US20040245118A1 - Method of recycling process gas in electrochemical processes - Google Patents

Method of recycling process gas in electrochemical processes Download PDF

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Publication number
US20040245118A1
US20040245118A1 US10/491,757 US49175704A US2004245118A1 US 20040245118 A1 US20040245118 A1 US 20040245118A1 US 49175704 A US49175704 A US 49175704A US 2004245118 A1 US2004245118 A1 US 2004245118A1
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Prior art keywords
gas
pressure
feed gas
electrochemical
jet pump
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Abandoned
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US10/491,757
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English (en)
Inventor
Fritz Gestermann
Thorsten Leidig
Alfred Soppe
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Covestro Deutschland AG
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Assigned to BAYER MATERIALSCIENCE AG reassignment BAYER MATERIALSCIENCE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GESTERMANN, FRITZ
Publication of US20040245118A1 publication Critical patent/US20040245118A1/en
Assigned to BAYER MATERIALSCIENCE AG reassignment BAYER MATERIALSCIENCE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEIDIG, THORSTEN, SOPPE, ALFRED, GESTERMANN, FRITZ
Priority to US12/436,559 priority Critical patent/US8377284B2/en
Abandoned legal-status Critical Current

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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 of recycling process gas in electrochemical processes involving gas diffusion electrodes.
  • a stoichiometric excess of feed gas is required, for example, where electrochemical cells based on gas diffusion electrodes are used.
  • gas diffusion electrodes permits alternative reaction routes in various electrochemical processes while avoiding undesirable or uneconomic by-products.
  • a gas diffusion electrode is the oxygen-consuming cathode.
  • This electrode is an open-pored membrane which is disposed between the electrolyte and the gas space and includes an electroconductive layer comprising catalyst. This arrangement ensures that the oxygen reduction at the three-phase boundary between electrolyte, catalyst and oxygen takes place as close as possible to the electrolyte.
  • oxygen-consuming cathodes are used, for example, in alkali metal halide electrolysis.
  • Gas jet pumps for generating a vacuum, mixing gases and recovering heat (thermocompressors/vapour compressors).
  • Gas jet pumps are working-fluid pumps which generate a negative pressure and are particularly suitable for use as a vacuum pump. Except for the choice of a gaseous working fluid, gas jet pumps correspond to liquid jet pumps.
  • a possible working fluid is steam.
  • the consumption of feed gases is to be reduced, and downscaling of requisite scrubbers is to be achieved, resulting in reduced consumption of scrubbing media.
  • the use of cost-intensive compressors should be done away with. At the same time, damage to the membrane and to the delicate gas diffusion electrode is to be avoided.
  • a method of recycling process gas in electrochemical processes, especially in electrolytic processes, involving at least one gas diffusion electrode comprises at least the following steps:
  • tail gas aspirating feed gas-containing process gas (tail gas) by means of the suction pressure generated in the gas jet pump and recycling tail gas into the electrochemical process.
  • a sigificant aspect of the invention is that the tail-gas excess produced in electrolytic processes involving gas diffusion electrodes and hitherto discharged as off-gas is recycled directly into the process. This results in reduced consumption of feed gas, without the operation of the delicate gas diffusion electrode being impaired.
  • the use of a gas jet pump allows the tail gas rich in feed gas to be recycled directly into the process, without any drying or cleaning being required.
  • a preferred embodiment of the invention therefore comprises recycling of tail gas into the process via a gas jet pump using the pressure differential of feed gas and process gas as the driving force, controlling the recycled gas flow rate, and the outflow of a tail gas substream to remove impurities and to avoid excess pressure.
  • the tail gas is preferably recycled into the process together with the feed gas via a gas jet pump.
  • the tail gas produced in HCl or NaCl membrane electrolysis mainly contains oxygen and additionally water vapour, HCl and, in the event of membrane damage, also contains chlorine.
  • the tail gas might contain traces of caustic soda (NaOH).
  • Discharging the tail gas as exhaust air would require a large-scale exhaust-air scrubber and high consumption of caustic soda solution for scrubbing.
  • the oxygen, employed in a 50% excess would be discharged as exhaust air. Because of the HCl and possible chlorine content of the tail gas, recycling into the process by means of a compressor would require expensive materials for the compressor or continuous scrubbing of the recycled amount of gas, with high consumption of caustic soda solution.
  • the inventive use of a gas jet pump now permits direct recycling of feed gas-containing tail gas into the process, without any drying or cleaning being required. Consequently, the previously required humidification of the feed gas can be dispensed with.
  • the oxygen consumption can be reduced by about 33%, since the excess required for the process is achieved by virtue of the recycled tail gas which, at a volume flow rate which is preferably greater than 90% of the tail-gas stream and, if required, can be adjusted via a control member, is available to the process once more.
  • the non-recycled fraction of the tail-gas stream is fed into the off-gas at a volume flow rate which is preferably less than about 10%, particularly preferably less than about 1% of the level of pure oxygen in the feed gas.
  • the method according to the invention can be employed in any electrochemical process which requires the use of gaseous feeds in stoichiometric excess.
  • the method according to the invention can make use of any type of gas diffusion electrode, e.g. an oxygen-consuming cathode.
  • the method according to the invention is preferentially used in electrochemical processes, especially in electrolytic processes, which proceed making use of an oxygen-consuming cathode.
  • the method is also preferentially employed in electrolytic processes in which essentially oxygen is introduced as a feed gas.
  • Examples of electrolytic processes which can be carried out in accordance with the method according to the invention include, in particular, NaCl and HCl electrolysis, but also e.g. methods of recycling ammonium sulphate or ammonium nitrate, making use of oxygen-consuming cathodes.
  • Particularly preferred electrolytic processes are NaCl electrolysis and HCl electrolysis involving oxygen-consuming cathodes, in which oxygen is introduced in about 50% stoichiometric excess, based on pure oxygen.
  • the process pressure at which the electrochemical process operates depends on the nature of the electrochemical process and the gas diffusion electrode chosen and is generally in the range of from 0.001 to 10 bar, preferably from 10 to 250 mbar, especially from 10 to 200 mbar, above atmospheric pressure, particularly preferably at atmospheric pressure.
  • the feed gas pressure applied to the gas jet pump generally exceeds the process pressure by from 0.1 to 40 bar.
  • the feed gas pressure exceeds the process pressure by from 0.5 to 25 bar, especially from 0.5 to 10 bar.
  • the process pressure applied to the gas jet pump is from 1 to 500 mbar, preferably from 50 to 200 mbar, below atmospheric pressure.
  • the off-gas is pressurized with the aid of a compressor or a blower for the purpose of ejecting it at atmospheric pressure.
  • the feed gas is fed to the gas jet pump at a flow rate which corresponds to a 1.01- to 10-fold excess, especially a 1.5 to 2-fold excess, based on pure feed gas, compared with the stoichiometric consumption of the electrochemical process.
  • the feed gas used contains impurities such as e.g. inert gases, the process must be run at a correspondingly higher superstoichiometry.
  • the feed gas is expanded to the process pressure and is introduced to the reaction chamber in which the electrochemical process takes place (e.g. into the cathode compartment of the electrolysis apparatus).
  • the process pressure preferably corresponds to the operating pressure of the gas diffusion electrode plus any pressure lost in the lines.
  • the process pressure approximately corresponds to atmospheric pressure.
  • a superstoichiometric fraction of the feed gas is passed out from the process as tail gas.
  • the suction pressure generated when the feed gas is expanded causes at least a fraction of the tail gas to be aspirated via the suction side of the gas jet pump and to be recycled into the process.
  • the suction rate of the gas jet pump can be controlled via the gradient between feed gas pressure and process pressure.
  • the tail-gas stream recycled into the electrolytic process is adjusted via a control member provided in the tail-gas stream, off-gas stream and/or recycling-gas stream.
  • the amount of the tail gas to be recycled into the process can be adjusted to from 0.01 to 100%, based on the tail gas.
  • the amount of the tail gas to be recycled into the process is adjusted to values of from 80 to 99.5%.
  • That proportion of the tail-gas stream which is not recycled into the process gas stream is fed into the off-gas.
  • the build-up of impurities in the process is thus restricted.
  • the outflow of this gas stream the build-up of an undesirably large excess pressure in the process is avoided. This is the case, in particular, in the event of the electrolysis having been switched off, since in this case oxygen is no longer consumed in the process.
  • a control member can be provided in the off-gas stream.
  • the method according to the invention is preferably implemented under essentially atmospheric process pressure with free outflow of the off-gas.
  • the oxygen-consuming cathode is preferably configured as described in EP-A-1 061 158.
  • the oxygen-consuming cathode preferably includes, as a metallic support for distributing the electrons, a fabric of silver wire or silvered nickel wire or some other alkali-resistant alloy, e.g. Inconel. So as to avoid poorly conductive oxide or hydroxide layers, the alloy in question should likewise be silvered or surface-treated in some other way.
  • a deeply patterned support such as e.g. felt made of fine fibres of the abovementioned fabric material.
  • the catalyst matrix preferably comprises a mixture of Teflon (to adjust the hydrophobicity and the porosity for gas diffusion), an electroconductive support, e.g. Vulcan black or acetylene black, and the catalyst material itself, which is finely dispersed therein and is mixed in in the form of catalytically active silver particles.
  • the catalyst matrix is preferably sinter-bonded or pressure-bonded to the support. Alternatively, it is possible to dispense with the carbon fractions (carbon black) if the catalyst density and/or the hydrophobic support which has been rendered conductive are adjusted in such a way that most of the catalyst particles are also in electrical contact.
  • the electrode matrix consists solely of Teflon and silver, the silver assuming the function of electron conduction as well as that of catalyst. Accordingly, a silver coverage is required which is sufficient for the particles to touch and to form conductive bridges between one another.
  • the support used can be in the form of the wire fabric, an expanded-metal foil, as known from battery technology, or a felt made of silver, silvered nickel or silvered alkali-resistant material, e.g. Inconel steel
  • the method according to the invention is employed in HCl membrane electrolysis with an oxygen-consuming cathode.
  • the method according to the invention is particularly suitable for implementation in conjunction with dimensionally stable gas diffusion electrodes, especially with the dimensionally stable gas diffusion electrode described below:
  • a dimensionally stable gas diffusion electrode preferentially usable in the method according to the invention comprises at least one electroconductive catalyst support material for accommodating a catalyst material-containing coating composition, in particular mixtures of finely dispersed silver powder or finely dispersed silver oxide powder or mixtures of silver powder and silver oxide powder and Teflon powder or mixtures of finely dispersed silver powder or silver oxide powder or mixtures of silver powder and silver oxide powder, carbon powder and Teflon powder, and an electrical connection, the catalyst support material being a fabric, bonded fibre web, sintered metal, foam or felt of electroconductive material, an expanded-metal plate or a metal plate that is provided with a multiplicity of perforations.
  • the catalyst material-containing coating composition is applied on top of said catalyst support material which has sufficient flexural strength for additional stiffening using an additional base plate to be dispensed with, or which is mechanically and electroconductively connected to a gas-permeable stiff metallic base plate or a stiff fabric or expanded metal, in particular made of nickel or its alloys or alkali-resistant metal alloys.
  • the open structure serving as a catalyst support material comprises, in particular, a fine wire fabric or a corresponding expanded-metal foil, filter screen, felt, foam or sintered material with which the catalyst material-containing coating composition interlocks when it is rolled in.
  • said open structure prior to the catalyst material-containing coating composition being pressed in or rolled in, is metallically bonded, e.g. by sinter-bonding, to the quite open, but more compact and stiff substructure itself.
  • the function of said substructure is that of an abutment during the operation of pressing in the catalyst material-containing coating composition which, in the process, is quite able to spread out even into structure-related interstices between the two layers and consequently to interlock even more effectively.
  • the metal for the base plate is preferably selected from the group consisting of nickel or an alkali-resistant nickel alloy or nickel coated with silver, or from an alkali-resistant metal alloy.
  • the base plate used can be a stiff foam or a stiff sintered structure or a perforated plate or a slotted plate made from a material from the group consisting of nickel, alkali-resistant nickel alloy or alkali-resistant metal alloy or nickel plated with silver.
  • the catalyst material-containing coating composition which, in a previous process step, has been rolled out into a rough sheet, is rolled directly into the base structure which at the same time acts as a catalyst support material. No additional catalyst support material is used therefore.
  • the catalyst support material preferably comprises carbon, metal, particularly nickel or nickel alloys or an alkali-resistant metal alloy.
  • the base plate preferably has a multiplicity of perforations, particularly slots or cylindrical holes.
  • the perforations preferably have a width of at most 2 mm, in particular at most 1.5 mm.
  • the slots can have a length of up to 30 mm.
  • the pores have a mean diameter of preferably at most 2 mm.
  • the structure is distinguished by high stiffness and flexible strength.
  • the gas diffusion electrode catalyst support material used is a foam or sintered-metal body, a rim provided for connecting the electrode to an electrochemical reaction apparatus being compressed in order to achieve the gas/liquid-tightness required.
  • 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 unperforated surrounding rim of a least 5 mm which serves to secure the electrode, especially by welding or soldering or by means of bolting or riveting or clamping or by using an electroconductive adhesive, to the rim 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 method according to the invention is characterized in that the catalyst support material and the catalyst material-containing coating composition are bonded together by dry calendering.
  • a preferred variant of the gas diffusion electrode which can be used in the method according to the invention is of such a design that the catalyst support material and the catalyst material-containing coating composition is applied to the catalyst support material by pouring or wet-rolling of the coating composition containing water and possibly organic solvent (e.g. alcohol), and is bonded by subsequent drying, sintering and possibly by densification.
  • the coating composition containing water and possibly organic solvent (e.g. alcohol)
  • an additional electroconductive gas distributor fabric especially made of carbon or metal, especially nickel, or an alkali-resistant nickel alloy or nickel coated in silver, or with an alkali-resistant metal alloy.
  • the base plate has an areal recess for accommodating the gas distributor fabric.
  • the layer of catalyst support material and catalyst material-containing coating composition forms a circumferentially gas-tight join to the rim of the base plate in the rim region of the electrode.
  • the gas-tight join can be achieved, for example, by sealing or, if required, by ultrasound-assisted flat-rolling.
  • a foam or porous sintered structure is used as the catalyst support material or the base plate, coating of the structure with catalyst material-containing coating composition is followed by firm pressure-bonding of a circumferential rim region to achieve a gas-tight rim region.
  • the gas diffusion electrode preferably has a rim without perforations or a rim sealed by pressure-bonding a porous base structure, and, at said unperforated rim, is joined gas-tightly and electroconductively to an electrochemical reaction apparatus, for example by means of welding, soldering, bolting, riveting, clamping or the use of alkali-resistant, electroconductive adhesive.
  • the unperforated rim is preferably free from silver.
  • the unperforated rim preferably contains silver.
  • the rim region of the base plate is advantageously sealed against the mounting plane of the electrochemical apparatus by means of a resilient liner.
  • FIG. 1 shows a schematic depiction of a specific embodiment of the method according to invention.
  • HCl membrane electrolysis was carried out using 76 cell elements of 2.5 m 2 each, using the configuration sketched in FIG. 1, using an oxygen-consuming cathode and a gas jet pump 1 from Körting, Hanover, at a specific current density of 4 kA/m 2 , the cathode compartment of the electrolyser being fed with 255 m 3 N /h of pure oxygen, i.e. in excess of about 50%.
  • the outflowing tail gas mainly contains oxygen and additionally water vapour and traces of HCl.
  • the oxygen was fed to the electrolysis process under a pressure of 4.8 bar (feed gas pressure) via a gas jet pump 1 and was expanded therein to about atmospheric pressure (process pressure), the resulting pressure differential serving as the driving force for aspirating and mixing the excess tail gas containing unconsumed oxygen.
  • the unconsumed oxygen is consequently available as a process gas to the oxygen-consuming cathode during the membrane electrolysis.
  • the feed gas-containing tail gas was once more fed into the process by the gas jet pump 1 via a control valve 2 .
  • a substream of the tail gas was fed, via a servo-valve 3 , into the off-gas stream, the off-gas stream being designed in such a way that it cannot be shut off, to prevent excess pressure from building up and to remove impurities.
  • the oxygen-rich tail gas was recycled into the process, without any drying or cleaning being required. Consequently, even feed gas humidification which had hitherto been required in NaCl electrolyses could be dispensed with.
  • the oxygen consumption could be reduced from 255 m 3 N /h to about 170 m 3 N /h, as the excess required for the process is achieved by virtue of the recycled tail gas. This means a saving of about 75 m 3 N /h compared with a non-recycling process.

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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)
US10/491,757 2001-10-09 2002-09-27 Method of recycling process gas in electrochemical processes Abandoned US20040245118A1 (en)

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DE10149779.2 2001-10-09
DE10149779A DE10149779A1 (de) 2001-10-09 2001-10-09 Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen
PCT/EP2002/010841 WO2003031691A2 (de) 2001-10-09 2002-09-27 Verfahren zur rückführung von prozessgas in elektrochemischen prozessen

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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)
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PT (1) PT1499756E (de)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080063910A1 (en) * 2004-12-28 2008-03-13 Gs Yuasa Ccorporation Fuel Cell Power Generating Device
US20080171244A1 (en) * 2004-12-28 2008-07-17 Gs Yuasa Corporation Standalone Hydrogen Generating System
US9422631B2 (en) 2011-03-04 2016-08-23 Covestro Deutschland Ag Method of operating an oxygen-consuming electrode
WO2022003114A1 (en) * 2020-07-02 2022-01-06 Katholieke Universiteit Leuven Electrochemical reduction of co2 to formic acid

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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
EP3680364B1 (de) * 2017-09-07 2022-01-05 De Nora Permelec Ltd Elektrolysevorrichtung
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

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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
US4632649A (en) * 1984-07-26 1986-12-30 Sihi Gmbh & Co. Kg Gas jet pump
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080063910A1 (en) * 2004-12-28 2008-03-13 Gs Yuasa Ccorporation Fuel Cell Power Generating Device
US20080171244A1 (en) * 2004-12-28 2008-07-17 Gs Yuasa Corporation Standalone Hydrogen Generating System
US9422631B2 (en) 2011-03-04 2016-08-23 Covestro Deutschland Ag Method of operating an oxygen-consuming electrode
WO2022003114A1 (en) * 2020-07-02 2022-01-06 Katholieke Universiteit Leuven Electrochemical reduction of co2 to formic acid

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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
JP4326333B2 (ja) 2009-09-02
PL372833A1 (en) 2005-08-08
EP1499756A2 (de) 2005-01-26
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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