EP0234256A1 - Procédé pour l'électrolyse avec membrane de l'acide chlorhydrique - Google Patents

Procédé pour l'électrolyse avec membrane de l'acide chlorhydrique Download PDF

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Publication number
EP0234256A1
EP0234256A1 EP87100678A EP87100678A EP0234256A1 EP 0234256 A1 EP0234256 A1 EP 0234256A1 EP 87100678 A EP87100678 A EP 87100678A EP 87100678 A EP87100678 A EP 87100678A EP 0234256 A1 EP0234256 A1 EP 0234256A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
carrying
hcl
membrane electrolysis
cell
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
Application number
EP87100678A
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German (de)
English (en)
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EP0234256B1 (fr
Inventor
Franz-Rudolf Dr. Minz
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.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0234256A1 publication Critical patent/EP0234256A1/fr
Application granted granted Critical
Publication of EP0234256B1 publication Critical patent/EP0234256B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof

Definitions

  • the present invention relates to an improved method for performing HCl membrane electrolysis.
  • a 20 to 26% strength aqueous hydrochloric acid is fed to the individual cells divided by a diaphragm and combined to form an electrolyzer of 30-45 units from two separate circuits for catholyte or anolyte acid, wherein the anolyte acid flows through all the anode compartments in parallel and at the same time the catholyte acid flows through all the cathode compartments in parallel.
  • 30% hydrochloric acid is fed into both circuits to strengthen the depleted acid (Winnacker Küchler: Chemical Technology, Volume 2, 4th edition 1982, p. 443 ff).
  • a disadvantage of this diaphragm method is that due to the permeability of the diaphragm for the electrolytes, an exchange of fluid inside the cells that cannot be controlled from the outside takes place. This is how the chlorine dissolved in the anolyte acid dissolves after it has passed through the catholyte side there partially expelled and thus contributes to the contamination of the hydrogen. Another part is reduced cathodically, thus leading to a reduction in the product current efficiency. Partial mixing of the chlorine and hydrogen gases produced in the electrolysis can also occur through the diaphragm.
  • This process described as a "solid polymer electrolyte” (SPE) system, has the advantage that only an anolyte circuit is required, since the protons discharged on the cathode side migrate from the anode side through the membrane, so theoretically no “depletion” in the catholyte Ion occurs. In practice, however, water of hydration passes over to the cathode side, which must be removed.
  • SPE solid polymer electrolyte
  • a disadvantage of this method is that the current transfer from the collector electrodes to the "working electrodes" lies within the electrolyte and thus defined current transfers are very difficult to set and cannot be controlled from the outside.
  • Electrocatalysts Reduced oxides from the group of noble metals, which are more or less mixed with graphite, are specified as electrocatalysts.
  • these systems are much less stable than graphite under operating conditions. But if, for reasons of durability, graphite has to be used for the collector electrodes and also for the electrocatalytic layers on the membranes, the solid graphite electrodes of the conventional type are no longer a significant disadvantage. In addition, the recurring difficulties in the adhesion of the electrocatalyst to the membrane are avoided .
  • a conductive electrolyte is also required on the cathode side.
  • the conductivity maximum of aqueous hydrochloric acid is at a concentration between 17 and 22% by weight of HCl. Since the concentration of the HCl solution in the cathode compartment decreases as a result of the transport of hydrated water through the membrane, the HCl solution must be renewed.
  • the object of the present invention is to provide a method for carrying out the HCl electrolysis to provide, which does not have the disadvantages of the methods described.
  • This process is intended to combine the advantage of the SPE cell with only one electrolyte circuit with the advantages of an electrolysis cell with a finite electrode / membrane spacing.
  • This object is achieved in a simple manner by a method for carrying out the HCl membrane electrolysis, in which at least part of the electrolyte leaving the cathode space is fed directly into the inlet of the anode chamber.
  • the concentrated hydrochloric acid to be electrolyzed is first fed into the catholyte chamber of a cell divided by a cation exchange membrane.
  • the escaping acid which is diluted by the hydrate water transported with the protons to the cathode side, is then introduced into the anolyte compartment of the cell.
  • the depleted acid runs off and can be re-saturated with gaseous HCl after the residual chlorine has been driven off.
  • the water of hydration penetrating the membrane is conducted in a short circle, the volume flow of the acid to be returned to the HCl absorption is reduced by this proportion.
  • FIG. 1 shows a cell (1) according to the invention.
  • An ion exchange membrane (4) of the Nafion NX 430 type from Du Pont divides the cell into a cathode compartment (2) and an anode compartment (3).
  • 0.2 l / h of 30% hydrochloric acid are fed into the catholyte circuit (5) of the cell, the mixture enters the cell from below.
  • a corresponding amount of 21% HCl overflows through line (6) to the anolyte side and is fed into the anolyte circuit (7).
  • the impoverished acid finally leaves the cell at around 18%.
  • the corresponding amount of HCl is removed from the anolyte cycle so that its volume remains constant.
  • a cell voltage of 1.9 to 2.1 volts is set, depending on the distance between the electrodes.
  • the chlorine and hydrogen gases formed during electrolysis leave the cell together with the electrolyte; the gas lift effect causes more electrolyte to leave the cell than fresh acid has to be added according to the current strength.
  • This excess quantity is immediately fed back into the cell inlet through the corresponding circuit lines (5) and (7).
  • the chlorine and hydrogen products are separated from the corresponding electrolytes in so-called gas separators at points C and D.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
EP87100678A 1986-01-30 1987-01-20 Procédé pour l'électrolyse avec membrane de l'acide chlorhydrique Expired - Lifetime EP0234256B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863602683 DE3602683A1 (de) 1986-01-30 1986-01-30 Verfahren zur durchfuehrung der hcl-membranelektrolyse
DE3602683 1986-01-30

Publications (2)

Publication Number Publication Date
EP0234256A1 true EP0234256A1 (fr) 1987-09-02
EP0234256B1 EP0234256B1 (fr) 1990-03-28

Family

ID=6292898

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87100678A Expired - Lifetime EP0234256B1 (fr) 1986-01-30 1987-01-20 Procédé pour l'électrolyse avec membrane de l'acide chlorhydrique

Country Status (4)

Country Link
US (1) US4725341A (fr)
EP (1) EP0234256B1 (fr)
JP (1) JPS62182292A (fr)
DE (2) DE3602683A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013105177A1 (de) 2013-05-21 2014-11-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Gewinnung metallischer Anteile sowie von metallabgereichertem Material aus metallhaltigen Materialien

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219671A (en) * 1985-12-04 1993-06-15 Solar Reactor Technologies, Inc. Hydrogen generation and utility load leveling system and the method therefor
US5443804A (en) * 1985-12-04 1995-08-22 Solar Reactor Technologies, Inc. System for the manufacture of methanol and simultaneous abatement of emission of greenhouse gases
DE4119606A1 (de) * 1991-06-14 1992-12-17 Sigri Great Lakes Carbon Gmbh Verfahren und vorrichtung zur aufarbeitung von salzsaeurehaltigem, mit begleitstoffen verunreinigtem wasser
JPH08507828A (ja) * 1993-03-15 1996-08-20 ライディングズ ピーティーワイ リミテッド 電解製造装置
US5976346A (en) * 1993-11-22 1999-11-02 E. I. Du Pont De Nemours And Company Membrane hydration in electrochemical conversion of anhydrous hydrogen halide to halogen gas
US5855759A (en) * 1993-11-22 1999-01-05 E. I. Du Pont De Nemours And Company Electrochemical cell and process for splitting a sulfate solution and producing a hyroxide solution sulfuric acid and a halogen gas
CA2408951C (fr) * 2002-10-18 2008-12-16 Kvaerner Canada Inc. Electrolyse assistee d'acides halogenes

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2447981A1 (fr) * 1979-02-02 1980-08-29 Chlorine Eng Corp Ltd Procede pour l'electrolyse de l'acide chlorhydrique

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4210501A (en) * 1977-12-09 1980-07-01 General Electric Company Generation of halogens by electrolysis of hydrogen halides in a cell having catalytic electrodes bonded to a solid polymer electrolyte
JPS6039757A (ja) * 1983-08-12 1985-03-01 Mitsubishi Electric Corp 放電灯装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2447981A1 (fr) * 1979-02-02 1980-08-29 Chlorine Eng Corp Ltd Procede pour l'electrolyse de l'acide chlorhydrique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 99, Nr. 18, Seite 538, Zusammenfassung Nr. 148510f, Columbus, Ohio, US; & JP-A-58 27 988 (CHLORINE ENGINEERS CORP., LTD) 18.02.1983 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013105177A1 (de) 2013-05-21 2014-11-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Gewinnung metallischer Anteile sowie von metallabgereichertem Material aus metallhaltigen Materialien

Also Published As

Publication number Publication date
DE3762054D1 (de) 1990-05-03
EP0234256B1 (fr) 1990-03-28
US4725341A (en) 1988-02-16
JPS62182292A (ja) 1987-08-10
DE3602683A1 (de) 1987-08-06

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