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WO1995024518A1 - Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation - Google Patents

Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation Download PDF

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Publication number
WO1995024518A1
WO1995024518A1 PCT/DE1995/000294 DE9500294W WO9524518A1 WO 1995024518 A1 WO1995024518 A1 WO 1995024518A1 DE 9500294 W DE9500294 W DE 9500294W WO 9524518 A1 WO9524518 A1 WO 9524518A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolysis
iron
pickling
catholyte
iii
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.)
Ceased
Application number
PCT/DE1995/000294
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German (de)
English (en)
Inventor
Uwe Landau
Sigrid Herrmann
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.)
Mib Metallurgie und Oberflachentechnik und Innovation In Berlin & Co GmbH
Original Assignee
Mib Metallurgie und Oberflachentechnik und Innovation In Berlin & Co 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 DE19944407448 external-priority patent/DE4407448C2/de
Application filed by Mib Metallurgie und Oberflachentechnik und Innovation In Berlin & Co GmbH filed Critical Mib Metallurgie und Oberflachentechnik und Innovation In Berlin & Co GmbH
Priority to DE59504691T priority Critical patent/DE59504691D1/de
Priority to EP95911208A priority patent/EP0748396B1/fr
Publication of WO1995024518A1 publication Critical patent/WO1995024518A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions

Definitions

  • the invention relates to an electrolysis process for regenerating an iron (III) chloride or iron (III) sulfate solution (pickling), in particular for spraying steel, according to the preamble of claim 1.
  • Enrich non-ferrous metals such as chrome, nickel, cobalt, manganese, vandium, copper, tin and lead in the pickling solution.
  • the etching speed and the sharpness of the contours of the structures to be etched are the content of iron (III) chloride, iron (II) chloride
  • Non-ferrous metals and free acid as well as the temperature, the pH value and the density of the pickling solution are decisive.
  • To achieve optimal pickling results it is necessary to keep the iron III chloride, non-metal content and density constant.
  • the iron (II) chloride content must be below 1 g / l.
  • electrolytic processes have been developed which are inexpensive, a metal deposition or a metal deposition and one
  • Diaphragm-free cells for the electrolysis of solutions containing nickel salt operate at a pH of "1". A current efficiency of 40-60% is achieved by adding buffer substances.
  • the processed electrolyte must be disposed of conventionally (US Pat. No. 4,087,338).
  • Electrolyte-permeable diaphragms (US-PS 4,073,709, DE-OS 25 39 137) are used. Diffusion of the anode into the
  • Cathode liquid is said to be high due to different levels
  • Electrolyte-permeable diaphragms are also used in the electrolysis of nickel and zinc from chloride-containing solutions. Sulfuric acid is added to the anode compartment to prevent the development of chlorine. Chloride ions that diffuse into the anode compartment are bound by the addition of silver sulfate (DE-OS 25 39 137). The addition of silver salts requires the processing of the resulting Silver chloride, which means that the process cannot be operated economically.
  • the use of a hydrogen diffusion electrode prevents the development of chlorine according to DD-PS 283 164.
  • the cathode and anode compartments are separated by an acid-resistant fabric or the hydrogen diffusion electrode is to be covered with a diaphragm in order to restrict the access of hydrogen ions to the cathode.
  • the working pressure is 6.7 kPa.
  • a dilute ferrous hydrochloric acid is obtained, which has to be evaporated for pickling.
  • Buffer substances are added for the deposition of iron-chromium-nickel and iron-chromium.
  • the hydrochloric acid formed cannot be used for pickling.
  • Electrolysis processes with ion exchange membranes are said to remove iron from sulfuric and hydrochloric acid stains (GB-PS 1 576 280). With this method, due to the use of extraction and electrolysis, the chemical and plant costs are unusually high. A very long payback period must be expected.
  • Electrolysis cells with cation exchange membranes used.
  • Sulfuric or hydrochloric acid stains containing iron and zinc are regenerated. Sulfuric acid is used as the anolyte. in the
  • Iron and zinc are to be separated from iron / zinc solutions containing 20 g / l hydrochloric acid or 50 g / l sulfuric acid, thereby obtaining a hydrochloric acid with a content of 150 g / l. These acids can be used again for pickling. This The method must work with very low current yields, since according to GB-PS 1 576 280 with a hydrochloric acid content of 100 g / l and one
  • the pickling agent is fed into a central space and cathode space, both of which are separated by an anion exchange membrane.
  • metal separation and acid recycling are to be achieved. Acids can only be obtained with very low concentrations, since otherwise only very little metal deposition is achieved.
  • Iron III chloride pickling can be regenerated if you remove the
  • Electrolysis plant in the cathode and anode space through a
  • Anion exchange membrane are separated, the anode compartment being filled with a FeCl 2 / FeCl 3 solution and the cathode compartment being filled with a NaCl / HCl solution.
  • Iron II ions are oxidized to iron III ions at the anode.
  • the missing chloride ion is delivered from the cathode compartment by transfer.
  • the electrolytic regeneration takes place at redox potentials which are below the chlorine development.
  • the solution when used for pickling steel, is increasingly enriched with nickel, chromium and other impurities over time, so that the process cannot be repeated as often as required.
  • 5 l of excess iron (III) chloride solution are produced per kg of etched steel, which then has to be disposed of (Galvanotechnik 84/1993, 10, p. 3276-32).
  • DD-PS 257 361 Another method is similar (DD-PS 257 361), which separates the anode and cathode compartments by means of a diaphragm. Iron II ions are oxidized to iron III ions in the anode compartment. Missing chloride ions are transferred to the anode compartment from the cathode compartment, which is filled with dilute hydrochloric acid, by means of positive pressure. The regenerated pickling solution is enriched with nickel and cobalt. The aim is to increase the service life of the pickling solution and improve it
  • the present invention is therefore an object of the invention to provide a method which allows an iron (III) chloride or iron (III) sulfate solution to be regenerated in such a way that after the
  • Regeneration in compliance with the desired parameters can be used for the spray etching of nickel alloy steel. This process should be ecologically sustainable and should not pose an increased safety risk for people and the environment.
  • the addition of iron III chloride to the stain should be largely avoided and chemical additives should be kept to a minimum be reduced.
  • the excess iron in the stain should be depleted together with the non-ferrous metals and a concentration of the stain with nickel, chromium and other metallic and non-metallic impurities should be avoided, so that a continuous
  • This object is achieved in a method according to the preamble of claim 1 in that a cation exchange membrane is used as the ion exchange membrane, through which iron II ions, an iron III excess and dissolved non-ferrous metals, such as in particular nickel and chromium, into the cathode compartment are transferred, the pickling solution in addition to iron III and preferably iron II and nickel ions being depleted.
  • a cation exchange membrane is used as the ion exchange membrane, through which iron II ions, an iron III excess and dissolved non-ferrous metals, such as in particular nickel and chromium, into the cathode compartment are transferred, the pickling solution in addition to iron III and preferably iron II and nickel ions being depleted.
  • Non-ferrous metal ions are preferred when the solution moves past the membrane and the mass transfer is thereby improved.
  • the transfer of the metal ions at higher temperatures is favored. The latter is made easier because the stain is used at 40-80oC.
  • hydrochloric acid must be added to replace the chloride depleted by the chlorine development.
  • the metal deposition can be carried out in the electrolysis used to deplete the metals or in a second downstream electrolysis.
  • composition of the iron and nickel to be depleted can be influenced by the temperature, the current density, the acid concentration in the catholyte and the electrolyte movement.
  • Depletion electrolysis should preferably only be in the form of powder, e.g. in the limit current density range, because the
  • Fig. 1 is a schematic representation of an electrolytic cell
  • Fig. 2 is a flow diagram of an embodiment of the
  • Fig. 3 is a flowchart of another exemplary embodiment
  • Fig. 1 shows an electrolyte cell 10, the anode space 12 and
  • Cathode compartment 14 is separated by a cation exchange membrane 16.
  • an iron III chloride pickling used for pickling steel with an iron content of 240 g / l and one
  • the iron (II) ions in the anode compartment 12 are oxidized to iron (III) ions, while iron (II), iron (III), nickel and other non-ferrous metal ions the cation exchange membrane 16 are transferred into the cathode space 14.
  • the transfer of iron and nickel into the cathode compartment 14 takes place here with a current efficiency of 27.5% (the calculation is based on the transfer of Fe ++ and Ni ++ .),
  • the transferred iron and nickel ions having a composition of 59%. Iron and 41% nickel.
  • the pickling solutions processed as described above contain about 50-300 g / l iron in the form of Fe III chloride, less than about 1 g / l iron II, less than about 40 g / l non-ferrous metals and less than 1 g / l Acid and can thus be used immediately for a new pickling process.
  • Composition of 56% iron and 44% nickel transferred to the cathode compartment.
  • the regeneration electrolysis consists of individual cells 10 connected in parallel to one another, which are separated by cation exchange membranes 16 in cathode 14 and anode spaces 12.
  • the pickling solution to be depleted is pumped through the anode spaces 12, and a dilute, highly conductive acid, such as hydrochloric acid or sulfuric acid, is pumped through the cathode spaces 14.
  • a dilute, highly conductive acid such as hydrochloric acid or sulfuric acid
  • the chlorine formed in the anode compartment 12 is suctioned off and fed directly into the pickling plant.
  • the regenerated anolyte is first passed through a filter 22 and then via a heat exchanger 24 into the anolyte 26 intermediate store.
  • the metal content, pH value and temperature are checked here.
  • the parameters necessary for pickling such as temperature, pH, density and the Fe-III and chloride concentration, are set in pickling bath buffer 28.
  • the transferred iron III to iron II ions are reduced, and portions of the dissolved iron and non-ferrous metals are separated out as a powder.
  • Powder separation is known per se and z. BN Ibl, Chemie-Ingenieur-Technik 36, 6, (1964). In addition to the Powder separation leads to hydrogen evolution.
  • the catholyte solution is passed through a filter 30 and
  • a control system can be set up that guarantees compliance with the pickling parameters of the iron III chloride pickling plant, which are within very limited limits. Any additions of chemicals required to adjust this are required to a much lesser extent than in previously known processes.
  • the composition of the pickling and catholyte solution can be checked both electrochemically and analytically.
  • the electrolysis process according to the invention accordingly enables, in a surprisingly simple manner, continuous regeneration of an iron (III) chloride pickling in a closed circuit with simultaneous depletion of the non-ferrous metals and the excess iron, and electrolytic deposition of the depleted metal ions.
  • Metal ions are not deposited as powder in the cathode compartment 14 as in the first exemplary embodiment. The deposition takes place rather
  • Anion exchange membrane 42 are separated.
  • the demetallized electrolyte is concentrated and transferred to the buffer store Katolyt 34, then, after setting the necessary
  • This structure has the advantage that the deposited metal can be drawn off continuously without interfering with the actual regeneration electrolysis.
  • a pickle used for pickling nickel-alloyed steel with approximately 297 g / l iron and approximately 38 g / l nickel is placed in the anode compartments of the electrolytic cell 10.
  • the content of sulfuric acid in the cathode spaces is 135 g / l.
  • the solutions are pumped through intermediate containers at a speed of 1.0 l / min.
  • iron and nickel are transferred into the cathode compartment with a current efficiency of ⁇ 90%.
  • the composition of the transferred iron and nickel ions is 66% iron and 34% nickel.
  • the iron- and nickel-containing solution with about 12.4 g / l nickel, 24.9 g / l iron and 112.9 g / l sulfuric acid is led from the cathode spaces into the cathode space of the downstream electrolysis cell, which contains a sulfuric acid in its anode space Contains 50 g / l.
  • Electrolysis voltage is 3 V at a current density of 0.5 A / cm 2 and a temperature of 50 ° C. Iron and nickel are deposited as powder with a current efficiency of 76%. As already described, the solution depleted of metal is transferred into the cathode spaces of the cells 10.
  • the electrolysis process according to the invention was described using the regeneration of an iron II chloride pickling as an example.
  • the present invention is equally advantageous for the regeneration of iron III sulfate pickling for spraying and pickling steel and
  • Nickel-based materials are used. The above statements apply equally to this type of stain.

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  • 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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

L'invention concerne un procédé électrolytique de régénération d'une solution de sulfate ou de chlorure ferrique (mordant), utile notamment pour le mordançage d'acier par pulvérisation. Le mordant à régénérer traverse en continu la chambre à anode (17) d'une cellule électrolytique (10) dont la chambre à cathode (14) est remplie d'un acide conducteur dilué. Les chambres à anode et à cathode (12 et 14) sont séparées par une membrane d'échange de cations (16) à travers laquelle des ions de Fe(II), l'excès de Fe(III) et des métaux non-ferriques dissous, notamment des ions de nickel et de chrome, parviennent à la chambre à cathode (14), alors que les ions de Fe(II) se transforment par oxydation en ions de Fe(III) au niveau de l'anode. Les métaux qui s'accumulent dans le catholyte précipitent sous forme d'une poudre de préférence dans la chambre à cathode (14), ou précipitent par électrolyse dans une cellule électrolytique située en aval dont les chambres à cathode et à anode sont séparées par une membrane à échange d'anions. Ce procédé permet de régénérer en continu le mordant en un circuit fermé, assure un appauvrissement en métaux non-ferriques et en excès de fer, ainsi qu'une précipitation par électrolyse des ions métalliques enlevés.
PCT/DE1995/000294 1994-03-07 1995-03-06 Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation Ceased WO1995024518A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59504691T DE59504691D1 (de) 1994-03-07 1995-03-06 Elektrolyseverfahren zum regenerieren einer eisen-iii-chlorid oder eisen-iii-sulfatlösung, insbesondere zum sprühätzen von stahl
EP95911208A EP0748396B1 (fr) 1994-03-07 1995-03-06 Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordan age d'acier par pulverisation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4407448.4 1994-03-07
DE19944407448 DE4407448C2 (de) 1994-03-07 1994-03-07 Elektrolyseverfahren zum Regenerieren einer Eisen-III-Chlorid- oder Eisen-III-Sulfatlösung, insbesondere zum Sprühätzen von Stahl

Publications (1)

Publication Number Publication Date
WO1995024518A1 true WO1995024518A1 (fr) 1995-09-14

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PCT/DE1995/000294 Ceased WO1995024518A1 (fr) 1994-03-07 1995-03-06 Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation

Country Status (3)

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EP (1) EP0748396B1 (fr)
DE (2) DE59504691D1 (fr)
WO (1) WO1995024518A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2175025C1 (ru) * 2000-02-15 2001-10-20 Нижегородский государственный технический университет Способ регенерации отработанных электролитов полирования и травления хромсодержащих сталей
RU2180693C2 (ru) * 2000-01-25 2002-03-20 Моисеева Таисия Федоровна Электролитический способ регенерации травильных растворов на основе хлоридов железа
CN115449849A (zh) * 2022-08-31 2022-12-09 长沙利洁环保科技有限公司 一种微蚀液在线电解提铜循环再生工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1290947B1 (it) 1997-02-25 1998-12-14 Sviluppo Materiali Spa Metodo e dispositivo per il decapaggio di prodotti in lega metallica in assenza di acido nitrico e per il recupero di soluzioni esauste
AT13805U1 (de) 2013-07-04 2014-09-15 Pureox Industrieanlagenbau Gmbh Verfahren zur elektrochemischen Oxidation von Fe-2+-Chlorid-Lösungen

Citations (9)

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Publication number Priority date Publication date Assignee Title
FR1227199A (fr) * 1958-06-19 1960-08-19 Chem Fab Budenheim Ag Procédé de régénération d'acides de décapage
DD257361A3 (de) * 1984-12-27 1988-06-15 Seghers A Mikroelektronik Veb Elektrochemisches kreislaufverfahren zum aetzen von eisen und seinen legierungen
WO1990005797A1 (fr) * 1988-11-24 1990-05-31 Hans Höllmüller Maschinenbau GmbH & Co. Installation de decapage d'objets
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
JPH03287790A (ja) * 1990-04-05 1991-12-18 Asahi Glass Co Ltd 鉄―ニッケル合金のエッチング液の処理方法
JPH0421792A (ja) * 1990-05-15 1992-01-24 Asahi Glass Co Ltd 第二鉄塩エッチング液の電解再生方法
EP0506000A2 (fr) * 1991-03-29 1992-09-30 Scientific Impex Establishment Appareil pour traitement chimique d'un métal
DE4118725A1 (de) * 1991-06-07 1992-12-10 Chema Technologien Gmbh Verfahren und vorrichtung zur vollstaendigen regeneration von aetzloesungen
JPH0718473A (ja) * 1993-07-06 1995-01-20 Nagai Seiyakushiyo:Kk エッチング液の能力回復維持方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4407448C2 (de) * 1994-03-07 1998-02-05 Mib Metallurg Und Oberflaechen Elektrolyseverfahren zum Regenerieren einer Eisen-III-Chlorid- oder Eisen-III-Sulfatlösung, insbesondere zum Sprühätzen von Stahl

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1227199A (fr) * 1958-06-19 1960-08-19 Chem Fab Budenheim Ag Procédé de régénération d'acides de décapage
DD257361A3 (de) * 1984-12-27 1988-06-15 Seghers A Mikroelektronik Veb Elektrochemisches kreislaufverfahren zum aetzen von eisen und seinen legierungen
WO1990005797A1 (fr) * 1988-11-24 1990-05-31 Hans Höllmüller Maschinenbau GmbH & Co. Installation de decapage d'objets
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
JPH03287790A (ja) * 1990-04-05 1991-12-18 Asahi Glass Co Ltd 鉄―ニッケル合金のエッチング液の処理方法
JPH0421792A (ja) * 1990-05-15 1992-01-24 Asahi Glass Co Ltd 第二鉄塩エッチング液の電解再生方法
EP0506000A2 (fr) * 1991-03-29 1992-09-30 Scientific Impex Establishment Appareil pour traitement chimique d'un métal
DE4118725A1 (de) * 1991-06-07 1992-12-10 Chema Technologien Gmbh Verfahren und vorrichtung zur vollstaendigen regeneration von aetzloesungen
JPH0718473A (ja) * 1993-07-06 1995-01-20 Nagai Seiyakushiyo:Kk エッチング液の能力回復維持方法

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DATABASE WPI Section Ch Week 0692, Derwent World Patents Index; Class M14, AN 92-044530 *
DATABASE WPI Section Ch Week 1395, Derwent World Patents Index; Class M14, AN 95-094261 *
KORSSE J: "ERFAHRUNGEN MIT DER REGENERATION VON EISEN(III)CHLORID", GALVANOTECHNIK, vol. 84, no. 4, 1 April 1993 (1993-04-01), SAULGAU, pages 1341 - 1348, XP000381409 *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 180 (C - 0935) 30 April 1992 (1992-04-30) *
VISSER A.: "Regenerieren von Eisenchloridlösung für das Sprühätzen von Edelstahl", GALVANOTECHNIK, vol. 84, no. 10, 1 October 1993 (1993-10-01), SAULGAU, pages 3276 - 3282 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2180693C2 (ru) * 2000-01-25 2002-03-20 Моисеева Таисия Федоровна Электролитический способ регенерации травильных растворов на основе хлоридов железа
RU2175025C1 (ru) * 2000-02-15 2001-10-20 Нижегородский государственный технический университет Способ регенерации отработанных электролитов полирования и травления хромсодержащих сталей
CN115449849A (zh) * 2022-08-31 2022-12-09 长沙利洁环保科技有限公司 一种微蚀液在线电解提铜循环再生工艺
CN115449849B (zh) * 2022-08-31 2023-06-02 长沙利洁环保科技有限公司 一种微蚀液在线电解提铜循环再生工艺

Also Published As

Publication number Publication date
EP0748396A1 (fr) 1996-12-18
DE19532784C2 (de) 1998-04-02
EP0748396B1 (fr) 1998-12-30
DE19532784A1 (de) 1997-03-13
DE59504691D1 (de) 1999-02-11

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