EP0051845B1 - Cellule d'électrolyse avec compartiment intermédiaire traversé par l'électrolyte et structure convenable pour un tel compartiment - Google Patents

Cellule d'électrolyse avec compartiment intermédiaire traversé par l'électrolyte et structure convenable pour un tel compartiment Download PDF

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Publication number
EP0051845B1
EP0051845B1 EP81109469A EP81109469A EP0051845B1 EP 0051845 B1 EP0051845 B1 EP 0051845B1 EP 81109469 A EP81109469 A EP 81109469A EP 81109469 A EP81109469 A EP 81109469A EP 0051845 B1 EP0051845 B1 EP 0051845B1
Authority
EP
European Patent Office
Prior art keywords
separators
middle chamber
electrolysis cell
supporting member
ion exchanger
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
Application number
EP81109469A
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German (de)
English (en)
Other versions
EP0051845A1 (fr
Inventor
Bernd Dieter Dr. Struck
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE3041823A external-priority patent/DE3041823C2/de
Priority claimed from DE3041799A external-priority patent/DE3041799C2/de
Application filed by Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP0051845A1 publication Critical patent/EP0051845A1/fr
Application granted granted Critical
Publication of EP0051845B1 publication Critical patent/EP0051845B1/fr
Expired 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
    • C25B13/00—Diaphragms; Spacing elements
    • 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 an electrolysis cell for the production of hydrogen and sulfuric acid from water and sulfur dioxide with an electrolyte-flow intermediate chamber which separates the anode and cathode compartments and is delimited by separators in the form of ion exchange membranes.
  • the invention relates in particular to such an electrolysis cell which is to be used in the context of a so-called “sulfuric acid hybrid cycle” with the most economical generation of hydrogen.
  • a further improvement of the method mentioned can be achieved by the electrodes or collectors making as close contact as possible with the adjacent separators of the intermediate chamber. Difficulties arise, however, since the mechanical stability of the separators is not very high, so that the use of increased contact pressures is practically impossible.
  • Support scaffolds made of polyethylene or Teflon®, such as z. B. in German patent 1 546 717 for aqueous electrolysis are generally proposed and would be useful for the application of contact pressures in a three-chamber cell for the production of hydrogen per se, increase the overall resistance of the cell very considerably, so that such support structures were rejected.
  • the electrolysis cell according to the invention of the type mentioned at the outset is therefore characterized by a porous support structure made of graphite or ion exchange material between the separators.
  • the porous support structure should have a strength that takes up the necessary contact pressure (for the separators to lie flat against the support structure) and the highest possible free volume between the support material. In this context, more or less large gaps are also referred to as “pores”.
  • the separators with electrodes directly adjoining them rest on the porous support frame filling the entire intermediate chamber.
  • the separators with electrodes directly adjoining them are pressed against the graphite support structure, which has the highest possible continuous (open) porosity, so that the interelectrolyte flow is not inadmissibly inhibited.
  • Particularly useful is porous graphite or graphite felt with about 95% "porosity”.
  • the continuous porosity of the graphite material used should expediently be at least 80%.
  • the ohmic resistance of the electrolysis cell can thus be kept low due to the low specific resistance of support structures made of easily wettable graphite.
  • Support structures made of ion exchange material which advantageously consists of the same material as the separators and can be welded to them, appear to be particularly favorable at the moment.
  • an intermediate chamber structure is obtained which can be provided in the form of sheet material, which facilitates the assembly of the cell and lowers its overall price.
  • the separators can only be pressed together with the electrodes.
  • the support structure should have sufficient mechanical strength and sufficient continuous porosity in the electrolyte flow direction between (i.e. parallel to) the separators.
  • the self-ion-conducting ion exchanger can support the charge transport across the intermediate chamber, so that in the case of the support structure made of ion exchange material, a high continuous porosity in this direction is desirable but not mandatory.
  • This essentially axially symmetrical cell is held together by outer plastic disks (e.g. made of polyvinylidene fluoride) 1 and 2, to which the housing halves 3 and 4 made of graphite are connected inwards.
  • Two copper rings 5 and 6 reinforce the graphite and simultaneously form power connections.
  • the housing halves 3 and 4 with the copper rings 5 and 6 are electrically separated from one another by the intermediate chamber frame made of plastic with a supporting structure 12.
  • the cathode 7 and the anode 8 are designed as flow electrodes and are in contact with the separators 9 and 10 which are designed as cation exchange membranes and which delimit the intermediate chamber 11.
  • the supply of the electrolyte currents is indicated on the drawing.
  • the separators 9 and 10 between the individual cell chambers were cation exchange membranes of the NEOSEPTA C 66-5T type, on which a platinum-coated graphite felt acted as the cathode and a graphite felt as the anode.
  • the ohmic internal resistance of the electrolytic cell can be calculated from the current-voltage characteristics of the electrolytic cell and the individual electrodes (measured against a comparison electrode). This generally consists essentially of the resistances of the cation exchange membranes, the resistance of the electrolytes in the intermediate chamber and the contact resistances which arise from the low contact pressure of the electrodes on the membranes or the collectors on the electrodes.
  • the ohmic resistance of the intermediate chamber through which the electrolyte flows is now increased on the one hand by using a support frame evenly distributed in the intermediate chamber.
  • the ohmic resistance of the electrolysis cell without a support structure is approximately 1 ohm. cm 2 and with a graphite felt support frame also approx. 1 ohm. cm 2 .
  • the electrolysis voltage at a current density of 200 mA / cm 2 simultaneously decreases from 625 mV to 565 mV, due to the improved catalytic effect of the platinum-coated graphite felt, which is pressed onto the cation-exchange membrane on the cathode side.

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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 (9)

1. Cellule d'électrolyse destinée à la production d'hydrogène et d'acide sulfurique à partir d'eau et de dioxyde de soufre, ayant un compartiment intermédiaire traversé par l'électrolyte, qui sépare le compartiment anodique du compartiment cathodique et qui est délimité par des séparateurs sous forme de membranes d'échange d'ions, caractérisée par un support d'appui poreux (12) en graphite ou en une matière échangeuse d'ions interposé entre les séparateurs (9, 10).
2. Cellule d'électrolyse suivant la revendication 1, caractérisée par un support d'appui poreux (12) en graphite ou en une matière échangeuse d'ions, qui emplit tout le compartiment intermédiaire (11) et sur lequel les séparateurs (9, 10) avec des électrodes (7, 8) s'y raccordant directement sont appliqués suivant leur surface.
3. Cellule d'électrolyse suivant la revendication 2, caractérisée par un support d'appui en graphite, sur lequel les séparateurs avec des électrodes s'y raccordant directement sont appliqués en y étant pressés.
4. Cellule d'électrolyse suivant l'une des revendications 1 à 3, caractérisée en ce que le support d'appui (12) présente une porosité ou une perméabilité continue aussi élevée que possible.
5. Cellule d'électrolyse suivant l'une des revendications précédentes, caractérisée en ce que le support d'appui est en la même matière que les séparateurs et est relié rigidement à ces derniers.
6. Cellule d'électrolyse suivant la revendication 1 ou 2, caractérisée en ce que le support d'appui (12) en une matière échangeuse d'ions est soudé aux membranes échangeuses d'ions (9, 10).
7. Cellule d'électrolyse suivant l'une des revendications précédentes, caractérisée par une distance aussi petite que possible entre les membranes formant séparateurs (9, 10) du compartiment intermédiaire (11), l'épaisseur du compartiment intermédiaire devant permettre cependant un courant d'électrolyte suffisant pour empêcher un débordement du dioxyde de soufre du compartiment anodique au compartiment cathodique.
8. Structure de compartiment intermédiaire pour des cellules d'électrolyse, caractérisée par un support d'appui (12) en une matière échangeuse d'ions, qui est limité par des séparateurs et dont sont solidaires des séparateurs (9, 10) sous forme de membranes échangeuses d'ions.
9. Structure de compartiment intermédiaire suivant la revendication 8, sous forme de nappes empilées ou enroulées de manière à supporter le stockage.
EP81109469A 1980-11-06 1981-10-31 Cellule d'électrolyse avec compartiment intermédiaire traversé par l'électrolyte et structure convenable pour un tel compartiment Expired EP0051845B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3041799 1980-11-06
DE3041823 1980-11-06
DE3041823A DE3041823C2 (de) 1980-11-06 1980-11-06 Elektrolysezelle mit elektrolytdurchströmter Zwischenkammer
DE3041799A DE3041799C2 (de) 1980-11-06 1980-11-06 Elektrolysezelle mit elektrolytdurchströmter Zwischenkammer und dafür geeignete Zwischenkammerstruktur

Publications (2)

Publication Number Publication Date
EP0051845A1 EP0051845A1 (fr) 1982-05-19
EP0051845B1 true EP0051845B1 (fr) 1984-09-19

Family

ID=25788943

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81109469A Expired EP0051845B1 (fr) 1980-11-06 1981-10-31 Cellule d'électrolyse avec compartiment intermédiaire traversé par l'électrolyte et structure convenable pour un tel compartiment

Country Status (3)

Country Link
US (1) US4443316A (fr)
EP (1) EP0051845B1 (fr)
CA (1) CA1172604A (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4734181A (en) * 1984-12-07 1988-03-29 The Dow Chemical Company Electrochemical cell
EP2521697A2 (fr) 2010-01-07 2012-11-14 Sealed Air Corporation (US) Système modulaire à cartouche pour appareil destiné à produire des solutions de nettoyage et/ou de désinfection
US8734623B1 (en) * 2010-10-01 2014-05-27 Powerquest Llc On-demand hydrogen generator
US8882972B2 (en) * 2011-07-19 2014-11-11 Ecolab Usa Inc Support of ion exchange membranes
KR101410911B1 (ko) * 2012-06-22 2014-06-23 한국에너지기술연구원 전기화학 공정을 이용한 이산화황 가스로부터의 수소 및 황산의 제조방법
CN111424286B (zh) * 2020-02-28 2021-06-08 清华大学 一种so2去极化电解池
CN111424287B (zh) * 2020-02-28 2021-09-21 清华大学 一种用于碘化氢浓缩的电解-电渗析池

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR87850E (fr) * 1962-08-24 1966-10-21 Siemens Ag Cellule électrochimique perfectionnée
DE1546717C3 (de) * 1964-05-14 1974-06-27 Siemens Ag, 1000 Berlin Und 8000 Muenchen Elektrochemische Zelle
US3356607A (en) * 1964-07-22 1967-12-05 Ionics Reinforced ion-exchange membranes
US3893901A (en) * 1973-12-04 1975-07-08 Vast Associates Inc J System for softening and dealkalizing water by electrodialysis
US4172774A (en) * 1975-10-30 1979-10-30 Clearwater Systems Inc. Method and apparatus for lessening ionic diffusion
US4165248A (en) * 1976-12-01 1979-08-21 Ppg Industries, Inc. Method of joining fluorocarbon membrane sheets with quaternary ammonium compounds
US4124458A (en) * 1977-07-11 1978-11-07 Innova, Inc. Mass-transfer membrane and processes using same
DE2743820C3 (de) * 1977-09-29 1981-10-22 Kernforschungsanlage Jülich GmbH, 5170 Jülich Anwendung eines Verfahrens zum elektrochemischen Umsetzen von in einer Elektrolytlösung befindlichen Stoffen beim Schwefelsäure-Hybrid-Prozeß
US4242193A (en) * 1978-11-06 1980-12-30 Innova, Inc. Layered membrane and processes utilizing same
US4361475A (en) * 1980-01-10 1982-11-30 Innova, Inc. Membrane block construction and electrochemical cell

Also Published As

Publication number Publication date
CA1172604A (fr) 1984-08-14
US4443316A (en) 1984-04-17
EP0051845A1 (fr) 1982-05-19

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