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EP1499756B1 - Procede de recyclage du gaz utilise dans des processus electrochimiques - Google Patents

Procede de recyclage du gaz utilise dans des processus electrochimiques Download PDF

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Publication number
EP1499756B1
EP1499756B1 EP02800578A EP02800578A EP1499756B1 EP 1499756 B1 EP1499756 B1 EP 1499756B1 EP 02800578 A EP02800578 A EP 02800578A EP 02800578 A EP02800578 A EP 02800578A EP 1499756 B1 EP1499756 B1 EP 1499756B1
Authority
EP
European Patent Office
Prior art keywords
gas
pressure
educt
jet pump
residual
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.)
Expired - Lifetime
Application number
EP02800578A
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German (de)
English (en)
Other versions
EP1499756A2 (fr
Inventor
Fritz Gestermann
Thorsten Leidig
Alfred Soppe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1499756A2 publication Critical patent/EP1499756A2/fr
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Publication of EP1499756B1 publication Critical patent/EP1499756B1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • 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.
  • gas diffusion electrodes enables alternative reaction paths in different electrochemical processes and avoids the formation of undesired or uneconomical by-products.
  • An example of a gas diffusion electrode is the oxygen-consuming cathode.
  • This electrode is an open-cell membrane arranged between the electrolyte and the gas space and has an electrically conductive layer with a catalyst. This arrangement ensures that the oxygen reduction takes place at the three-phase boundary between the electrolyte, catalyst and oxygen as close as possible to the electrolyte.
  • oxygen-consuming cathodes are used in alkali halide electrolysis.
  • oxygen is added as reactant gas.
  • the resulting, still oxygen-containing residual gas is discharged from the process and fed to the exhaust gas without further use.
  • a disadvantage of the previous procedure on the one hand, the high oxygen consumption and, on the other hand, before the release of the residual gas to the environment required complex purification, eg by means of wash columns.
  • the residual gas can also be worked up for a new use, but this also washing columns or filters and compressors for the return to the process are required.
  • Gas jet pumps for vacuum generation, gas mixing and heat recovery (thermocompressor / bridge compressor).
  • Gas jet pumps are propellant pumps which generate a negative pressure and are particularly suitable for use as a vacuum pump.
  • gas jet pumps are in agreement with the liquid jet pumps.
  • blowing agent for example, steam can be used.
  • the invention has for its object to provide a recycling process for residual gases in electrolysis processes with Gasdif colsionselektroden that does not have the aforementioned disadvantages.
  • the consumption of educt gases should be reduced and a smaller dimensioning of required scrubbers and thus also a reduction in the consumption of scrubbing media should be achieved.
  • the use of costly compressors should be eliminated. At the same time damage to the membrane and the sensitive gas diffusion electrode should be avoided.
  • An essential aspect of the invention is the residual gas excess in electrolysis processes with gas diffusion electrodes, which was previously discharged as exhaust gas, directly attributable to the process. This leads to a reduction in the consumption of reactant gas without affecting the function of the sensitive gas diffusion electrode is impaired.
  • the use of a gas jet pump allows the direct recirculation of eduktgastechnik residual gas in the process, without drying or cleaning is necessary.
  • a preferred embodiment of the invention thus comprises the recycling of residual gas in the process via a gas jet pump using the pressure difference of educt gas and process gas as the driving force, the regulation of the recycled gas and the outflow of a residual gas partial flow to the discharge of impurities and to avoid overpressure ,
  • the residual gas is recycled via the gas jet pump together with the educt gas in the process.
  • the residual gas produced in HC1 or NaCl membrane electrolysis mainly contains oxygen as well as water vapor, HCl and, in the event of membrane damage, also chlorine.
  • the residual gas may contain traces of caustic soda (NaOH).
  • NaOH caustic soda
  • the delivery of the residual gas as exhaust air would require a large-scale exhaust air scrubber and a high consumption of sodium hydroxide solution for laundry.
  • the oxygen used with a 50% excess would be discharged 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 under high sodium hydroxide consumption due to the HCl and possible chlorine content of the residual gas.
  • the use according to the invention of a gas jet pump now allows the direct recirculation of educt gas-containing residual gas into the process, without drying or cleaning being necessary. This eliminates the previously necessary moistening of the educt gas.
  • the oxygen consumption can be reduced by about 33%, since the excess necessary for the process is achieved by the recycled residual gas, which with a volume flow, which is preferably greater than 90% of the residual gas stream and can optionally be adjusted via a control element, the process again is available.
  • the non-recycled portion of the residual gas stream is fed to the exhaust gas at a volumetric flow which is preferably less than about 10%, more preferably less than about 1% of the pure oxygen content of the educt gas.
  • the volume control in the recycled gas stream and the outflow of the discharged residual gas avoid overpressure or pressure fluctuations in the cathode compartment of the electrolysis, which can lead to membrane and electrode damage. Due to the effluent of the non-recycled portion of the residual gas stream, the accumulation of impurities, in particular inert gases, in the process is furthermore avoided.
  • the process according to the invention can be used in any electrochemical processes which require the use of gaseous educts in stoichiometric excess.
  • any gas diffusion electrodes can 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 proceed with the use of an oxygen-consuming cathode.
  • the method is also preferably used in electrolysis processes, in which essentially oxygen is added as reactant gas.
  • electrolysis processes which can be carried out by the process according to the invention are, in particular, the NaCl and HCl electrolysis, but also, for example, Process for ammonium sulphate or ammonium nitrate recycling using oxygen-consuming cathodes.
  • Particularly preferred electrolysis processes are NaCl electrolysis and HCl electrolysis with oxygen-consuming cathodes, in which oxygen is added at about 50% stoichiometric excess, based on pure oxygen.
  • the process pressure at which the electrochemical process is operated depends on the nature of the electrochemical process and the selected gas diffusion electrode and is generally in the range of 0.001 to 10 bar, preferably 10 to 250 mbar, in particular 10 to 200 mbar, above atmospheric pressure , more preferably at atmospheric pressure.
  • the educt gas pressure applied to the gas jet pump is generally 0.1 to 40 bar greater 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 exhaust gas is pumped up by means of a compressor or a blower for discharging at atmospheric pressure.
  • the educt gas is supplied with a flow rate of the gas jet pump, which is 1.01 to 10 times, in particular a 1.5 to 2-fold excess, based on pure reactant gas, compared to the stoichiometric consumption of the electrochemical process corresponds. If the reactant gas used contains impurities such as inert gases, the process must be run with a correspondingly higher superstoichiometry.
  • the educt gas is depressurized to the process pressure and introduced into the reaction space in which the electrochemical process takes place (for example, into the cathode compartment of the electrolysis apparatus).
  • 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 corresponds to about atmospheric pressure.
  • the superstoichiometric proportion of the educt gas is led out of the process as residual gas.
  • the suction power of the gas jet pump can be regulated via the gradient between the educt gas pressure and the process pressure.
  • the recycled residual gas stream in the electrolysis process is set via a control element provided in the residual gas, exhaust gas and / or recycling gas stream.
  • the amount of residual gas to be returned to the process can be adjusted to 0.01% to 100%, based on the residual gas.
  • the amount of residual gas to be recycled in the process is set to values of 80 to 99.5%.
  • the portion of the residual gas stream which is not recycled into the process gas stream is fed to the exhaust gas. This limits the accumulation of impurities in the process. Furthermore, the emergence of an undesirably large overpressure in the process is avoided by the outflow of this gas stream. This is especially true in the case of a shutdown of the electrolysis, since in this case no more oxygen is consumed in the process.
  • a control element may be provided in the exhaust stream.
  • the process according to the invention is preferably carried out under substantially atmospheric process pressure with free outflow of the exhaust gas.
  • the oxygen-consuming cathode preferably has in the EP-A-1 061 158 described structure.
  • the oxygen-consuming cathode preferably has, as a metallic support for distributing the electrons, a fabric made of silver wire or silver-plated nickel wire or another alkali-resistant alloy, eg Inconel.
  • the respective alloy should also be silvered or otherwise finished.
  • a deep-structured carrier such as felt of fine fibers of the above-mentioned fabric material.
  • the catalyst matrix preferably consists of a mixture of Teflon (for adjusting the hydrophobicity and the porosity for the gas diffusion), an electrically conductive support, for example Vulkanruß or acetylene black, and the finely divided therein catalyst material itself, which is mixed in the form of catalytically active silver particles.
  • the catalyst matrix is preferably sintered or pressed with the carrier. Alternatively, it is also possible to dispense with the carbon components (soot) if the catalyst density and / or the conductive hydrophobic carrier have been adjusted so that the predominant amount of the catalyst particles are also contacted electrically.
  • both the wire mesh, a fine expanded metal, as known from battery technology, as also a felt made of silver, silver-plated nickel or silver-plated lye-resistant material, eg Inconel steel serve.
  • the method according to the invention is used in the HCl membrane electrolysis with an oxygen-consuming cathode.
  • the method according to the invention is particularly suitable for carrying out in conjunction with dimensionally stable gas diffusion electrodes, in particular with the dimensionally stable gas diffusion electrode described below:
  • a dimensionally stable gas diffusion electrode preferably usable in the process according to the invention consists of at least one electrically conductive catalyst support material for receiving a coating material 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 of mixtures of fine distributed silver or silver oxide or mixtures of silver and silver oxide, carbon and Teflon powder, and an electrical connection, wherein the catalyst support material, a woven, nonwoven, sintered metal, foam or felt of electrically conductive material, an expanded metal plate or with a Variety of openings provided metal plate is applied to the catalyst material-containing coating composition, and which has a sufficient bending strength, so that an additional stiffening by using an additional Gru ndplatten can be omitted, or with a gas-permeable rigid metallic base plate or a rigid fabric or expanded metal in particular made of nickel or its alloys or alkali-resistant metal alloys, mechanically and electrically conductive.
  • a coating material containing catalyst material in particular mixtures
  • the open structure serving as the catalyst support material consists in particular of a fine wire mesh or a corresponding fine expanded metal, filter screen, felt, foam or sintered material, in which the coating material containing the catalyst material clamps during rolling.
  • This open structure in one embodiment, prior to pressing in or rolling in the catalyst material-containing coating composition, is already metallic with the quite open but more compact and rigid substructure, e.g. by sintering, connected.
  • this substructure is that of an abutment when pressing in the catalyst material containing coating mass, which in this case also spread out in structurally related spaces between the two layers and thus can clamp even better.
  • the metal for the base plate is preferably selected from the series nickel or a lye-resistant nickel alloy or nickel which is coated with silver, or from an alkali-resistant metal alloy.
  • a rigid foam or a rigid sintered structure or a perforated or slotted sheet of a material of the series nickel, alkali-resistant nickel alloy or alkali metal alloy or nickel, which is coated with silver can be used as the base plate.
  • the coating material containing a catalyst material which has been rolled out into a coat in a previous working step 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 thus not used.
  • the catalyst support material is preferably made of carbon, metal, in particular nickel or nickel alloys or a laugenfesten metal alloy.
  • the base plate has for improved passage of reaction gas preferably a plurality of openings, in particular slots or holes.
  • 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 not more than 2 mm.
  • the structure is characterized by a high rigidity and flexural strength.
  • a foam or sintered metal body is used as the catalyst support material of the gas diffusion electrode, wherein an edge provided for connecting the electrode to an electrochemical reactor is compressed in order to achieve the required gas / liquid tightness.
  • a preferred variant of the gas diffusion electrode which 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 suitable for fastening the electrode, in particular by welding or soldering, or with screws or rivets or clamps or by using electrically conductive Adhesive to the edge of the gas pocket to be connected to the electrode serves.
  • 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 containing the catalyst material are connected to one another by dry calendering.
  • a preferred variant of the gas diffusion electrode which 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 casting or wet rolling the water and possibly organic solvent (eg alcohol) containing coating composition is applied to the catalyst support material and is connected by subsequent drying, sintering and possibly compacting.
  • organic solvent eg alcohol
  • the gas diffusion electrode For improved uniform fumigation of the gas diffusion electrode is in a special design between the base plate and the catalyst support an additional electrically conductive gas distribution fabric, in particular carbon or metal, especially nickel, or a laugenfesten nickel alloy or nickel, which is coated with silver, or a laugenfesten metal Allocation provided.
  • an additional electrically conductive gas distribution fabric in particular carbon or metal, especially nickel, or a laugenfesten nickel alloy or nickel, which is coated with silver, or a laugenfesten metal Allocation provided.
  • the base plate has a planar 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 catalyst material containing coating mass is circumferentially gas-tightly connected to the edge of the base plate in the edge region of the electrode.
  • the gas-tight connection can be done, for example, by sealing or, if necessary, ultrasound-assisted, low-rolling.
  • a peripheral edge zone is strongly pressed after coating the structure with a catalyst material-containing coating material in order to obtain a gas-tight edge region.
  • 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 connected to an electrochemical reactor, for example by means of welding, soldering, screws, rivets, terminals or use of laugenfestem, electrically conductive adhesive.
  • the opening-free edge is preferably free of silver.
  • the opening-free edge is preferably silver-containing.
  • FIG. 1 shows FIG. 1 a schematic representation of an embodiment of the method according to the invention.
  • the oxygen was fed to the electrolysis process under a pressure of 4.8 bar (educt gas pressure) via a gas jet pump 1 and in this relaxed to about atmospheric pressure (process pressure).
  • the resulting pressure difference serves as a driving force for the suction and mixing of the excess, unused oxygen-containing residual gas.
  • the unused oxygen is the oxygen-consuming cathode in the membrane electrolysis process gas available.
  • the eduktgas Vietnamese residual gas was fed via a control valve 2 by the gas jet pump 1 again the process.
  • a partial flow of the residual gas was supplied via a control valve 3 to the exhaust gas stream, wherein the exhaust stream is designed to be unabsperrbar to avoid the emergence of overpressure and professionschleusen impurities.
  • 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 3 N / h to about 170 m 3 N / h, since the excess necessary for the process is achieved by the recycled residual gas. This represents a saving of about 75 m 3 N / h compared to a non-recycled process. Due to the free outflow of the discharged residual gas, the formation of overpressure and / or pressure fluctuations in the cathode compartment of the electrolysis, which can lead to membrane and electrode damage, was avoided.

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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)

Claims (10)

  1. Procédé de recyclage de gaz de processus dans un processus électrochimique avec au moins une électrode à diffusion de gaz, caractérisé par au moins les étapes suivantes:
    - apport de gaz éduit dans le processus électrochimique via une pompe à jet de gaz (1) sous une pression qui est supérieure à la pression de processus,
    - détente du gaz éduit à la pression de processus dans une pompe à jet de gaz (1) avec génération d'une pression d'aspiration qui est inférieure à la pression de processus, et
    - aspiration de gaz de processus contenant du gaz éduit (gaz restant) via la pression d'aspiration générée dans une pompe à jet de gaz et recyclage du gaz restant dans le processus électrochimique.
  2. Procédé suivant la revendication 1, caractérisé en ce que le recyclage du gaz restant dans le processus électrochimique se fait via au moins un organe de réglage (2).
  3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'une partie du gaz restant est évacuée du processus sous la forme d'un flux de gaz d'échappement.
  4. Procédé suivant l'une des revendications précédentes, caractérisé en ce que la pression de processus est réglée via un organe de réglage (3) supplémentaire dans le flux de gaz d'échappement.
  5. Procédé suivant l'une des revendications précédentes, caractérisé en ce que le gaz restant est amené dans le processus en même temps que le gaz éduit via la pompe à jet de gaz.
  6. Procédé suivant l'une des revendications précédentes, caractérisé en ce que l'amenée de gaz éduit et de gaz restant via la pompe à jet de gaz se fait de telle manière que le gaz de processus est proposé avec un excédent stoechiométrique de 1,01 à 10 fois, rapporté à la consommation de gaz éduit du processus électrochimique.
  7. Procédé suivant l'une des revendications précédentes, caractérisé en ce que la pression de processus se situe à 0,001 à 10 bars au-dessus de la pression atmosphérique.
  8. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce que le processus se déroule sous pression atmosphérique.
  9. Procédé suivant l'une des revendications 1 à 6, caractérisé en ce que la pression de processus se situe à 1 à 500 mbar en dessous de la pression atmosphérique.
  10. Procédé suivant l'une des revendications précédentes, caractérisé en ce que la pression de gaz éduit se situe à 0,1 à 40 bars au-dessus de la pression de processus.
EP02800578A 2001-10-09 2002-09-27 Procede de recyclage du gaz utilise dans des processus electrochimiques Expired - Lifetime EP1499756B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10149779 2001-10-09
DE10149779A DE10149779A1 (de) 2001-10-09 2001-10-09 Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen
PCT/EP2002/010841 WO2003031691A2 (fr) 2001-10-09 2002-09-27 Procede de recyclage du gaz utilise dans des processus electrochimiques

Publications (2)

Publication Number Publication Date
EP1499756A2 EP1499756A2 (fr) 2005-01-26
EP1499756B1 true EP1499756B1 (fr) 2008-03-05

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EP02800578A Expired - Lifetime EP1499756B1 (fr) 2001-10-09 2002-09-27 Procede de recyclage du gaz utilise dans des processus electrochimiques

Country Status (16)

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US (2) US20040245118A1 (fr)
EP (1) EP1499756B1 (fr)
JP (1) JP4326333B2 (fr)
KR (1) KR100932343B1 (fr)
CN (1) CN100385043C (fr)
AR (1) AR036661A1 (fr)
AT (1) ATE388253T1 (fr)
AU (1) AU2002333884A1 (fr)
BR (1) BR0213191B1 (fr)
DE (2) DE10149779A1 (fr)
ES (1) ES2298427T3 (fr)
HU (1) HUP0500575A3 (fr)
PL (1) PL202569B1 (fr)
PT (1) PT1499756E (fr)
TW (1) TWI250228B (fr)
WO (1) WO2003031691A2 (fr)

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DE102013011298A1 (de) 2013-07-08 2015-02-12 Uhdenora S.P.A. Vorrichtung und Verfahren zum Betrieb einer Elektrolyse mit einer Sauerstoff-Verzehr Kathode

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CA3072021C (fr) * 2017-09-07 2021-10-19 De Nora Permelec Ltd Dispositif electrolytique
WO2022003114A1 (fr) * 2020-07-02 2022-01-06 Katholieke Universiteit Leuven Réduction électrochimique du co2 en acide formique
EP4095092A1 (fr) * 2021-05-26 2022-11-30 Yara International ASA Système d'évacuation de gaz nox à partir d'un réservoir de stockage d'acide nitrique
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Publication number Priority date Publication date Assignee Title
DE102013011298A1 (de) 2013-07-08 2015-02-12 Uhdenora S.P.A. Vorrichtung und Verfahren zum Betrieb einer Elektrolyse mit einer Sauerstoff-Verzehr Kathode

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KR100932343B1 (ko) 2009-12-16
AR036661A1 (es) 2004-09-22
US8377284B2 (en) 2013-02-19
PT1499756E (pt) 2008-04-09
DE10149779A1 (de) 2003-04-10
BR0213191B1 (pt) 2011-11-16
HUP0500575A3 (en) 2008-07-28
JP4326333B2 (ja) 2009-09-02
KR20040049863A (ko) 2004-06-12
US20040245118A1 (en) 2004-12-09
PL372833A1 (en) 2005-08-08
DE50211864D1 (de) 2008-04-17
JP2005524765A (ja) 2005-08-18
TWI250228B (en) 2006-03-01
BR0213191A (pt) 2005-04-26
CN1656253A (zh) 2005-08-17
HUP0500575A2 (hu) 2005-09-28
WO2003031691A3 (fr) 2004-11-11
AU2002333884A1 (en) 2003-04-22
CN100385043C (zh) 2008-04-30
US20090211915A1 (en) 2009-08-27
WO2003031691A2 (fr) 2003-04-17
PL202569B1 (pl) 2009-07-31
ES2298427T3 (es) 2008-05-16
ATE388253T1 (de) 2008-03-15
EP1499756A2 (fr) 2005-01-26

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