EP0575699A2 - Procédé et appareil de régénération d'une solution aqueuse contenant des ions métalliques et de l'acide sulfurique, ainsi que l'utilisation - Google Patents

Procédé et appareil de régénération d'une solution aqueuse contenant des ions métalliques et de l'acide sulfurique, ainsi que l'utilisation Download PDF

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Publication number
EP0575699A2
EP0575699A2 EP93104001A EP93104001A EP0575699A2 EP 0575699 A2 EP0575699 A2 EP 0575699A2 EP 93104001 A EP93104001 A EP 93104001A EP 93104001 A EP93104001 A EP 93104001A EP 0575699 A2 EP0575699 A2 EP 0575699A2
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EP
European Patent Office
Prior art keywords
sulfuric acid
anolyte
ions
catholyte
solution containing
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.)
Withdrawn
Application number
EP93104001A
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German (de)
English (en)
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EP0575699A3 (en
Inventor
Ulrich Dr. Ströder
Lothar Schneider
Wolfgang Dr. Blatt
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.)
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektrochemie GmbH
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Publication date
Application filed by Heraeus Elektrochemie GmbH filed Critical Heraeus Elektrochemie GmbH
Publication of EP0575699A2 publication Critical patent/EP0575699A2/fr
Publication of EP0575699A3 publication Critical patent/EP0575699A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the invention relates to a method for regenerating an aqueous solution containing metal ions and sulfuric acid, in particular a solution containing zinc ions, nickel ions, iron ions and / or copper ions, in an electrolytic cell, the metal ions being deposited on the surface of the cathode and on the anode by water decomposition Oxygen and protons are formed, as well as the use of the method and device.
  • Such a direct regeneration of a zinc chloride solution is known from DE-OS 25 39 137, according to which the chloride ion-containing solution is introduced into a cathode chamber of an electrolysis cell, which is divided into 3 chambers, namely an anode chamber, a cathode chamber and an electrolyte chamber arranged between them ; the anode chamber is bounded by a porous diaphragm of low permeability, which separates the anolyte from the electrolyte, the anolyte containing sulfuric acid.
  • the anions of the anolyte have an oxidation potential that is high enough to ensure that essentially only the decomposition of water at the anode takes place under operating conditions, while the cathode chamber is delimited by a relatively high permeability through a diaphragm.
  • the anolyte has a substance capable of combining with the chloride ions entering the anode chamber so as to prevent oxidation of chloride ions at the anode.
  • the liquid level of the anolyte if necessary, is always kept so that the liquid level lies above the liquid level of the neighboring electrolyte, so as to maintain the desired flow rate through the diaphragm in order to achieve the technical purposes.
  • the anolyte contains a silver sulfate additive to ensure the precipitation of the chloride as silver chloride.
  • a problem with this arrangement is the comparatively complex division of the electrolyte space into 3 chambers and the use of diaphragms, the permeability of which can change significantly in the course of the electrolytic process.
  • Other problems include the addition of chemicals to silver sulfate, the formation of silver chloride and its removal from the cell, and the risk of diaphragm blockages due to silver chloride precipitation.
  • the object of the invention is to provide a method and a device by means of which sulfuric acid pickling or extraction solutions which are heavily contaminated with metal ions are to be demetallized to the greatest possible extent, at the same time a pure, highly concentrated sulfuric acid is to be obtained.
  • the cathodic deposition of hydrogen as can occur in particular in aqueous solutions with a relatively low metal ion concentration, should be avoided with certainty.
  • the process is to be used as an intermediate stage of a chlorine gas-free regeneration of pickling or extraction solutions.
  • the invention is achieved in that the solution containing metal ions is introduced as a catholyte into an electrolysis cell which is subdivided using an anion exchange membrane which is stable to sulfuric acid, sulfate ions from the catholyte passing through the anion exchange membrane due to the voltage applied to the electrodes in the solution Anolytes migrate and sulfuric acid is generated with the anodically formed protons and the sulfuric acid concentration in the anolyte is constantly increased.
  • the concentrated sulfuric acid is removed from the anolyte.
  • a major advantage of the process is that the concentrated sulfuric acid can be returned to the pickling or extraction process as a fresh solution component in the manner of a cycle, and that the cathodically deposited metal can also be recycled.
  • the process can be carried out either batchwise or continuously, with a solution being supplied as catholyte in batch operation, the sulfuric acid concentration of which corresponds in each case to the initial concentration of the anolyte; on the other hand, if the solution is fed continuously as catholyte, its sulfuric acid concentration must generally always be below the sulfuric acid concentration of the anolyte.
  • a solution with a sulfuric acid concentration in the range from 60 to 80 g / l is supplied as the catholyte.
  • the cathodic deposition takes place at a current density in the range from 250 to 1500 A / m 2.
  • the cathode is removed from the catholyte space after the metal deposition has reached a predetermined layer thickness.
  • the electrolytic cell is divided into an anolyte space and a catholyte space by means of an anion exchange membrane which is stable with respect to sulfuric acid, in that the catholyte space has at least one opening for supplying the solution containing metal ions and the anolyte space has at least one opening for removing electrolysis formed sulfuric acid, the cathode being electrically and mechanically detachable for removing the deposited metal.
  • the process according to the invention is preferably used as a subsequent process step in a pickling or extraction process, in which, in a first process step, a solution containing chloride ions is converted into a solution containing sulfate ions by means of the ion exchange process.
  • a major advantage of the invention is the fact that the metal can be separated from a metal ion-containing sulfate solution in a simple, inexpensive manner, at the same time a concentration of the sulfuric acid of the anolyte takes place in the form of a cycle, which in turn is used to continue the regeneration process .
  • Figure 1 shows schematically in longitudinal section an electrolysis cell.
  • Figure 2 shows schematically the process flow in the form of a circuit.
  • the electrolysis device has a trough 1, the interior of which is divided into an anolyte space 3 and a catholyte space 4 by means of an anion exchange membrane 2.
  • the anode 5 located in the anolyte compartment 3 consists of a dimensionally stable valve metal electrode, in particular titanium electrode, which is connected to the positive pole 6 of a DC voltage source 7.
  • the basic structure of such dimensionally stable valve metal electrodes, in particular titanium electrodes, is known from chloralkali electrolysis and is described, for example, in DE-OS 20 41 250.
  • the cathode 8 located in the catholyte space 4 is made of expanded copper, it is connected via a detachable electrical connection 9 to the negative pole 10 of the direct voltage source.
  • an aqueous sulfuric acid solution which is fed in at the beginning of the process via feed line 11 to produce the ion conduit, water possibly being added during the electrolysis process and the additional sulfuric acid formed being able to be removed via outlet 12 of the anolyte compartment 3 and the regeneration process, for example pickling can be fed again.
  • the sulfate solution containing zinc ions is fed continuously to the catholyte space 4 via feed line 13, the sulfuric acid concentration of the catholyte generally corresponding at most to that of the anolyte; the sulfuric acid concentration of the anolyte is in the range of 70 g / l.
  • the electrolysis process begins, the charge being transported by applying the voltage source 7 during the electrolysis through the ion exchange membrane 2 by means of the sulfate ions, which are symbolically designated by reference number 13.
  • the zinc ions are symbolically provided with reference number 14 and are discharged at the cathode 8, metallic zinc being deposited.
  • the anolyte compartment 3 there is a decomposition of the water portion of the anolyte solution, the oxygen being removed as gas from the open trough 1 and the hydrogen ions being recombined together with the sulfate ions to form sulfuric acid, which is concentrated in the course of the electrolysis process and via the outlet 12 is removed to the pickling process.
  • the sulfuric acid concentration of the anolyte is adjusted with the aid of pH-value meters and a control circuit, which maintains the predetermined sulfuric acid concentration or the sulfuric acid by removing the concentrated sulfuric acid and supplying water via line 11 adjusts the concentration of the catholyte.
  • the catholyte supplied as a pickling solution has a zinc ion concentration of approximately 170 g / l and a sulfuric acid concentration in the range of 70 g / l.
  • the cathode 8 is made in the form of a copper expanded metal, while the anode 5 consists of the dimensionally stable titanium anode already mentioned. Zinc is applied to the cathode 8 in a compact deposition quality.
  • the current density of the cathode is in the range from 250 to 1500 A / m 2 .
  • the same electrolysis device can also be used for batchwise operation, in which case the anolyte is removed batchwise or continuously within certain concentration ranges, while the catholyte side is replenished in batches.
  • the sulfate solution containing zinc ions flowing out of outlet 21 of a pickling device 20 is fed via feed line 13 to the catholyte compartment 4 of the electrolysis cell having a trough 1 with an anion exchange membrane 2, the zinc deposited in the catholyte compartment - represented schematically by reference number 22 - from the catholyte compartment 4 is discharged.
  • the concentrated aqueous sulfuric acid solution which forms in the anolyte compartment 3 is fed via outlet 12 and line 23 as a fresh component for the pickling process via feed 24 to the pickling device 20.
  • the process cycle of the solution containing sulfuric acid is shown in FIG. 2, the used pickling solution being fed as an aqueous sulfate solution containing metal ions to the electrolytic cell via outlet 21 of the pickling device 20 and feed line 13 of the cell, while the practically pure concentrated sulfuric acid is in turn fed via line 23 to the cell Pickling process is supplied.
  • the deposited zinc is removed from this cell cycle by removal from the cell; it can also be used again.
  • a membrane of the ARA type from MORGANE (France) is used as the anion exchange membrane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP19930104001 1992-06-10 1993-03-12 Process and apparatus for regenerating metal ions and sulfuric acid containing aqueous solutions and use thereof Withdrawn EP0575699A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4218915 1992-06-10
DE19924218915 DE4218915A1 (de) 1992-06-10 1992-06-10 Verfahren und Vorrichtung zur Regenerierung einer Metallionen und Schwefelsäure enthaltenden wäßrigen Lösung sowie Verwendung

Publications (2)

Publication Number Publication Date
EP0575699A2 true EP0575699A2 (fr) 1993-12-29
EP0575699A3 EP0575699A3 (en) 1994-06-01

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ID=6460669

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EP19930104001 Withdrawn EP0575699A3 (en) 1992-06-10 1993-03-12 Process and apparatus for regenerating metal ions and sulfuric acid containing aqueous solutions and use thereof

Country Status (4)

Country Link
EP (1) EP0575699A3 (fr)
JP (1) JPH0688275A (fr)
CA (1) CA2097868A1 (fr)
DE (1) DE4218915A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19521132C1 (de) * 1995-06-09 1996-10-17 Poligrat Holding Gmbh Verfahren zum Entmetallisieren von hochsauren Bädern und Verwendung dieses Verfahrens beim Elektropolieren von Edelstahloberflächen
DE19521596C1 (de) * 1995-06-14 1996-11-28 Ksd Innovations Gmbh Umwelt U Verfahren und Vorrichtung zur elektolytischen Abscheidung von Zink und Kupfer aus saurer Lösung
DE19850524C2 (de) * 1998-11-03 2002-04-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Nitratfreies Recycling-Beizverfahren für Edelstähle
DE19850525A1 (de) * 1998-11-03 2000-05-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Verfahren zum elektrochemischen Regenerieren von Schwefelsäure-Eisen-III-sulfat-Beizlösungen für Edelstähle
US20110089045A1 (en) * 2008-04-11 2011-04-21 Francois Cardarelli Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors
DE102008056776A1 (de) 2008-11-11 2010-05-12 Enthone Inc., West Haven Galvanisches Bad und Verfahren zur Abscheidung von zinkhaltigen Schichten
WO2022070119A1 (fr) * 2020-10-02 2022-04-07 Zincovery Process Technologies Limited Processus d'extraction électrochimique de métaux dissous et appareil associé
WO2022204394A1 (fr) 2021-03-24 2022-09-29 Electrasteel, Inc. Système de conversion de fer en 2 étapes

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2810686A (en) * 1954-11-09 1957-10-22 Rohm & Haas Electrolytic treatment of waste sulfate pickle liquor
DE1621577A1 (de) * 1966-01-22 1971-07-08 Gewerk Keramchemie Verfahren zur selektiven Entfernung von Zinkionen aus stark salzsauren Eisenbeizen
JPS50151793A (fr) * 1974-05-29 1975-12-05
DE2539137A1 (de) * 1974-09-04 1976-03-25 Atok Platinum Mines Proprietar Verfahren zur elektrolytischen gewinnung von nickel und zink sowie elektrolysezelle hierfuer
US4148700A (en) * 1976-10-14 1979-04-10 David B. Dean Method for purifying the liquor of a galvanizing process plant after contamination
US4149951A (en) * 1978-05-22 1979-04-17 Eddleman William L Frame filter press and apparatus
FR2645044A1 (fr) * 1989-03-30 1990-10-05 Morgane Membrane echangeuse d'ions pour electrodialyse et procede de recuperation d'acides mineraux mettant en oeuvre une telle membrane
EP0435382A1 (fr) * 1989-12-28 1991-07-03 METALLGESELLSCHAFT Aktiengesellschaft Procédé électrolytique pour le traitement de décapants usés ou flux de produits contenant des ions métalliques

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5021541B2 (fr) * 1972-08-22 1975-07-23
FR2273082B1 (fr) * 1974-05-28 1978-03-31 Seprac
JPS5411153B2 (fr) * 1974-10-04 1979-05-12
JPS51135173A (en) * 1975-05-19 1976-11-24 Asahi Glass Co Ltd Method of treating waste liquor containing acids and metal salts there of
JPS52101690A (en) * 1976-02-24 1977-08-25 Asahi Glass Co Ltd Separation of acid and metal from solution containing acid and its met al salts and recovery of them
JPS5311814A (en) * 1976-07-21 1978-02-02 Nakamura Minoru Electrolytic recovering method of nickel using ion exchange membranes
JPS5544588A (en) * 1978-09-26 1980-03-28 Sumitomo Metal Ind Ltd Recovering method for mixture of hydrofluoric acid and nitric acid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2810686A (en) * 1954-11-09 1957-10-22 Rohm & Haas Electrolytic treatment of waste sulfate pickle liquor
DE1621577A1 (de) * 1966-01-22 1971-07-08 Gewerk Keramchemie Verfahren zur selektiven Entfernung von Zinkionen aus stark salzsauren Eisenbeizen
JPS50151793A (fr) * 1974-05-29 1975-12-05
DE2539137A1 (de) * 1974-09-04 1976-03-25 Atok Platinum Mines Proprietar Verfahren zur elektrolytischen gewinnung von nickel und zink sowie elektrolysezelle hierfuer
US4148700A (en) * 1976-10-14 1979-04-10 David B. Dean Method for purifying the liquor of a galvanizing process plant after contamination
US4149951A (en) * 1978-05-22 1979-04-17 Eddleman William L Frame filter press and apparatus
FR2645044A1 (fr) * 1989-03-30 1990-10-05 Morgane Membrane echangeuse d'ions pour electrodialyse et procede de recuperation d'acides mineraux mettant en oeuvre une telle membrane
EP0435382A1 (fr) * 1989-12-28 1991-07-03 METALLGESELLSCHAFT Aktiengesellschaft Procédé électrolytique pour le traitement de décapants usés ou flux de produits contenant des ions métalliques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 84, no. 16, 19. April 1976, Columbus, Ohio, US; abstract no. 109068p, KANAGAWA 'Recovery of iron and acid from waste acid' Seite 226 ; & JP-A-50 151 793 (KANAGAWA) *
INDUSTRIAL AND ENGINEERING CHEMISTY Bd. 47, Nr. 1 , 1. Januar 1955 Seiten 67 - 70 BRAMER H. C. 'Electrolytic Regeneration of Spent Pickling solutions' *

Also Published As

Publication number Publication date
DE4218915A1 (de) 1993-12-16
CA2097868A1 (fr) 1993-12-11
JPH0688275A (ja) 1994-03-29
EP0575699A3 (en) 1994-06-01

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