WO1995023880A1 - Traitement de solutions d'electrolytes - Google Patents

Traitement de solutions d'electrolytes Download PDF

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Publication number
WO1995023880A1
WO1995023880A1 PCT/AU1995/000109 AU9500109W WO9523880A1 WO 1995023880 A1 WO1995023880 A1 WO 1995023880A1 AU 9500109 W AU9500109 W AU 9500109W WO 9523880 A1 WO9523880 A1 WO 9523880A1
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WO
WIPO (PCT)
Prior art keywords
anolyte
catholyte
iron
compartment
chloride
Prior art date
Application number
PCT/AU1995/000109
Other languages
English (en)
Inventor
Neal Barr
Original Assignee
Spunboa Pty. Limited
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
Application filed by Spunboa Pty. Limited filed Critical Spunboa Pty. Limited
Priority to AU18855/95A priority Critical patent/AU1885595A/en
Publication of WO1995023880A1 publication Critical patent/WO1995023880A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury

Definitions

  • the present invention relates to the treatment of electrolyte solutions.
  • the invention has particular, but not exclusive, application to the treatment of spent pickle liquor from the hot dip galvanising industry. BACKGROUND ART
  • the metal preparation line of a hot dip galvanizing plant includes an acid pickling stage in which rust and scale are removed from the steel prior to galvanizing.
  • Hydrochloric acid is the acid most commonly used in the pickling operation and as a batch of this acid, referred to as pickle liquor, is used its strength decreases and it becomes contaminated with dissolved iron.
  • pickle liquor When the acid strength decreases to a level where the pickling rate becomes unacceptable slow the acid is said to be "spent” and it is discarded and replaced by a fresh batch.
  • the spent acid before the spent acid is discarded it is used as a "stripping acid” to remove zinc from jigs and from work which requires reprocessing. Spent acid from these plants is thus contaminated with dissolved zinc as well as dissolved iron.
  • the rate at which spent pickling acid is generated varies widely depending on individual plant practices and up to 40 litres of spent acid may be generated for every tonne of steel dipped.
  • the compositions of these spent acids also vary widely. They may contain over 100 grams per litre of iron, over 100 grams per litre of zinc and the chloride concentration may be as high as 330 grams per litre.
  • Present practice is to dispose of these liquors at approved liquid waste disposal sites and the total cost of this practice, including the loss of metal and chloride value of the acid as well as the disposal charges varies from one country to another. In Australia the disposal charge is approximately A$20 per dipped tonne. If spent pickle liquor is to be recycled, the metal contaminants must be removed and the acid concentration of the solution must be increased.
  • An anion exchange membrane separates each of the cathodic compartments from the intermediate compartments
  • a cation exchange membrane separates each of the intermediate compartments from the anodic compartment.
  • hydrogen ions migrate from the anodic compartment into each of the intermediate compartments
  • chloride ions migrate from each of the cathodic compartments into each of the intermediate compartments thereby generating a weak hydrochloric acid solution in each of the intermediate compartments.
  • the present invention provides a technique whereby metals can be plated from hydrochloric acid metal salt solutions without the difficulties associated with the use of anion exchange membranes and, in addition, provides a technique for reducing salt solution concentration for disposal.
  • the present invention provides a method of treating a hydrohalic acid/metal salt solution in an electrolytic cell having a cation exchange membrane dividing the cell into an anodic compartment containing an anode and a cathodic compartment containing a cathode, the method comprising the steps of:
  • the soluble non-plating metal salt is a halide salt and the halide ions migrate to the anode where the halide is oxidised to produce the corresponding halogen.
  • the halide is chloride and chlorine gas is produced at the anode. The chlorine gas can be collected and converted to hydrogen chloride and thence to hydrochloric acid.
  • the soluble non-plating metal is a metal less noble than zinc such as an alkali metal or alkaline earth metal.
  • the soluble non-plating metal may be selected from sodium, potassium, calcium, magnesium and aluminium but it is particularly preferred that the soluble non-plating metal is sodium.
  • the anolyte is preferably a sodium chloride solution.
  • a sodium chloride anolyte is progressively depleted of both sodium and chloride as the cell operates and thus the sodium chloride solution becomes progressively more dilute. Therefore, it is advantageous to supply a strong sodium chloride solution to the anodic compartment as the anolyte.
  • the sodium chloride solution supplied to the anodic compartment is a saturated sodium chloride solution, and more preferably, the source of the sodium chloride solution is maintained as a saturated solution during operation of the cell.
  • the hydrohalic acid/metal salt solution may be a hydrochloric acid, a hydrobromic acid or a hydrofluoric acid solution containing metal salt(s).
  • the catholyte is a hydrochloric acid solution containing metal salt(s). It will be appreciated that the catholyte is progressively depleted in metal cations as the cell operates and that these cations are replaced by the soluble non-plating metal cations. However, because anions cannot readily cross the cation exchange membrane, the anion concentration remains relatively constant, with the exception of concentration changes resulting from water transport across the cation exchange membrane.
  • the catholyte is a spend pickle liquor comprising a hydrochloric acid solution containing dissolved iron as iron chloride, or a hydrochloric acid solution containing dissolved iron and dissolved zinc as iron chloride and zinc chloride respectively.
  • the catholyte may be a hydrochloric acid solution containing dissolved copper as copper chloride.
  • Such a solution may be derived from hydrochloric acid etching of circuit boards or from hydrochloric acid pickling of copper in preparation for chrome plating of the copper.
  • the catholyte is a hydrochloric acid/iron chloride solution and the anolyte is sodium chloride
  • the iron cations plate onto the cathode as metal or electroprecipitate as iron hydroxide and sodium cations migrate across the cation exchange membrane into the cathodic compartment as the cell operates. Accordingly, the catholyte is progressively depleted in iron but enriched in sodium to create a strong sodium chloride solution.
  • the strong sodium chloride solution so created can be used as a source of anolyte for the anodic compartment.
  • the anolyte concentration may be increased by evaporation if desired.
  • a plurality of cells may be utilised, for example a series of cells may be utilised in treating a hydrochloric acid/iron chloride/zinc chloride catholyte solution.
  • a series of cells can be operated with the result that zinc is plated early in the series with iron not being plated until the zinc is virtually depleted from the catholyte.
  • the flow of catholyte close to the cathode can affect plating of the metals with iron plating being favoured where turbulence is induced in the proximity of the cathode. It is therefore preferred to avoid turbulence in the proximity of cathodes early in a series of cells where it is desirable to plate zinc prior to plating iron.
  • the present invention provides a method of treating a dilute salt solution in an electrolytic cell having a cation exchange membrane dividing the cell into an anodic compartment containing an anode and a cathodic compartment containing a cathode, the method comprising the steps of:
  • the second aspect of the present invention can be used to strip salt from the dilute salt solution.
  • the anolyte is a dilute sodium chloride solution with the result that sodium cations migrate into the cathodic compartment, chlorine is generated at the anode, and a very dilute salt solution suitable for disposal is produced in the anodic compartment.
  • the catholyte is dilute sodium hydroxide which is concentrated by operating the cell.
  • liquid turbulence can be induced as the solutions flow through the cell to enhance mass transport.
  • Figure 1 is a schematic representation of an electrolytic cell which can be used in accordance with the present invention.
  • Figure 2 is a schematic representation of the electrolytic cell illustrated in Figure 1 which illustrates the electrochemical reactions occurring within the cell;
  • Figure 3 is a schematic representation of electrolytic cell modules
  • Figure 4 is a schematic representation of a plurality of electrolytic cell modules housed within a tank
  • Figure 5 is a schematic representation of a series of electrolytic cells for treating a spent pickle liquor catholyte
  • Figure 6 is a schematic representation of a series of electrolytic cells for treating a spend pickle liquor catholyte
  • Figure 7 is a schematic representation of a series of electrolytic cells for treating a dilute salt solution in a salt stripping process
  • Figures 8, 9 and 10 are plots illustrating the variation of % HC1, g/L zinc and g/L iron respectively against amp hours passed during the process reported in the Example.
  • the electrolytic cell 10 is divided into a cathodic compartment 11 and an anodic compartment 12 by a cation exchange membrane 13.
  • the cathodic compartment 11 and the anodic compartment 12 house cathode 14 and anode 15 respectively.
  • the catholyte is introduced via line 16 and is pumped by pump 17 in a closed loop upwards and over the surface of the cathode 14 where metal cations are removed from the catholyte and deposited onto the surface of the cathode 14 as metal.
  • the metal cations in particular iron cations, can precipitate as metal hydroxide.
  • the anolyte is introduced from anolyte holding tank 18 and is pumped by pump 19 upwards over the surface of the anode 15 where anolyte anions are oxidised with anolyte cations crossing the cation exchange membrane 13 from anodic compartment 12 into cathodic compartment 11.
  • Anolyte is recycled to anolyte holding tank 18 via line 20.
  • the main processes which determine the performance of the cell 10 are the electrochemical reactions which occur at the cathode 14 and the anode 15 and the diffusion processes which occur across the membrane 13.
  • the cell 10 is capable of operating with current densities up to 800 amps/m 2 and cell voltages less than 4 volts.
  • the cathode 14 may be made of any suitable material but mild steel, titanium and stainless steel are preferred. Electrodes from which deposited metal can be easily peeled (“peel electrodes") may be used to allow easy harvesting of the deposited metal.
  • Suitable cation exchange membranes 13 are any chlor-alkali membranes and particular examples of these are NAFION (product of Dupont) and FLEMION (product of Asahi Glass) . These membranes are not chlorine sensitive and so do not suffer from possible degradation through reaction with chlorine as do the anion exchange membranes used in previous methods.
  • the anode 15 may be made of any suitable material. Preferably, the anode is made from titanium coated with mixed metal oxides and is of the type known as a dimensionally stable anode (DSA) .
  • DSA dimensionally stable anode
  • the catholyte is a spent pickle liquor (hydrochloric acid containing iron chloride) and the anolyte is a saturated sodium chloride solution.
  • iron (II) cations are removed and deposited as metallic iron on the surface of the cathode 14.
  • An electrochemical balance is maintained in the cathodic compartment 11 because the iron (II) cations that are removed from the catholyte are replaced by an electrochemically equivalent quantity of sodium cations which diffuse across the membrane 13 from anolyte in the anodic compartment 12.
  • Sodium ions in the cathodic compartment 11 have effectively no tendency to plate sodium metal on the cathode and remain in solution in that compartment, together with the chloride ions which were present initially and which, although having a tendency to migrate to the anode 15, are effectively prevented from leaving the cathodic compartment 11 by the cation exchange membrane 13.
  • the electrochemical balance in anodic compartment 12 is also maintained because a quantity of chloride anions electrochemically equivalent to the sodium cations is also removed from the anolyte as chlorine is generated at the surface of the anode 15 by oxidation.
  • the concentration of sodium cations decreases with a corresponding decrease in the concentration of chloride anions.
  • the chlorine gas which bubbles off may be collected to subsequently be combusted with hydrogen, or some other source of hydrogen such as natural gas, to produce hydrogen chloride which may be absorbed into water to produce fresh hydrochloric acid or absorbed into a weak pickle liquor to enhance its acid strength.
  • Sodium chloride produced in the cathodic compartment 11 may be used as a source of anolyte.
  • electrolytic cells 10 are most effectively used in the form of modules which contain a plurality of cells 10.
  • Cathodic compartments 11 and anodic compartments 12 may be formed by the use of cathodes 14, half-anode assemblies 21 and full-anode assemblies 22 which are housed within a tank 23 which is made from glass-reinforced polymer and which has very high chemical and dimensional stability.
  • the modular arrangement illustrated in Figure 4 consists of tank 23, two half-anode assemblies 21, four cathodes 14 and three full-anode assemblies 22. Catholyte is gravity fed into one end of the tank 23 via line 24 and leaves the tank 23 via an overflow weir (not shown) and line 25.
  • the catholyte is pumped upwardly over the cathodes 14 by a catholyte pump (not shown) which maintains a high recirculation ratio.
  • Anolyte from the holding tank (not shown) is gravity fed to the anode assemblies at a constant head and flows upwardly over the surface of the anodes 15 with the anolyte recirculation rate also being maintained at a high level to ensure efficient flushing of chlorine from the anode assemblies.
  • the cathodes 14 are routinely removed from the tank 23 for recovery of deposited metal. Modules can be operated in a variety of configurations depending upon the nature of the catholyte and the rate at which the catholyte is to be treated.
  • a series of eight cells 30-37 are configured for treatment of a spent pickle liquor catholyte (hydrochloric acid containing iron chloride and zinc chloride) .
  • Each cell 30-37 comprises a cathodic compartment (indicated by a minus sign (-)) and an anodic compartment (indicated by a plus sign (+) ) .
  • the catholyte is introduced into the cathodic compartment of cell 30 via line 38.
  • the catholyte contains iron (II) cations and zinc cations, zinc metal is anomalously and preferentially plated on the cathode and because of the inherent inefficiency of this process, hydrogen is evolved at the same time and acid is destroyed.
  • the solution leaving the cathodic compartment of cell 30 enters the cathodic compartment of cell 31 depleted in zinc cations, enriched in sodium cations and with reduced acid strength.
  • the solution passes from cathodic compartment to cathodic compartment along the series of cells 30-37 with zinc being deposited on the cathodes of cells 30-34 until the concentration of zinc cations falls to the point where zinc is no longer deposited and iron is deposited on the cathodes of cells 35-37.
  • turbulence is avoided in the proximity of the cathodes of these cells.
  • the concentrated of sodium cations in the cathodic compartments increases with the result that a concentrated sodium chloride solution exits cell 37 via line 39 and is transferred to anolyte holding tank 18.
  • the solution entering anolyte holding tank 18 is essentially free of zinc cations and iron (II) cations.
  • the current in each cell 30-37 is adjusted to give the optimum current density for the catholyte being processed in the particular cathodic compartment.
  • Anolyte from the anolyte holding tank 18 is fed via lines 40 to the anodic compartment of each cell 30-37. Chlorine generated in the anodic compartment of each cell 30-37 is swept to the anolyte holding tank 18 by recirculating anolyte via line 41.
  • Air is introduced into anolyte holding tank via line 42 with air/chlorine removed from anolyte holding tank 18 via line 43 for production of hydrochloric acid.
  • An electrochemical balance is maintained over the complete system with sodium chloride effectively cycling through the system and evaporative losses from the anolyte holding tank 18 via line 44 assist in maintaining a water balance in the system.
  • Zinc can be recovered at purities better than 99.9% which enables recovered zinc to be returned directly to a zinc bath in a galvanising process.
  • a series of four cells 50-53 are configured for treatment of a spent pickle liquor catholyte. The arrangement is similar to that illustrated in Figure 5 but with the important difference that the anolyte holding tank has been omitted.
  • the catholyte is introduced via line 38 to the cathodic compartment of the first cell 50 in the series and passes sequentially through the cathodic compartments of cells 50-53 with a concentrated sodium chloride solution exiting cell 53 via line 39.
  • the concentrated sodium chloride solution is then cycled into the anodic compartment of cell 53 and sequentially through the anodic compartments of cells 52, 51 and 50.
  • the sodium chloride solution passes through the anodic compartments of cells 53-50, it is progressively depleted of sodium cations and chloride anions as the sodium cations pass across the cation exchange membranes and the chloride anions are oxidised to chlorine at the anodes until the solution emerging from the anodic compartment of cell 50 via line 54 is a dilute sodium chloride solution.
  • This arrangement has the advantage over that illustrated in Figure 5 of maintaining a water balance; however, a dilute sodium chloride solution is produced.
  • the dilute sodium chloride solution can be treated as illustrated in Figure 7.
  • the dilute sodium chloride solution is introduced into the anodic compartment of cell 60 (which is of the same type as that illustrated in Figure 1) via line 61.
  • additional sodium cations migrate across the cation exchange membrane into the cathodic compartment and additional chloride anions are oxidised at the anode.
  • the anolyte emerges from the anodic compartment of cell 60 depleted in sodium cations and chloride anions and then is further depleted of these ions in the anodic compartments in each of cells 62, 63 and 64 to emerge from the anodic compartment of cell 64 via line 65 as a very dilute salt solution which is suitable for disposal.
  • Dilute sodium hydroxide solution is introduced into the cathodic compartment of cell 64 via line -66.
  • the sodium hydroxide solution is strengthened as it passes progressively through each of cells 64, 63, 62 and 60, until a more concentrated sodium hydroxide solution emerges from the cathodic compartment of cell 60 via line 67.
  • hot sodium hydroxide solution is used in most galvanising and metal preparation lines, the solution is continually in need of water top-up. A reasonably dilute stream of sodium hydroxide is thus useful.
  • a 6 litre sample of spent hydrochloric acid pickle liquor from a general galvanising plant was treated in accordance with the present invention. Ignoring minor components, the pickle liquor contained 115.2 g/L zinc, 78.6 g/L iron, 3.48% hydrochloric acid with the balance being chloride.
  • the treatment produced 416g of zinc and 318g of iron in the form of recyclable zinc and zinc/iron alloy.
  • the current efficiency based upon the combined removal of hydrogen ion, zinc and iron from the treatment sample was, after adjustment for analytical sample removal, approximately 100%.
  • the present invention is broadly applicable to the treatment of a range of hydrohalic acid/metal salt solutions to recover metal and halide values.
  • the present invention can be very usefully applied to the treatment of spent pickle liquor from the hot dip galvanizing industry and can be incorporated into an existing hot dip galvanizing process, thus avoiding the need to dispose of spent pickle liquor.
  • Iron and, where applicable, zinc can be recovered from the spent liquor at sufficient purities to enable sale or re-use; chlorine is generated in sufficient quantities to be used in the manufacture of hydrochloric acid; and generated sodium chloride can be re-used directly as anolyte or supplement a supply of anolyte.
  • An important feature of the present invention is its ability to treat a spent pickle liquor which has also been used as a stripping acid and therefore contains both iron and zinc.
  • the present invention allows for recovery of zinc at purities approaching 100% and hence for the re-use of recovered zinc in the zinc bath of a galvanizing plant.
  • the zinc is recovered at under 4MWh per tonne in the zinc electrowin stage and, when this is coupled with savings in spent pickle liquor disposal costs, an economic benefit in more fully using spent pickle layer as a stripping acid results.
  • the present invention provides for versatility of use in a galvanizing plant.
  • the present invention can be used to remove essentially all the acid, zinc and iron from a spent pickle liquor with the exhausted catholyte either transferred to an anolyte holding tank or directly introduced into an electrolytic cell as anolyte, and with the produced chlorine being sent to a conventional hydrogen chloride synthesis unit to produce hydrochloric acid.
  • exhausted catholyte is directly introduced to a cell as anolyte
  • the present invention can also be used to strip salt from the resulting exhausted anolyte, allowing for its inexpensive disposal with the resulting caustic solution suitable for re-use elsewhere in the galvanizing plant.
  • the present invention can be used to remove only the acid and the zinc from spent pickle liquor with the iron being removed in a conventional sedimentation step and the chlorine being recovered using modified chloralkali technology and again being used to produce hydrochloric acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

Une liqueur épuisée de décapage qui comprend une solution d'acide chlorhydrique contenant du fer dissous sous forme de chlorure de fer est traitée dans une cellule électrolytique (10) divisée en un compartiment cathodique (11) et un compartiment anodique (12) par une membrane échangeuse de cations (13). Une cathode (14) et une anode (15) sont situées respectivement dans le compartiment cathodique (11) et le compartiment anodique (12). La liqueur épuisée de décapage est introduite dans le compartiment cathodique (11) en tant que catholyte et une solution de chlorure de sodium saturée est introduite dans le compartiment anodique en tant qu'anolyte. Pendant le fonctionnement de la cellule (10), des cations de fer (II) issus du catholyte se plaquent sur la cathode (11) sous forme de fer métallique, des cations de sodium issus de l'anolyte traversent la membrane (13) et pénètrent dans le compartiment cathodique (11) et des anions de chlorure issus de l'anolyte sont oxydés en gaz chloré au niveau de l'anode (12).
PCT/AU1995/000109 1994-03-04 1995-03-06 Traitement de solutions d'electrolytes WO1995023880A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU18855/95A AU1885595A (en) 1994-03-04 1995-03-06 Treatement of electrolyte solutions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPM4248A AUPM424894A0 (en) 1994-03-04 1994-03-04 Treatment of electrolyte solutions
AUPM4248 1994-03-04

Publications (1)

Publication Number Publication Date
WO1995023880A1 true WO1995023880A1 (fr) 1995-09-08

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034212A1 (fr) * 2006-09-21 2008-03-27 Qit-Fer & Titane Inc. Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorures métalliques riches en fer
WO2009114925A1 (fr) * 2008-03-20 2009-09-24 Qit-Fer & Titane Inc. Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorure métallique riche en fer
CN101517129B (zh) * 2006-09-21 2011-05-11 魁北克钛铁公司 从富铁金属氯化物废料回收有价值的金属铁和氯的电化学方法
FR2977804A1 (fr) * 2011-07-15 2013-01-18 Tredi Procede de traitement d'effluents liquides en milieu chlorure et separation du zinc et du nickel, installation pour sa mise en oeuvre et application aux effluents industriels metalliferes
CN103422154A (zh) * 2012-05-24 2013-12-04 叶福祥 电路板酸性废蚀刻液氯化亚铜(Cu+,CuCL)离子隔膜电积再生
CN110902781A (zh) * 2019-12-14 2020-03-24 西安建筑科技大学 一种铁-空气电池处理含磷废水并回收磷资源的装置及方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514270A (en) * 1981-09-25 1985-04-30 Hitachi, Ltd. Process for regenerating cleaning fluid
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
WO1993006262A1 (fr) * 1991-09-24 1993-04-01 Metallgesellschaft Aktiengesellschaft Procede et dispositif pour la regeneration de decapants recuperes
WO1993006261A1 (fr) * 1991-09-23 1993-04-01 Spunboa Pty Ltd Extraction electrolytique de metaux a partir de solutions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4514270A (en) * 1981-09-25 1985-04-30 Hitachi, Ltd. Process for regenerating cleaning fluid
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
WO1993006261A1 (fr) * 1991-09-23 1993-04-01 Spunboa Pty Ltd Extraction electrolytique de metaux a partir de solutions
WO1993006262A1 (fr) * 1991-09-24 1993-04-01 Metallgesellschaft Aktiengesellschaft Procede et dispositif pour la regeneration de decapants recuperes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034212A1 (fr) * 2006-09-21 2008-03-27 Qit-Fer & Titane Inc. Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorures métalliques riches en fer
CN101517129B (zh) * 2006-09-21 2011-05-11 魁北克钛铁公司 从富铁金属氯化物废料回收有价值的金属铁和氯的电化学方法
AU2007299519B2 (en) * 2006-09-21 2011-12-15 Qit-Fer & Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes
WO2009114925A1 (fr) * 2008-03-20 2009-09-24 Qit-Fer & Titane Inc. Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorure métallique riche en fer
AU2008352881B2 (en) * 2008-03-20 2013-04-04 Rio Tinto Iron & Titanium Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes
US8784639B2 (en) 2008-03-20 2014-07-22 Rio Tinto Fer Et Titane Inc. Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes
FR2977804A1 (fr) * 2011-07-15 2013-01-18 Tredi Procede de traitement d'effluents liquides en milieu chlorure et separation du zinc et du nickel, installation pour sa mise en oeuvre et application aux effluents industriels metalliferes
CN103422154A (zh) * 2012-05-24 2013-12-04 叶福祥 电路板酸性废蚀刻液氯化亚铜(Cu+,CuCL)离子隔膜电积再生
CN110902781A (zh) * 2019-12-14 2020-03-24 西安建筑科技大学 一种铁-空气电池处理含磷废水并回收磷资源的装置及方法

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