EP1499756A2 - Verfahren zur rückführung von prozessgas in elektrochemischen prozessen - Google Patents
Verfahren zur rückführung von prozessgas in elektrochemischen prozessenInfo
- Publication number
- EP1499756A2 EP1499756A2 EP02800578A EP02800578A EP1499756A2 EP 1499756 A2 EP1499756 A2 EP 1499756A2 EP 02800578 A EP02800578 A EP 02800578A EP 02800578 A EP02800578 A EP 02800578A EP 1499756 A2 EP1499756 A2 EP 1499756A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- gas
- pressure
- residual
- jet pump
- electrochemical
- 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
- 238000000034 method Methods 0.000 title claims abstract description 137
- 230000008569 process Effects 0.000 title claims abstract description 106
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 29
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 155
- 239000000463 material Substances 0.000 description 40
- 239000003054 catalyst Substances 0.000 description 31
- 238000005868 electrolysis reaction Methods 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 13
- 239000004332 silver Substances 0.000 description 13
- 239000012528 membrane Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910001092 metal group alloy Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000035508 accumulation Effects 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000036284 oxygen consumption Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002759 woven fabric Substances 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
- C25B15/00—Operating or servicing cells
-
- 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
Definitions
- the invention relates to a method for recycling process gas in electrochemical processes with gas diffusion electrodes.
- a stoichiometric excess of educt gas is required, for example, when using electrochemical cells based on gas diffusion electrodes.
- gas diffusion electrodes enables alternative reaction paths in different electrochemical processes and prevents the formation of undesirable or uneconomical by-products.
- An example of a gas diffusion electrode is the oxygen-nerzehr cathode.
- This electrode is an open-pore membrane which is arranged between the electrolyte and the gas space and has an electrically conductive layer with a catalyst. This arrangement ensures that the oxygen reduction at the three-phase boundary between the electrolyte, catalyst and oxygen takes place as close as possible to the electrolyte.
- oxygen-nerzehr cathodes are used, for example, in alkali metal halide electrolysis.
- oxygen is added as the starting gas in the oxygen-nerzehr cathode.
- the resulting residual oxygen gas is removed from the process and fed to the exhaust gas without further use.
- Disadvantages of the previous procedure are, on the one hand, the high oxygen consumption and, on the other hand, the time-consuming cleaning required before releasing the residual gas to the environment, for example using washing columns.
- the residual gas can also be worked up for reuse, but this also requires scrubbing columns or filters as well as compressors for the return to the process.
- the return to the process by means of a compressor requires the hydrogen chloride (HC1) and possible chlorine content of the
- Residual gas high-quality materials for the compressor or alternatively a constant washing of the recycled gas with a large amount of sodium hydroxide.
- Gas jet pumps are propellant pumps that generate a vacuum and are particularly suitable for use as a vacuum pump. Except for the choice of a ' gaseous propellant, gas jet pumps match the liquid jet pumps. Steam, for example, can be used as the blowing agent.
- the invention has for its object to provide a reprocessing process for residual gases in electrolysis processes with gas diffusion electrodes, which does not have the aforementioned disadvantages.
- the consumption of reactant gases is to be reduced and the dimensions of the necessary scrubbers and thus also the washing media consumption are to be reduced.
- the use of cost-intensive compressors should be avoided.
- damage to the membrane and the sensitive gas diffusion electrode should be avoided.
- a method for recycling process gas in electrochemical processes, in particular in electrolysis processes, with at least one gas diffusion electrode has been found, which comprises at least the following steps:
- An essential aspect of the invention is the excess gas in
- Electrolysis processes with gas diffusion electrodes, which were previously released as exhaust gas, can be directly returned to the process. This leads to a reduction in the
- a gas jet pump enables the educt gas-rich residual gas to be returned directly to the process without drying or cleaning being necessary.
- a preferred embodiment of the invention thus includes the return of residual gas to the process via a gas jet pump using the pressure difference between the starting gas and process gas as the driving force, the regulation of the recycled gas quantity and the outflow of a residual gas partial flow in order to discharge impurities and to avoid them of overpressure.
- the residual gas is preferably returned to the process together with the starting gas via the gas jet pump.
- the residual gas generated by HC1 or NaCl membrane electrolysis mainly contains oxygen and also water vapor, HC1 and, in the event of membrane damage, also chlorine.
- the residual gas can contain traces of sodium hydroxide solution (NaOH).
- NaOH sodium hydroxide solution
- the discharge of the residual gas as exhaust air would require a large-sized exhaust air scrubber and a high consumption of sodium hydroxide solution for washing.
- the oxygen used with a 50% excess would be released as exhaust air.
- the return to the process by means of a compressor would require expensive materials for the compressor or a constant washing of the recycled gas quantity with a high consumption of sodium hydroxide solution due to the HC1 and possible chlorine content of the residual gas.
- the use of a gas jet pump according to the invention now enables the feed gas containing residual gas to be returned directly to the process without drying or cleaning being necessary. As a result, the previously necessary humidification of the feed gas can be dispensed with.
- the oxygen consumption can be reduced by about 33%, since the excess necessary for the process is achieved by the recycled residual gas, which can be adjusted again with a volume flow, which is preferably greater than 90% of the residual gas flow and, if necessary, via a control element is available.
- the non-recycled portion of the residual gas flow is fed to the exhaust gas with a volume flow that is preferably less than about 10%, particularly preferably less than about 1%, of the pure oxygen content of the feed gas.
- the quantity control in the recycled gas flow and the outflow of the discharged residual gas avoid excess pressure or pressure fluctuations in the cathode compartment of the electrolysis, which can lead to membrane and electrode damage.
- the outflow of the non-recycled portion of the residual gas stream further prevents the accumulation of impurities, in particular inert gases, in the process.
- the process according to the invention can be used in any electrochemical processes which require the use of gaseous starting materials in a stoichiometric excess.
- Any gas diffusion electrodes can also be used in the method according to the invention, e.g. an oxygen-consuming cathode.
- the method according to the invention is preferably used in electrochemical processes, in particular in electrolysis processes, which take place using an oxygen-consuming cathode.
- the method is also preferably used in electrolysis processes in which oxygen is essentially added as the starting gas.
- electrolysis processes which can be carried out using the process according to the invention are, in particular, NaCl and HCl electrolysis, but also, for example, processes for recycling ammonium sulfate or ammonium nitrate using oxygen-consuming cathodes.
- Particularly preferred electrolysis processes are NaCl electrolysis and HCl electrolysis with oxygen-consuming cathodes, in which oxygen is added with about 50% stoichiometric excess, based on pure oxygen.
- the process pressure at which the electrochemical process is operated depends on the type of electrochemical process and the gas diffusion electrode selected and is generally in the range from 0.001 to 10 bar, preferably 10 to 250 mbar, in particular 10 to 200 mbar, above atmospheric pressure , particularly preferred at atmospheric pressure.
- the feed gas pressure applied to the gas jet pump is generally 0.1 to 40 bar higher than the process pressure.
- the educt gas pressure is preferably 0.5 to 25 bar, in particular 0.5 to 10 bar, above the process pressure.
- the process pressure applied to the gas jet pump is 1 to 500 mbar, preferably 50 to 200 mbar, less than the atmospheric pressure.
- the feed gas is preferably fed to the gas jet pump with a flow rate which is a 1.01 to 10-fold, in particular a 1.5 to 2-fold excess, based on pure feed gas, compared to the stoichiometric consumption of the corresponds to the electrochemical process. If the feed gas used contains impurities such as inert gases, the process must be run with a correspondingly higher overstoichiometry.
- the educt gas is expanded to the process pressure in the gas jet pump and into the
- the process pressure preferably corresponds to the operating pressure of the gas diffusion electrode plus a possible pressure loss in the lines.
- the process pressure preferably corresponds to approximately atmospheric pressure.
- the superstoichiometric proportion of the feed gas is as
- Residual gas is removed from the process.
- the suction power of the gas jet pump can be regulated via the gradient between the educt gas pressure and the process pressure.
- the residual gas stream returned to the electrolysis process is adjusted via a control element provided in the residual gas, exhaust gas and / or recycling gas stream.
- the amount of the residual gas to be returned to the process can be set to 0.01% to 100%, based on the residual gas.
- the amount of residual gas to be returned to the process is preferably set to values of 80 to 99.5%.
- Residual gas can be provided in the exhaust gas flow.
- the method according to the invention is preferably carried out under essentially atmospheric process pressure with the exhaust gas flowing freely.
- the oxygen-consuming cathode preferably has the structure described in EP-A-1 061 158.
- the oxygen-consuming cathode preferably has, as a metallic carrier for distributing the electrons, a fabric made of silver wire or silver-plated nickel wire or another leach-proof alloy, e.g. Inconel, on.
- the respective alloy should also be silver-plated or otherwise refined. It is particularly advantageous to use a deeply structured support such as Felt made from fine fibers of the above-mentioned fabric material.
- the catalyst matrix preferably consists of a mixture of Teflon (to adjust the hydrophobicity and porosity for gas diffusion), an electrically conductive carrier, e.g. Vulcan black or acetylene black, and the finely divided catalyst material itself, which is mixed in the form of catalytically active silver particles.
- the catalyst matrix is preferably sintered or pressed with the support.
- the carbon components (soot) can also be dispensed with if the catalyst density and / or the rendered hydrophobic support are set such that the majority of the catalyst particles are also contacted electrically.
- the presence of carbon black in the oxygen-consuming electrode can be dispensed with, particularly in the case of NaCl electrolysis, so that the electrode matrix consists only of Teflon and silver.
- silver In addition to acting as a catalyst, silver also takes on the role of electron conduction. Accordingly, such a high silver loading is necessary that the particles touch and form conductive bridges with one another.
- Both the wire mesh, a fine expanded metal, as known from battery technology can be used as the carrier a felt made of silver, silver-plated nickel or silver-plated alkali-resistant material, eg Inconel steel, can also be used.
- the method according to the invention is used in HCl membrane electrolysis with an oxygen-consuming cathode.
- the method according to the invention is particularly suitable for implementation in connection with dimensionally stable gas diffusion electrodes, in particular with the dimensionally stable gas diffusion electrode described below:
- a dimensionally stable gas diffusion electrode which can preferably be used in the process according to the invention consists of at least one electrically conductive catalyst support material for receiving a coating composition containing catalyst material, in particular mixtures of finely divided silver or finely divided silver oxide or mixtures of silver and silver oxide and Teflon powder or from mixtures of finely divided silver or silver oxide or mixtures of silver and silver oxide, carbon and Teflon powder, and an electrical connection, the catalyst support material being a woven fabric, fleece, sintered metal, foam or
- the open structure serving as catalyst support material consists in particular of a fine wire mesh or a corresponding fine expanded metal, filter screen, felt, foam or sintered material, into which the coating material containing the catalyst material is clamped during rolling.
- this open structure is metallic, e.g. with the thoroughly open, but more compact and stiff substructure, before the pressing or rolling in of the coating material containing catalyst material, e.g. connected by sintering.
- this substructure is that of an abutment when the coating material containing the catalyst material is pressed in, which in this case can also spread into structure-related gaps between the two layers and thus clamp together even better.
- the metal for the base plate is preferably selected from the series consisting of nickel or an alkali-resistant nickel alloy or nickel, which is coated with silver, or an alkali-resistant metal alloy.
- a rigid foam or rigid structure or a perforated or slotted plate made of a material from the series nickel, alkali-resistant nickel alloy or alkali-resistant metal alloy or nickel, which is coated with silver can be used as the base plate.
- the coating material which has been rolled out into a fur and contains catalyst material is rolled directly into the basic structure, which at the same time has the function of a catalyst support material. An additional catalyst support material is therefore not used.
- the catalyst support material preferably consists of carbon, metal, in particular nickel or nickel alloys or an alkali-resistant metal alloy.
- the base plate preferably has a plurality of openings, in particular slots or bores, for improved passage of reaction gas.
- the openings are preferably at most 2 mm, in particular at most 1.5 mm wide.
- the slots can have a length of up to 30 mm.
- the pores When using a foam or a porous sintered structure, the pores have an average diameter of preferably at most 2 mm.
- the structure is characterized by high rigidity and flexural strength.
- a foam or sintered metal body is preferably used as the catalyst support material of the gas diffusion electrode, an edge provided for connecting the electrode to an electrochemical reaction apparatus being pressed together in order to achieve the required gas / liquid tightness.
- a preferred variant of the gas diffusion electrode that can be used in the method according to the invention is characterized in that the base plate has an opening-free peripheral edge of at least 5 mm, which is used to fasten the electrode, in particular by welding or soldering, or with screws or rivets or clamps or by use electrically conductive adhesive to the edge of the gas pocket to be connected to the electrode.
- a further preferred form of the gas diffusion electrode which can be used in the process according to the invention is characterized in that the catalyst support material and the coating material comprising the catalyst material are connected to one another by dry calendering.
- a preferred variant of the gas diffusion electrode that can be used in the process according to the invention is designed such that the catalyst support material and the coating material containing the catalyst material are obtained by pouring or wet rolling the coating composition containing water and possibly organic solvent (for example alcohol) is applied to the catalyst support material and is connected by subsequent drying, sintering and possibly compression.
- organic solvent for example alcohol
- an additional electrically conductive gas distributor fabric in particular made of carbon or metal, in particular nickel, or an alkali-resistant nickel alloy or of nickel, which is coated with silver, or an alkali-resistant metal Alloy provided.
- the base plate has a flat recess for receiving the gas distributor fabric.
- gas diffusion electrode has proven to be particularly suitable for use in the method according to the invention, in which the layer of catalyst support material and coating material containing catalyst material in the edge region of the electrode is connected to the edge of the base plate in a gastight manner all around.
- the gas-tight connection can be made, for example, by sealing or, if necessary, ultrasonically supported, rolling down.
- a peripheral edge zone is strongly pressed in order to obtain a gas-tight edge area.
- the gas diffusion electrode preferably has an edge without openings or an edge sealed by pressing a porous basic structure and is on this opening-free edge gas-tight and electrically conductive with an electrochemical reaction apparatus, for example by means of welding, soldering, screwing, riveting, clamping or using alkali-resistant, electrically conductive adhesive.
- the opening-free edge is preferably silver-free.
- the opening-free edge is preferably silver-containing.
- Figure 1 shows a schematic representation of an exemplary embodiment of the inventive method.
- Figure 1 outlined structure using an oxygen-consuming cathode and a gas jet pump 1 from Körting, Hanover carried out at a specific current density of 4 kA / m 2 .
- the cathode compartment of the electrolyzer
- Residual gas mainly contained oxygen as well as water vapor and traces of HCl.
- the oxygen was subjected to the electrolysis process under a pressure of 4.8 bar
- the oxygen-rich residual gas was returned to the process without drying or cleaning being necessary.
- the oxygen consumption could be reduced from 255 m h to approx. 170 mV h, since the excess gas required for the process is achieved by the returned residual gas. This means a saving of around 75 mVh compared to a non-recycled process. Due to the free discharge of the discharged residual gas, the
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10149779A DE10149779A1 (de) | 2001-10-09 | 2001-10-09 | Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen |
DE10149779 | 2001-10-09 | ||
PCT/EP2002/010841 WO2003031691A2 (de) | 2001-10-09 | 2002-09-27 | Verfahren zur rückführung von prozessgas in elektrochemischen prozessen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1499756A2 true EP1499756A2 (de) | 2005-01-26 |
EP1499756B1 EP1499756B1 (de) | 2008-03-05 |
Family
ID=7701913
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02800578A Expired - Lifetime EP1499756B1 (de) | 2001-10-09 | 2002-09-27 | Verfahren zur rückführung von prozessgas in elektrochemischen prozessen |
Country Status (16)
Country | Link |
---|---|
US (2) | US20040245118A1 (de) |
EP (1) | EP1499756B1 (de) |
JP (1) | JP4326333B2 (de) |
KR (1) | KR100932343B1 (de) |
CN (1) | CN100385043C (de) |
AR (1) | AR036661A1 (de) |
AT (1) | ATE388253T1 (de) |
AU (1) | AU2002333884A1 (de) |
BR (1) | BR0213191B1 (de) |
DE (2) | DE10149779A1 (de) |
ES (1) | ES2298427T3 (de) |
HU (1) | HUP0500575A3 (de) |
PL (1) | PL202569B1 (de) |
PT (1) | PT1499756E (de) |
TW (1) | TWI250228B (de) |
WO (1) | WO2003031691A2 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1843424A1 (de) * | 2004-12-28 | 2007-10-10 | GS Yuasa Corporation | Brennstoffzellen-stromerzeugungseinrichtung |
KR20070097050A (ko) * | 2004-12-28 | 2007-10-02 | 가부시키가이샤 지에스 유아사 코포레이션 | 독립형 수소 제조 시스템 |
DE102011005133A1 (de) | 2011-03-04 | 2012-09-06 | Bayer Materialscience Aktiengesellschaft | Verfahren zum Betrieb einer Sauerstoffverzehrelektrode |
DE102013011298A1 (de) * | 2013-07-08 | 2015-02-12 | Uhdenora S.P.A. | Vorrichtung und Verfahren zum Betrieb einer Elektrolyse mit einer Sauerstoff-Verzehr Kathode |
EP3680364B1 (de) * | 2017-09-07 | 2022-01-05 | De Nora Permelec Ltd | Elektrolysevorrichtung |
WO2022003114A1 (en) * | 2020-07-02 | 2022-01-06 | Katholieke Universiteit Leuven | Electrochemical reduction of co2 to formic acid |
EP4123057A1 (de) | 2021-07-19 | 2023-01-25 | Covestro Deutschland AG | Optimierter flüssigkeitsablauf aus membranelektrolyseuren |
KR102409451B1 (ko) * | 2022-03-31 | 2022-06-15 | 주식회사 블루텍 | 연소배기가스를 이용한 황산암모늄 제조장치 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US3652431A (en) * | 1970-03-12 | 1972-03-28 | Julian Louis Reynolds | Method of operating an electrolysis cell for the production of gases under hydrostatic pressure |
US3718506A (en) * | 1971-02-22 | 1973-02-27 | Bbc Brown Boveri & Cie | Fuel cell system for reacting hydrocarbons |
US4173524A (en) * | 1978-09-14 | 1979-11-06 | Ionics Inc. | Chlor-alkali electrolysis cell |
DE3427645A1 (de) | 1984-07-26 | 1986-01-30 | Sihi Gmbh & Co Kg, 2210 Itzehoe | Gasstrahlpumpe |
US4657651A (en) * | 1986-04-04 | 1987-04-14 | The Dow Chemical Company | Vertical gas electrode operation |
DE4440646A1 (de) * | 1994-11-14 | 1996-05-15 | Bayer Ag | Verfahren zur Oxidation von Chlorwasserstoff |
US5441821A (en) * | 1994-12-23 | 1995-08-15 | Ballard Power Systems Inc. | Electrochemical fuel cell system with a regulated vacuum ejector for recirculation of the fluid fuel stream |
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- 2001-10-09 DE DE10149779A patent/DE10149779A1/de not_active Withdrawn
-
2002
- 2002-09-27 BR BRPI0213191-9A patent/BR0213191B1/pt not_active IP Right Cessation
- 2002-09-27 PL PL372833A patent/PL202569B1/pl not_active IP Right Cessation
- 2002-09-27 JP JP2003534657A patent/JP4326333B2/ja not_active Expired - Lifetime
- 2002-09-27 US US10/491,757 patent/US20040245118A1/en not_active Abandoned
- 2002-09-27 ES ES02800578T patent/ES2298427T3/es not_active Expired - Lifetime
- 2002-09-27 KR KR1020047005122A patent/KR100932343B1/ko not_active IP Right Cessation
- 2002-09-27 PT PT02800578T patent/PT1499756E/pt unknown
- 2002-09-27 WO PCT/EP2002/010841 patent/WO2003031691A2/de active IP Right Grant
- 2002-09-27 CN CNB02819845XA patent/CN100385043C/zh not_active Expired - Lifetime
- 2002-09-27 AU AU2002333884A patent/AU2002333884A1/en not_active Abandoned
- 2002-09-27 DE DE50211864T patent/DE50211864D1/de not_active Expired - Lifetime
- 2002-09-27 AT AT02800578T patent/ATE388253T1/de not_active IP Right Cessation
- 2002-09-27 EP EP02800578A patent/EP1499756B1/de not_active Expired - Lifetime
- 2002-09-27 HU HU0500575A patent/HUP0500575A3/hu unknown
- 2002-09-30 AR ARP020103691A patent/AR036661A1/es not_active Application Discontinuation
- 2002-10-08 TW TW091123142A patent/TWI250228B/zh not_active IP Right Cessation
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2009
- 2009-05-06 US US12/436,559 patent/US8377284B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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See references of WO03031691A2 * |
Also Published As
Publication number | Publication date |
---|---|
TWI250228B (en) | 2006-03-01 |
HUP0500575A2 (hu) | 2005-09-28 |
EP1499756B1 (de) | 2008-03-05 |
HUP0500575A3 (en) | 2008-07-28 |
US8377284B2 (en) | 2013-02-19 |
AU2002333884A1 (en) | 2003-04-22 |
CN100385043C (zh) | 2008-04-30 |
CN1656253A (zh) | 2005-08-17 |
DE10149779A1 (de) | 2003-04-10 |
WO2003031691A3 (de) | 2004-11-11 |
DE50211864D1 (de) | 2008-04-17 |
KR100932343B1 (ko) | 2009-12-16 |
PT1499756E (pt) | 2008-04-09 |
AR036661A1 (es) | 2004-09-22 |
PL202569B1 (pl) | 2009-07-31 |
KR20040049863A (ko) | 2004-06-12 |
ATE388253T1 (de) | 2008-03-15 |
BR0213191B1 (pt) | 2011-11-16 |
US20040245118A1 (en) | 2004-12-09 |
JP4326333B2 (ja) | 2009-09-02 |
PL372833A1 (en) | 2005-08-08 |
JP2005524765A (ja) | 2005-08-18 |
WO2003031691A2 (de) | 2003-04-17 |
ES2298427T3 (es) | 2008-05-16 |
US20090211915A1 (en) | 2009-08-27 |
BR0213191A (pt) | 2005-04-26 |
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