhängigkeit des gewünschten Wertproduktes ausgewählt werden. As anion-selective membranes commercially avai ¬ che membranes can be used. In particular, these include the Selemiom AMV from AGC Chemicals, the Neosepta from Tokuyama or the Fumasep FAß from Fuma GmbH. In these membranes positive charges, in particular quaternary amines NR 4 + immobili ¬ Siert. The total charge of the membrane is counterbalanced by mobile counterions dissolved in the aqueous phase, in particular by hydroxide ions. These anion-selective membrane advantageously prevents hydrogen ions are transported to the Ka ¬ Thode. Advantageously, the choice of Ka ¬ method material can then be very flexible. The cathode materials can then be selected depending on the desired product of value.
Die zweite Membran grenzt wenigstens teilweise unmittelbar an die Kathode. Die Kathode wird zur Nutzung der inneren Ober- fläche der Kathode an die Anionen-selektive Membran über Mak- roporen angebunden. Die Makroporen haben dabei typischerweise einen Durchmesser von wenigsten einem Mikrometer. Das Anbinden der Kathode an die Anionen-selektive Membran kann in vor¬ teilhafter Weise über ein Anionen-selektives Polymer erfol- gen. Bevorzugt erfolgt die Anbindung mittels einer Lösung desselben Polymers, das bei der Präparation in einen Teil der membranseitigen Kathodenporen eindringt. Insbesondere die Oberfläche der Kathode wird mit einer Lösung des Membran¬ materials benetzt und dann auf die zweite Membran gepresst. The second membrane is at least partially directly adjacent to the cathode. The cathode is connected to the anion-selective membrane via macropores to utilize the inner surface of the cathode. The macropores typically have a diameter of at least one micrometer. The binding of the cathode to the anion-selective membrane laboration may take more advantageous before ¬ manner over an anion-selective polymer. Preferably carried out the connection by means of a solution of the same polymer which penetrates in the preparation in a portion of the diaphragm side cathode pores. In particular, the surface of the cathode is wetted with a solution of the membrane ¬ material and then pressed onto the second membrane.
Die Flüssigphase umfasst ionische Komponenten, insbesondere Hydroxidionen und Hydrogencarbonat , welche an der Kathode ge¬ bildet werden und auch in der Anionen-selektiven Membran mobil sind, so dass sievorteilhaft durch die Membran transpor- tiert werden können. Dies ermöglicht die Verbindung der Ka¬ thode mit der Anionen-selektiven Membran und somit auch die Reduzierung des Kohlenstoffdioxids . Wichtig ist dabei, dass in der Kathode dasselbe Ion wie in der Anionen-selektiven Membran mobil ist, im Falle des Wassers insbesondere The liquid phase includes ionic components, in particular hydroxide ions and hydrogen carbonate which are ge at the cathode forms ¬ and are mobile in the anion-selective membrane so that the membrane sievorteilhaft can be trans- ported. This allows the connection of the Ka ¬ method with the anion-selective membrane and thus the reduction of the carbon dioxide. It is important that in the cathode the same ion as in the anion-selective membrane is mobile, in the case of the water in particular
Hydroxidionen. Die Anbindung der Anionen leitenden Membran an die Kathode erfolgt dabei typischerweise durch Imprägnieren der Membranseite der Kathode mit einem Anionen-leitenden Polymer. Dabei grenzt die Anionen-selektive zweite Membran wenigsten teilweise unmittelbar an die Kathode an. Das aufge- brachte Polymer wird durch die Polymerisation zu einem Teil der Membran.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbildung der Erfindung ist zwischen der ersten und der zweiten Membran eine gemeinsame Kontaktfläche angeordnet, wobei die Größe der Kontaktfläche in dem Bereich von wenigstens 80% bis zu 98 % der Membranfläche der ersten Membran liegt. Die Memb¬ ranen berühren sich in der Elektrolysezelle, allerdings be¬ rühren sie sich nicht vollständig. Zum einen ist es von Vor¬ teil, wenn sie sich nicht vollständig berühren, da dann Hydroxide ions. The connection of the anion-conducting membrane to the cathode is typically carried out by impregnating the membrane side of the cathode with an anion-conducting polymer. In this case, the anion-selective second membrane at least partially adjoins the cathode directly. The applied polymer becomes part of the membrane due to the polymerization. In a further advantageous embodiment and development of the invention, a common contact surface is arranged between the first and the second membrane, wherein the size of the contact surface is in the range of at least 80% to 98% of the membrane area of the first membrane. The Memb ¬ Ranen touch in the electrolytic cell, however, be ¬ they do not move completely. On the one hand, it is of advantage if they do not touch completely, because then
Flusskanäle oder Poren geöffnet bleiben, um nicht umgesetztes Kohlenstoffdioxid und gebildetes Wasser aus dem Kontaktbe¬ reich der beiden Membranen herausführen zu können. Andererseits ist es von Vorteil, wenn sich die erste und die zweite Membran großflächig berühren, um eine möglichst hohe Leitfähigkeit innerhalb der Elektrolysezelle aufrechtzuerhalten und somit den Energiebedarf der Elektrolysezelle möglichst nied¬ rig, das heißt effizient, zu gestalten. Flow channels or pores remain open to be able to lead unreacted carbon dioxide and water formed from the Kontaktbe ¬ rich of the two membranes. On the other hand, it is advantageous if the first and the second diaphragm touch a large area in order to maintain a high conductivity as possible within the electrolytic cell, and thus the energy requirement of the electrolytic cell as possible nied ¬ rig, that is, to improve its efficiency.
In einer weiteren Ausgestaltung und Weiterbildung der Erfindung umfasst die Kathode und/oder die zweite Membran Entlas- tungsöffnungen, um das Kohlenstoffdioxid und das Wasser aus der Abstandshaltevorrichtung in den gasseitigen Kathodenraum zu führen. Der gasseitige Kathodenraum befindet sich auf der anodenabgewandten Seite der Kathode. Aus diesem gasseitigen Kathodenraum wird das Edukt Kohlenstoffdioxid zugeführt. Ein Führen des in der Abstandshaltevorrichtung entstehenden Wassers und Kohlenstoffdioxids in den gasseitigen Kathodenraum ermöglicht vorteilhaft einen höheren Umsatz des Kohlenstoff¬ dioxids und somit auch eine höhere Effizienz. In einer weiteren vorteilhaften Ausgestaltung und Weiterbildung der Erfindung ist zwischen der ersten und zweiten Membran eine Abstandshaltevorrichtung angeordnet. Diese Abstands¬ haltevorrichtung kann Maschen, Gitter oder eine poröse Struktur umfassen. Vorteilhafterweise lässt sich so die Kontakt- fläche zwischen der ersten und zweiten Membran definiert vorgeben, sodass einerseits für ausreichend Flusskanäle für frei werdendes Kohlenstoffdioxid, und andererseits für eine aus¬ reichende Leitfähigkeit der Elektrolysezelle gesorgt ist.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbildung der Erfindung umfasst die Kathode wenigstens eines der Elemente Silber, Kupfer, Blei, Indium, Zinn oder Zink. Die Auswahl des Kathodenmaterials hängt insbesondere von dem ge¬ wünschten Wertprodukt der Kohlenstoffdioxidzerlegung ab. Insbesondere wird mit dem Einsatz einer Silberkathode Kohlen- stoffmonoxid hergestellt. Mit dem Einsatz einer Kupferkathode wird Ethylen und mit dem Einsatz einer Bleikathode wird Amei- sensäure produziert. Vorteilhaft kann mit dem Aufbau derIn a further embodiment and further development of the invention, the cathode and / or the second membrane comprises relief openings in order to guide the carbon dioxide and the water from the spacer device into the gas-side cathode space. The gas-side cathode compartment is located on the anode side facing away from the cathode. From this gas-side cathode space, the starting material carbon dioxide is supplied. Guiding the resulting in the spacer device water and carbon dioxide in the gas-side cathode space advantageously allows a higher conversion of carbon dioxide ¬ and thus a higher efficiency. In a further advantageous embodiment and development of the invention, a spacer device is arranged between the first and second membrane. This spacer ¬ holding device may comprise mesh, grid or a porous structure. Advantageously, as can be the contact surface between the first and second membrane defining pretend so that it is ensured on the one hand for sufficient flow channels for liberated carbon dioxide, and on the other hand, for reaching from ¬ conductivity of the electrolysis cell. In a further advantageous embodiment and development of the invention, the cathode comprises at least one of the elements silver, copper, lead, indium, tin or zinc. The choice of the cathode material depends especially on the ge ¬ desired value of the product Kohlenstoffdioxidzerlegung. In particular, the use of a silver cathode produces carbon monoxide. With the use of a copper cathode, ethylene is produced and with the use of a lead cathode, formic acid is produced. Advantageously, with the structure of
Elektrolysezelle die freie Wahl des Kathodenmaterials erfol¬ gen und gleichzeitig die Produktion von unerwünschtem Wasserstoff an der Kathode unterbunden werden. Die Kathode ist da¬ bei typischerweise als eine Gasdiffusionselektrode ausgebil- det. Unter einer Gasdiffusionselektrode versteht man eine gut elektronisch leitfähige, poröse Katalysatorstruktur, die teilweise mit dem angrenzenden Membranmaterial benetzt ist, wobei verbleibende Porenräume zur Gasseite hin geöffnet sind. In einer vorteilhaften Ausgestaltung und Weiterbildung derElectrolysis cell the free choice of the cathode material suc ¬ conditions and simultaneously the production of unwanted hydrogen are prevented at the cathode. The cathode is then ¬ at typically as a gas diffusion electrode trained det. A gas diffusion electrode is understood as meaning a well-electronically conductive, porous catalyst structure which is partially wetted by the adjacent membrane material, remaining pore spaces being open towards the gas side. In an advantageous embodiment and development of
Erfindung wird das nicht umgesetzte und daher wieder freige¬ setzte Kohlenstoffdioxid als Edukt zurück in den Elektroly- seur geführt. Vorteilhaft wird dadurch die Effizienz der Elektrolyse gesteigert, da möglichst viel Kohlenstoffdioxid umgesetzt wird. Invention, the unreacted and therefore released again ¬ carbon dioxide is fed as educt back into the electroly- se. Advantageously, the efficiency of the electrolysis is increased because as much carbon dioxide is reacted.
In einer weiteren vorteilhaften Ausgestaltung und Weiterbildung der Erfindung wird der Elektrolyseur mit reinem Wasser betrieben. Als reines Wasser wird hierbei Wasser bezeichnet, welches eine Leitfähigkeit von weniger als 1 mS/cm aufweist. Vorteilhaft wird dadurch vermieden, dass Salze, insbesondere Hydrogencarbonate, in der Elektrolysezelle ausfallen und so¬ mit zu einer verkürzten Lebenszeit der Elektrolysezelle füh¬ ren . In a further advantageous embodiment and development of the invention, the electrolyzer is operated with pure water. As pure water in this case water is called, which has a conductivity of less than 1 mS / cm. , Is avoided by advantageous that salts, in particular hydrogen carbonates, precipitated in the electrolytic cell and so ¬ with a shortened lifetime of the electrolysis cell füh ¬ ren.
Weitere Ausgestaltungsform und weitere Merkmale der Erfindung werden anhand der folgenden Figuren näher erläutert. Dabei handelt es sich um rein beispielhafte Ausgestaltungsformen
und Merkmalskombinationen, die keine Einschränkung des Further embodiment and further features of the invention will be explained in more detail with reference to the following figures. These are purely exemplary embodiments and feature combinations that do not limit the
Schutzbereiches bedeutet. Merkmale mit derselben Wirkungswei¬ se und derselben Bezeichnung, aber in unterschiedlichen Ausgestaltungsformen werden dabei mit denselben Bezugszeichen versehen. Protected area means. Features with the same Wirkungswei ¬ se and the same name, but in different embodiments are given the same reference numerals.
Dabei zeigen: Showing:
Fig. 1 eine Elektrolysezelle mit einer Anionen-selektiven Fig. 1 is an electrolytic cell with an anion-selective
Membran, Membrane,
Fig. 2 eine Abstandshalterung für die Elektrolysezelle mit einer Anionen-selektiven Membran. Die Elektrolysezelle 1 umfasst einen Kathodenraum 14 und ei¬ nen Anodenraum 13. Der Kathodenraum 14 wird vom Anodenraum 13 über eine Abstandshaltevorrichtung 11 getrennt. In dem Anodenraum 13 ist eine Kationen-selektive Membran 3 angeordnet. An diese grenzt direkt eine Anode 4 an . In dem Kathoden- räum 14 ist eine Anionen-selektive Membran 2 angeordnet. An diese grenzt die Kathode 5 an. Die Kathode 5 ist mit der An¬ ionen-selektiven Membran 2 über ein Anionen-selektives Polymer verbunden. Zwischen der Anionen-selektiven Membran 2 und der Kationen-selektiven Membran ist eine Abstandshalterung 11 angeordnet. Die Membranen berühren sich zu 90 % über die Kontaktflächen 9. Fig. 2 shows a spacer for the electrolysis cell with an anion-selective membrane. The electrolytic cell 1 comprises a cathode chamber 14 and egg ¬ nen anode compartment 13. The cathode compartment 14 is separated from the anode compartment 13 via a spacer device 11. In the anode compartment 13, a cation-selective membrane 3 is arranged. An anode 4 directly adjoins this. An anion-selective membrane 2 is arranged in the cathode space 14. At this the cathode 5 adjoins. The cathode 5 is connected to the on ¬ ion-selective membrane 2 through an anion-selective polymer. Between the anion-selective membrane 2 and the cation-selective membrane, a spacer 11 is arranged. The membranes touch 90% over the contact surfaces. 9
Zweckmäßigerweise wird die Elektrolysezelle 1 mit Spannung versorgt, sodass eine Elektrolyse stattfinden kann. In der Elektrolysezelle 1 wird Kohlenstoffdioxid zu Kohlenstoffmono- xid reduziert. Dies geschieht typischerweise an einer Silber¬ kathode. Sowohl in der Anionen-selektiven Membran 2 als auch in der Kationen-selektiven Membran 3 liegt Wasser vor. In der Kationen-selektiven Membran 3, an welche bevorzugt immobili- sierte negative Ladungen, insbesondere deprotonierte Sulfon- säuregruppen, angebunden sind, kann sich positive Ladung, insbesondere ein Proton, bewegen. Dies wird durch das Konzentrationsprofil des Wasserstoffions 7 in dem Anodenraum 13
gezeigt. An der Anionen-selektiven Membran 2 hingegen sind typischerweise quartäre Amine NR4 + immobilisiert, was zu ei¬ ner Ladungsoberfläche mit einer positiven Ladung führt. Durch diese positiv geladene Oberfläche können sich insbesondere negativ geladene Hydroxidionen durch diese Membran bewegen. Dies wird verdeutlicht durch das Konzentrationsprofil des Hydroxidions 6. Negative Ladungen können innerhalb der Anio¬ nen-selektiven Membran 2 in Form von Hydrogencarbonat oder Carbonat vorliegen und transportiert werden (In Konzentrati- onsprofil nicht gezeigt) . Conveniently, the electrolytic cell 1 is supplied with voltage, so that electrolysis can take place. In the electrolysis cell 1, carbon dioxide is reduced to carbon monoxide. This typically happens at a silver cathode ¬. Both in the anion-selective membrane 2 and in the cation-selective membrane 3 water is present. In the cation-selective membrane 3, to which preferably immobilized negative charges, in particular deprotonated sulfonic acid groups, are attached, positive charge, in particular a proton, can move. This is due to the concentration profile of the hydrogen ion 7 in the anode compartment 13 shown. Quaternary amines NR 4 + are typically immobilized on the anion-selective membrane 2 on the other hand, resulting in egg ¬ ner surface charge with a positive charge. As a result of this positively charged surface, negatively charged hydroxide ions in particular can move through this membrane. This is illustrated by the concentration profile of the hydroxide 6. Negative charges may be present within the Anio ¬ NEN-selective membrane 2 in the form of bicarbonate or carbonate and transported (in concentration profile not shown).
Liegt nun eine Spannung an der Elektrolysezelle 1 an, so wird an der Kathode 5, welche Silber umfasst, das Kohlenstoffdio- xid zu Kohlenstoffmonoxid reduziert. Zeitgleich wird in dem Anodenraum 13 Wasser zu Protonen und Sauerstoff zerlegt. Der Sauerstoff kann den Anodenraum verlassen. Die Protonen können über die Kationen-selektive Membran 3 in den Zwischenraum zwischen Gitterstäben 8 des Gitters des Abstandshalters 11 migrieren. Nicht-umgesetztes Kohlenstoffdioxid kann mit If a voltage is applied to the electrolysis cell 1, the carbon dioxide is reduced to carbon monoxide at the cathode 5, which comprises silver. At the same time, water is decomposed into protons and oxygen in the anode compartment 13. The oxygen can leave the anode compartment. The protons can migrate via the cation-selective membrane 3 into the gap between bars 8 of the grid of the spacer 11. Unreacted carbon dioxide can with
Hydroxidionen zu Carbonat oder Hydrogencarbonat reagieren und durch die Anionen-selektive Membran migrieren. Das Hydrogencarbonat oder Carbonat und die Wasserstoffionen können dann in dem Zwischenraum innerhalb der Gitterstruktur 8 zu Kohlenstoffdioxid und Wasser reagieren. Das Kohlenstoffdioxid kann so aus der Elektrolysezelle wieder freigesetzt werden, wäh¬ rend das Wasser zurück in die beiden Membranen diffundieren kann. Weiterhin wird vorteilhaft die Bildung von Wasserstoff an der Kathode vermieden, da das Proton aufgrund seiner positiven Ladung die Anionen-selektive Membran nicht durchqueren kann. Hydroxide ions react to carbonate or bicarbonate and migrate through the anion-selective membrane. The bicarbonate or carbonate and the hydrogen ions may then react in the space within the lattice structure 8 to carbon dioxide and water. The carbon dioxide can thus be released from the electrolytic cell again, currency ¬ rend the water can diffuse back into the two membranes. Furthermore, the formation of hydrogen at the cathode is advantageously avoided, since the proton can not cross the anion-selective membrane due to its positive charge.
Typischerweise werden Anionen-selektive Membranen, welche kommerziell erhältlich sind, verwendet. Um die Anionen-selek¬ tive Membran 2 fest mit der Kathode 5 zu verbinden, werden die Anionen-selektive Membran 2 und die Kathode 5 über ein Anionen-selektives Polymer 12 fest miteinander verbunden.
Dieses Anionen-selektive Polymer 12 benetzt die Kathode 5 nicht vollständig, sodass zum Gasraum durchgehende Öffnungen bzw. Poren bleiben, durch welche das Kohlenstoffdioxid dif¬ fundieren kann. Aus der Kathode 5 werden unter Nutzung der inneren Oberfläche der Kathode 5 durch die Makroporen Typically, anion-selective membranes that are commercially available are used. To connect the anion-selec tive membrane ¬ 2 fixedly connected to the cathode 5, the anion-selective membrane 2 and the cathode 5 are fixedly connected to each other through an anion-selective polymer 12th This anion-selective polymer 12 not completely wetted the cathode 5, so that the gas space through openings or pores remain through which the carbon dioxide can dif ¬ substantiate. From the cathode 5 are using the inner surface of the cathode 5 through the macropores
Hydroxidionen ausgeleitet. Dies stellt sicher, dass der Io¬ nentransport von der Kathode 5 zur Anionen-selektiven Membran 2 erfolgt. Die Kathode 5 ist typischerweise als Gasdiffusionselektrode ausgestaltet . Hydroxide ions discharged. This ensures that the Io ¬ nentransport from the cathode 5 is carried to the anion selective membrane. 2 The cathode 5 is typically designed as a gas diffusion electrode.
In Figur 2 ist abschnittsweise die Abstandshaltevorrich- tung 10 als Gitterstruktur 8 gezeigt. Die schraffierten Flä- chen beschreiben hier die Kontaktflächen der Anionen-selektiven Membran 2 und der Kationen-selektiven Membran 3. Die weiße Fläche zwischen der Kontaktfläche und der Gitterstruk¬ tur 8 bezeichnet Flusskanäle 10 durch welche das im Zwischen¬ raum entstehende Kohlenstoffdioxid die Elektrolysezelle ver- lassen kann. Es ist vorteilhaft möglich durch die Abstands- halterung 11 das Kohlenstoffdioxid und das Kohlenstoffmonoxid vom Anodengas Sauerstoff zu trennen. Weiterhin ist es mög¬ lich, lediglich Wasser zum Betreiben der Elektrolysezelle 1 einzusetzen. Dies ist dadurch möglich, dass die Anode und die Kathode derart zueinander angeordnet sind, dass die Leitfä¬ higkeit über die Anionen-selektive Membran 2 und die Katio¬ nen-selektive Membran 3 ausreichend hoch ist. Es wird also vorteilhaft vermieden, ein Leitsalz oder einen Puffer zu verwenden. Vorteilhafterweise kann es dadurch nicht zu einem Ausfallen von insbesondere Hydrogencarbonaten als Feststoff kommen. Die Lebensdauer der Elektrolysezelle wird so vorteil¬ haft erhöht. Weiterhin steigert das vorteilhaft die Effizienz der Elektrolysezelle.
In FIG. 2, the spacer device 10 is shown in sections as a lattice structure 8. The hatched spots on describe the contact surfaces of the anion-selective membrane 2 and the cation selective membrane 3. The white area between the contact surface and the grating structural ¬ tur 8 denotes flow channels 10 through which the resulting in the intermediate ¬ space carbon dioxide, the electrolytic cell ver - can let. It is advantageously possible by means of the spacer holder 11 to separate the carbon dioxide and the carbon monoxide from the anode gas oxygen. Furthermore, it is mög ¬ Lich to use only water to operate the electrolysis cell. 1 This is possible because the anode and the cathode are arranged to one another such that the Leitfä ¬ capability is sufficiently high on the anion-selective membrane 2 and the Katio ¬ NEN-selective membrane. 3 It is thus advantageously avoided to use a conductive salt or a buffer. Advantageously, this can not lead to a precipitation of particular hydrogencarbonates as a solid. The life of the electrolytic cell is increased so advantageous ¬ . Furthermore, this advantageously increases the efficiency of the electrolysis cell.
Claims
1. Elektrolyseur zur elektrochemischen Nutzung von Kohlenstoffdioxid umfassend wenigstens eine Elektrolysezelle (1), wobei die Elektrolysezelle (1) 1. Electrolyzer for the electrochemical use of carbon dioxide comprising at least one electrolysis cell (1), the electrolysis cell (1)
- einen Anodenraum (13) mit einer Anode (4) und einen Kathodenraum (14) mit einer Kathode (5) umfasst , - an anode compartment (13) with an anode (4) and a cathode compartment (14) with a cathode (5),
- zwischen dem Anodenraum (13) und dem Kathodenraum (14) eine erste Kationen-permeable Membran (3) angeordnet ist und - A first cation-permeable membrane (3) is arranged between the anode space (13) and the cathode space (14) and
- die Anode (4) direkt an die erste Membran (3) im Anodenraum (13) grenzt, dadurch gekennzeichnet, dass zwischen der ersten Membran (3) und der Kathode (5) eine zweite Anionen-selektive Membran (2) angeordnet ist und die zweite Membran (2) wenigs- tens teilweise aber nicht vollständig unmittelbar an die ers¬ te Membran (3) grenzt und wobei die zweite Membran (2) we¬ nigstens teilweise unmittelbar an die Kathode (5) grenzt. - the anode (4) borders directly on the first membrane (3) in the anode space (13), characterized in that a second anion-selective membrane (2) is arranged between the first membrane (3) and the cathode (5) and the second membrane (2) at least partially but not completely borders directly on the first membrane (3) and the second membrane (2) at least partially borders directly on the cathode (5).
2. Elektrolyseur nach Anspruch 1, wobei zwischen der ersten (3) und zweiten Membran (2) eine gemeinsame Kontaktfläche2. Electrolyzer according to claim 1, wherein a common contact surface between the first (3) and second membrane (2).
(9) angeordnet ist, wobei die Größe der Kontaktflächen (9) in einem Bereich von wenigstens 80% bis zu 98 % der Membranfläche der ersten und/oder zweiten Membran liegt. (9) is arranged, the size of the contact surfaces (9) being in a range of at least 80% up to 98% of the membrane area of the first and / or second membrane.
3. Elektrolyseur nach einem der vorhergehenden Ansprüche, wobei zwischen der ersten (3) und zweiten (2) Membran eine Ab- standshaltevorrichtung (11) angeordnet ist. 3. Electrolyzer according to one of the preceding claims, wherein a spacer device (11) is arranged between the first (3) and second (2) membrane.
4. Elektrolyseur nach einem der vorhergehenden Ansprüche, wo- bei die Kathode (5) und/oder die zweite Membran (2) Entlas¬ tungsöffnungen zum Führen von Kohlenstoffdioxid und Wasser aus der Abstandshaltevorrichtung (11) in den gasseiteigen Kathodenraum umfassen. 4. Electrolyzer according to one of the preceding claims, wherein the cathode (5) and / or the second membrane (2) comprise discharge openings for guiding carbon dioxide and water from the spacer device (11) into the gas-side cathode space.
5. Elektrolyseur nach Anspruch 3 oder 4, wobei die Abstandshaltevorrichtung (11) Maschen, Gitter (8) oder eine poröse Struktur umfasst.
5. Electrolyser according to claim 3 or 4, wherein the spacer device (11) comprises meshes, grids (8) or a porous structure.
6. Elektrolyseur nach einem der vorhergehenden Ansprüche, wobei zwischen der Kathode (5) und der zweiten Membran (2) wenigstens teilweise ein Anionen-leitendes Polymer (12) ange¬ ordnet ist. 6. Electrolyzer according to one of the preceding claims, wherein an anion-conducting polymer (12) is at least partially arranged between the cathode (5) and the second membrane (2).
7. Elektrolyseur nach einem der vorhergehenden Ansprüche, wobei die Kathode (5) wenigstens eines der Elemente Silber, Kupfer, Blei, Indium, Zinn oder Zink umfasst. 7. Electrolyzer according to one of the preceding claims, wherein the cathode (5) comprises at least one of the elements silver, copper, lead, indium, tin or zinc.
8. Elektrolyseur nach einem der vorhergehenden Ansprüche, wobei die Kathode (5) eine Gasdiffusionselektrode umfasst. 8. Electrolyzer according to one of the preceding claims, wherein the cathode (5) comprises a gas diffusion electrode.
9. Verfahren zum Betreiben eines Elektrolyseurs zur elektro¬ chemischen Nutzung von Kohlenstoffdioxid mit folgenden 9. Method for operating an electrolyzer for the electrochemical use of carbon dioxide with the following
Schritten: Steps:
- Bereitstellen eines Elektrolyseurs mit einer Elektrolyse¬ zelle (1) mit einem Anodenraum (13) mit einer Anode (4) und einem Kathodenraum (14) mit einer Kathode (5), wobei zwischen dem Anodenraum (13) und dem Kathodenraum (14) eine erste Ka- tionen-permeable Membran (3) angeordnet ist und die Anode (4) direkt an die erste Membran (3) grenzt, und zwischen der ers¬ ten Membran (3) und der Kathode (5) eine zweite Anionen- selektive Membran (2) angeordnet ist und die zweite Membran (2) wenigstens teilweise aber nicht vollständig unmittelbar an die erste Membran (3) grenzt, - Providing an electrolyzer with an electrolysis cell (1) with an anode compartment (13) with an anode (4) and a cathode compartment (14) with a cathode (5), with between the anode compartment (13) and the cathode compartment (14) a first cation-permeable membrane (3) is arranged and the anode (4) borders directly on the first membrane (3), and between the first ¬th membrane (3) and the cathode (5) a second anion-selective Membrane (2) is arranged and the second membrane (2) at least partially but not completely borders directly on the first membrane (3),
- Zerlegen von Kohlenstoffdioxid zu einem Produkt an der Ka¬ thode (5) in dem Kathodenraum (14), - decomposing carbon dioxide into a product at the cathode (5) in the cathode compartment (14),
- Transportieren von nicht umgesetztem Kohlenstoffdioxid als Carbonat oder Hydrogencarbonat von der Kathode (5) durch die zweite Membran (2), - Transportieren von Wasserstoffionen von der Anode (4) durch die erste Membran (3) ,
- Reagieren der Wasserstoffionen und des Carbonats oder - Transporting unreacted carbon dioxide as carbonate or hydrogen carbonate from the cathode (5) through the second membrane (2), - Transporting hydrogen ions from the anode (4) through the first membrane (3), - Reaction of the hydrogen ions and the carbonate or
Hydrogencarbonats zu Kohlenstoffdioxid und Wasser zwischen der ersten (3) und der zweiten Membran (2), - Freisetzen des Kohlenstoffdioxids über Flusskanäle oder Po¬ ren zwischen der ersten (3) und der zweiten Membran (2) . Hydrogen carbonate to carbon dioxide and water between the first (3) and the second membrane (2), - releasing the carbon dioxide via flow channels or Po ¬ ren between the first (3) and the second membrane (2).
10. Verfahren nach Anspruch 9, wobei das freigesetzte Kohlenstoffdioxid als Edukt zurück in den Elektrolyseur geführt wird. 10. The method according to claim 9, wherein the released carbon dioxide is fed back into the electrolyzer as starting material.
11. Verfahren nach einem der Ansprüche 9 oder 10, wobei der Elektrolyseur mit reinem Wasser betrieben wird. 11. The method according to any one of claims 9 or 10, wherein the electrolyzer is operated with pure water.
12. Verfahren nach einem der Ansprüche 9 bis 11, wobei die12. The method according to any one of claims 9 to 11, wherein the
Flusskanäle oder Poren mittels einer Abstandshaltevorrichtung (11) ausgebildet werden. Flow channels or pores are formed by means of a spacer device (11).
13. Verfahren nach einem der Ansprüche 9 bis 12, wobei we- nigstens eins der Produkte Kohlenstoffmonoxid, Ethylen oder Ameisensäure hergestellt werden.
13. The method according to any one of claims 9 to 12, wherein at least one of the products carbon monoxide, ethylene or formic acid is produced.
Priority Applications (1)
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| PL17724515T PL3414362T3 (en) | 2016-05-31 | 2017-05-08 | Device and method for the electrochemical utilisation of carbon dioxide |
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| DE102016209451.3A DE102016209451A1 (en) | 2016-05-31 | 2016-05-31 | Apparatus and method for the electrochemical use of carbon dioxide |
| PCT/EP2017/060885 WO2017207220A1 (en) | 2016-05-31 | 2017-05-08 | Device and method for the electrochemical utilisation of carbon dioxide |
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| EP (1) | EP3414362B1 (en) |
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| DE102016209451A1 (en) | 2016-05-31 | 2017-11-30 | Siemens Aktiengesellschaft | Apparatus and method for the electrochemical use of carbon dioxide |
| CN113795611A (en) * | 2019-05-05 | 2021-12-14 | 多伦多大学管理委员会 | Conversion of carbonates to synthesis gas or C2+ products in an electrolytic cell |
| CN115380132A (en) | 2019-11-25 | 2022-11-22 | 十二益公司 | Membrane electrode assembly for COx reduction |
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| EP0612864B1 (en) | 1993-02-26 | 1999-05-06 | Permelec Electrode Ltd. | Electrolytic cell and processes for producing alkali hydroxide and hydrogen peroxide |
| JP2006219746A (en) | 2005-02-14 | 2006-08-24 | Nippon Telegr & Teleph Corp <Ntt> | Hydrogen production method and device |
| JP5373079B2 (en) | 2008-07-16 | 2013-12-18 | カレラ コーポレイション | Use of CO2 in electrochemical systems |
| CN101649464A (en) | 2008-08-11 | 2010-02-17 | 浙江工业大学 | Carbon dioxide decomposing oxygen generator |
| DE102009013207A1 (en) * | 2009-03-17 | 2010-09-23 | Rheinisch-Westfälische Technische Hochschule Aachen | Bipolar membrane |
| US9370773B2 (en) | 2010-07-04 | 2016-06-21 | Dioxide Materials, Inc. | Ion-conducting membranes |
| US10047446B2 (en) * | 2010-07-04 | 2018-08-14 | Dioxide Materials, Inc. | Method and system for electrochemical production of formic acid from carbon dioxide |
| US8529758B2 (en) * | 2011-03-22 | 2013-09-10 | Dionex Corporation | CO2-removal device and method |
| ITMI20110500A1 (en) * | 2011-03-29 | 2012-09-30 | Industrie De Nora Spa | CELL FOR DEPOLARIZED ELECTRODIALISIS OF SALINE SOLUTIONS |
| CN103160851B (en) | 2011-12-12 | 2015-11-25 | 清华大学 | Membrane reactor |
| US8845876B2 (en) | 2012-07-26 | 2014-09-30 | Liquid Light, Inc. | Electrochemical co-production of products with carbon-based reactant feed to anode |
| CN102912374B (en) | 2012-10-24 | 2015-04-22 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank |
| CN103191633B (en) * | 2013-04-09 | 2014-08-13 | 浙江大学 | Device and method for electrically acquiring and purifying carbon dioxide |
| CA2960595C (en) * | 2014-09-08 | 2022-04-12 | 3M Innovative Properties Company | Ionic polymer membrane for a carbon dioxide electrolyzer |
| US20160253461A1 (en) | 2014-10-01 | 2016-09-01 | Xsolis, Llc | System for management and documentation of health care decisions |
| CN105297067B (en) | 2015-11-16 | 2018-02-09 | 昆明理工大学 | A kind of multicell diaphragm electrolysis method and apparatus by carbon dioxide electroreduction for carbon monoxide |
| DE102016209451A1 (en) | 2016-05-31 | 2017-11-30 | Siemens Aktiengesellschaft | Apparatus and method for the electrochemical use of carbon dioxide |
| DE102016209447A1 (en) * | 2016-05-31 | 2017-11-30 | Siemens Aktiengesellschaft | Process and apparatus for the electrochemical use of carbon dioxide |
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| ES2795037T3 (en) | 2020-11-20 |
| US11193213B2 (en) | 2021-12-07 |
| US20200325587A1 (en) | 2020-10-15 |
| SA518400459B1 (en) | 2022-05-08 |
| WO2017207220A1 (en) | 2017-12-07 |
| AU2017273604A1 (en) | 2018-10-25 |
| EP3414362B1 (en) | 2020-03-25 |
| PL3414362T3 (en) | 2020-08-24 |
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| AU2017273604B2 (en) | 2020-01-02 |
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