EP0506000A2 - Appareil pour traitement chimique d'un métal - Google Patents

Appareil pour traitement chimique d'un métal Download PDF

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Publication number
EP0506000A2
EP0506000A2 EP92105107A EP92105107A EP0506000A2 EP 0506000 A2 EP0506000 A2 EP 0506000A2 EP 92105107 A EP92105107 A EP 92105107A EP 92105107 A EP92105107 A EP 92105107A EP 0506000 A2 EP0506000 A2 EP 0506000A2
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EP
European Patent Office
Prior art keywords
rinsing
station
iron
chloride solution
pickling
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Withdrawn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
EP92105107A
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German (de)
English (en)
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EP0506000A3 (en
Inventor
Markus Dr. Ing. Bringmann
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SCIENTIFIC IMPEX ESTABLISHMENT
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SCIENTIFIC IMPEX ESTABLISHMENT
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Publication of EP0506000A2 publication Critical patent/EP0506000A2/fr
Publication of EP0506000A3 publication Critical patent/EP0506000A3/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Withdrawn legal-status Critical Current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
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • 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
    • C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
    • 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
    • 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 device for chemical metalworking, in particular for pickling or etching metallic raw products and semi-finished and finished products.
  • Iron chloride has long been a well-known medium in metalworking for metalworking. As a 20 to 45% solution, it is quite universal for the treatment of most metallic materials, e.g. B. copper and its alloys, aluminum, nickel, iron and steel, Kovar and also stainless steels can be used.
  • Iron (III) chloride can also be used excellently as a pickling medium for almost all metals, especially those containing iron. It combines the advantages of conventional iron pickling, such as hydrochloric and sulfuric acid, namely high pickling speed, which depending on the metal is often higher than that of hydrochloric acid, and thus high efficiency of the existing production facilities, easily controllable properties of the metal surfaces, low and easily removable pickling residues, no tendency to emit acidic vapors and therefore little nuisance to the environment.
  • a new regeneration method (DE-OS 37 19 604) of iron (III) chloride is based on the anodic oxidation of iron (III) ions to iron (II) ions according to the reaction Fe+2-e ⁇ Fe+3 in a series of anolyte cells that are separated from cathodes by means of anion-permeable ion exchange membranes.
  • An alkali metal chloride solution acidified with hydrochloric acid is used as the catholyte.
  • 2H3O + 2e ⁇ H2 + 2H2O free hydrogen gas is formed from the hydronium ions belonging to the dissociated hydrochloric acid.
  • the current flow in both electrolytes takes place through the movement of chloride ions from the catholyte into the iron chloride solution, where they form the dissociated iron (III) chloride with the resulting iron (III) ions, which leads to the summary reaction Fe+3 + 3Cl ⁇ (from Katholytlsg.) ⁇ FeCl3 can be represented.
  • the anodic oxidation process is monitored and regulated by measuring the reduction and oxidation potential of the iron chloride solution.
  • the measuring and control system consists of a comparative measuring amplifier and two measuring chains, which ensures a correspondingly high level of security for continuous process controllability.
  • metal dissolution takes place in the process solution, which results in an increase in the density of the iron chloride solution.
  • This change in density is recorded in the electromechanical density controller and automatically corrected with rinsing water from cascade rinsing sections.
  • a new ferric chloride solution which is collected in the collecting container, is thus produced during the treatment of ferrous metals.
  • This iron (III) chloride solution which has a market concentration of 40% by weight, is an economic commodity and can also be used for the production of non-ferrous metal parts or printed circuit boards. Should the treated metal only The iron chloride solution obtained, which has a sufficient degree of purity, is widely used as a precipitant, flocculant or conditioning agent, which is used in very large quantities in wastewater and water treatment.
  • a corresponding iron chloride regeneration plant (DE-PS 36 18 769) consists of an electrolytic cell container which, with the aid of at least one ion exchange membrane, is inserted in a catholyte space filled with a catholyte with at least one cathode and in at least one anolyte space filled with the iron chloride solution as anolyte an anode of a feed line continuously supplying at least partially used iron chloride solution and a return line discharging continuously regenerated iron chloride solution is subdivided.
  • the ion exchange membrane in each case consists of a 0.05 to 0.50 mm, in particular 0.15 to 0.25 mm thick carrier film made of polyester, polyethylene or polyvinyl chloride with an applied exchange resin made of vinyl pyridinium halide.
  • the carrier film material is preferably fluorinated.
  • the applied exchange resin consists of vinyl pyridinium halide, especially bromide.
  • Such ion exchange membranes are particularly suitable, provided they have a specific electrical resistance of at most 7 ohm / cm2 and a selectivity of at least 95% (0.5 N KCl). Ion exchange membranes with the properties mentioned are commercially available.
  • the individual plates are inexpensively designed as molded parts and have grooves for receiving sealing cords and O-rings to seal the anolyte and catholyte spaces from each other, as well as the inlets and outlets.
  • the electrodes are clamped between the individual cell plates on the front of the plates against the next plate and sealed as described above.
  • Each electrolytic cell consists of four plates, two electrodes and two membranes. The composition of several cells results in a complete electrolysis unit that can be expanded or reduced as required depending on the capacity requirements.
  • the entire cell system is clamped between two steel end plates by tie rods or hydraulically.
  • the entire cell block is mounted in a frame.
  • the frame also serves as the upper and lower guide for the cell block.
  • This construction thus relates to an electrolytic cell block consisting of a plurality of electrolytic cells arranged one behind the other, each electrolytic cell having two plate-shaped electrodes parallel to one another in a cell trough and a membrane parallel to these being arranged between adjacent electrodes.
  • the cell troughs are each made up of four profile plates, which form the electrodes and membranes between the receiving electrolyte space halves, and the profile plates of the cell troughs are clamped together in a block frame with two parallel block end plates arranged on the end face.
  • the profile plates can be manufactured more easily and at lower cost than conventional welded structures. Since the distances between the electrodes are smaller than before, the power consumption is low and the capacity is high.
  • the profile plates can also be optimally designed with regard to the hydraulic flows in the individual cells, so that there is also a high process yield. So the profile plates are preferably made of injection molded parts. With regard to electrolyte supply and drainage, the least problems arise if at least the profile plates are provided in their corner regions with electrolyte supply and drain holes perpendicular to the profile plates, the latter being optionally provided, ie depending on the size, in the plate-shaped electrodes.
  • the profile plates are expediently provided with clamping ribs and associated clamping grooves for holding the membranes.
  • the profile plates are also recommended to provide the profile plates with grooves for sealing cords and O-rings. Easy manipulation in the course of the variation in the number of cells results if the profile plates are held together in pairs with the associated membranes with the aid of catches.
  • the profile plates are held together with guide recesses for horizontal crossbars of the block frame.
  • the block end plates are expediently made of steel. They can be held together with the profile plates using tie rods.
  • a hydraulic tension e.g.
  • one block end plate is fixed and the other block end plate is mounted in the block frame so that it can be moved in parallel. In any case, it is advisable to provide the fixed block end plate with electrolyte supply and drain connections.
  • the invention has for its object to design the flow of chemicals and rinse water used in a device of the type mentioned so that a wastewater-free and waste-free circulation system is formed.
  • the device is characterized by a pretreatment station in which coarse scale, rust and other oxide layers are removed from the metal surface, a metal processing station in which the metallic product to be treated is chemically processed, in particular etched or pickled, using iron (III) chloride solution and the desired machining finishing is achieved, a regeneration system in which the iron chloride solution used in the metalworking station is chemically or, in particular, electrochemically regenerated without residue, a rinsing station in which the surface of the chemically processed product, the chemicals used for its processing are removed without residue and a rinse water concentration unit in which the concentration of the rinsed chemicals is increased to the desired setpoint.
  • a pretreatment station in which coarse scale, rust and other oxide layers are removed from the metal surface
  • a metal processing station in which the metallic product to be treated is chemically processed, in particular etched or pickled, using iron (III) chloride solution and the desired machining finishing is achieved
  • a regeneration system in which the iron chloride solution used in the metalworking station is chemically or, in particular,
  • the regeneration system is designed as has already been described above.
  • the invention also relates to a device for chemical metal processing, in particular for pickling or etching metallic raw products and semi-finished and finished products, with a metal processing station and a rinsing station, the metal processing station being a processing container with an iron (III) chloride solution which is circulated via a regenerator connected to the processing tank, and the washing station has a washing tank containing washing water with a fresh water supply line.
  • the rinsing station is to be integrated into the device for chemical metal processing in such a way that it is no longer necessary to dispose of the rinsing water enriched with iron (III) chloride.
  • the rinsing station is assigned a rinse water concentration unit with a rinse water inlet line led out of the rinse tank, an eluate outlet line returned to the rinse tank and a concentrate outlet line led into the processing tank.
  • the invention is based on the knowledge that a Treatment of rinsing water to be discarded can be omitted if the rinsing water is circulated and the rinsing water is removed from the rinsing water in the course of this circulation by appropriate concentration to such an extent that the corresponding concentrate is discharged into the processing tank without adversely affecting the metalworking can. The result is a considerable saving in running operating costs.
  • the rinse water concentration unit consists of an evaporator and / or an electrodialysis machine.
  • the latter is preferred, but can also be used in parallel or in series with an evaporator.
  • the iron (III) chloride solution return to the metalworking station to keep the density of the iron (III) chloride solution in the processing tank constant;
  • the concentrate outlet line is additionally guided into the rinsing container via an intermediate metering element and a branch line, and the processing container is equipped with a sensor of a density control device that measures the density of the iron (III) chloride solution, to which the metering element acts as an actuator is connected, with the concentrate a particularly sensitive density adjustment is possible.
  • Optimal rinsing over a long period of time is possible if the rinsing station is a multi-stage rinsing cascade is executed, the first cascade of the rinse water inlet line and possibly the branch line and the last cascade of which are assigned the fresh water supply line and the eluate outlet line. Otherwise, it is advisable to interpose an actuator controlled by a rinse water level sensor in the fresh water line so that the amount of liquid transferred from the rinse station to the metalworking station is automatically replaced by a corresponding amount of fresh water.
  • pickling iron chloride has several advantages, of which the very high pickling speed, which guarantees a correspondingly high efficiency of the existing plant technology, is of the utmost importance. With the pickling, however, apart from the removal of the scale layers and corrosion products, other tasks are often connected at the same time. B. to create a surface with certain properties, to shine or matt it. For subsequent painting, gluing or metal spraying, on the other hand, a certain roughening is desired for improved adhesion. These often very different and additional tasks of pickling as well as the different strengths and forms of the pieces to be treated make it understandable that it is of the greatest advantage to design the pickling process in two stages.
  • the so-called pickling 1 the coarse layers of scale and rust are removed first. This can be done in different ways, such as. B. Use of a pickle in the form of a high hydrochloric iron (II) chloride solution or switching on an electrolytic pickle.
  • the base material always having a higher potential than its oxides.
  • the inhibitors in the liquid are also present as colloids or as ions. These particles are attracted to the oppositely charged areas of the metal surface, are discharged there after electron acceptance or release and act as a protective layer, in particular by preventing the escape of electrons or metal ions or gases and thus hindering the dissolution of the base metal.
  • anionic inhibitors in which predominantly negatively charged particles of the stain act, and cationic inhibitors, the protective layer being formed primarily from positively charged particles.
  • a other types of inhibitors primarily provide protection through absorption.
  • the modern pickling inhibitors which are used for iron, steel and ferrous metals, increase the redox potential of the entire pickling solution, which means that the hydrogen development can be completely suppressed at higher concentrations of the inhibitor.
  • the inhibitors that are already commercially available today have a very high potency and resistance, and this at a proportion of 0.1% and below.
  • the effect of the inhibitors can be increased accordingly by adding wetting agents. By reducing the surface tension, wetting agents cause the surface of the pickling material to come into contact with the pickling liquid.
  • the discharge of the pickling solution by wetting agents is significantly reduced, which also has a positive effect on the amount of rinsing water and its concentration. Wetting agents also accelerate the removal of contaminants.
  • the inhibitors and wetting agents commercially available for hydrochloric acid should be used depending on the type of metal and its impurities and scaling.
  • electrolytic pickling Another type of pickling is electrolytic pickling, which can be divided into cathodic and anodic pickling.
  • cathodic pickling the base material is protected against attack by the pickling solution.
  • the pickling effect is primarily due to the hydrogen produced, which may mechanically blast off the impurities to be removed after conversion.
  • Anodic pickling also removes scale and rust parts that cannot be removed with conventional pickling, very quickly.
  • the base material is also dissolved, so that there is the possibility of excessive removal.
  • the loosening of the metal on the surface breaks the bond between the workpiece and the contaminants to be removed.
  • a good compromise between the advantages and disadvantages of both methods is the so-called polarity reversal method, in which short treatment times have an advantageous effect on the pasting process.
  • a good way to optimally design the pickling is to use neutral electrolytes for electrolytic pickling. These electrolytes consist primarily of sodium salts, which easily dissolve in water. During the electrolysis, free acid is generated at the anode, which brings the rust and scale into solution. At the same time, sodium hydroxide forms on the cathode, which precipitates the dissolved iron, with the original salt regressing.
  • the subsequent treatment step is the main pickling with ferric chloride.
  • This solution has a very high removal rate for iron and steel. Therefore, relatively short treatment times are recommended.
  • the desired finishing of the surface can be precisely influenced by the appropriate combination of the pickling parameters, especially the redox potential of this solution, the temperature, the concentration and the proportion of free acid.
  • the regeneration system 4 is connected directly to the iron chloride pickling bath.
  • the iron chloride solution is continuously removed from the pickling bath 3 and pumped through the electrolysis block in a circuit, the corresponding conversion of iron (II) chloride to iron (III) chloride taking place.
  • the speed of regeneration is precisely regulated by the redox potential.
  • By the circular process one achieves a uniform pickling rate and thus constant product quality.
  • the energy requirement of approx. 4 kWh per kilo of iron converted from Fe+2 to Fe+3 can be recovered for the most part by a heat exchanger 5 on the anolyte side and used for heating the other baths.
  • a wetting agent By adding small parts of a wetting agent, the amount of the pickling solution carried out into the downstream rinsing system 6 can be reduced accordingly.
  • the iron chloride solution attacks the base material very quickly after prolonged exposure and should therefore be removed as quickly as possible from the surface of the pickled material after the pickling process has ended.
  • the pickled goods are placed in the washing and rinsing containers after a short drip and the rinsing water is mixed with small amounts of the wetting agent.
  • the rinsing and washing should be carried out so that the pickling material comes into contact with the water quickly and on all sides.
  • the use of rinsing baths in cascade form in connection with a concentration system 7 largely eliminates the rinse water to be treated.
  • the rinse water of the first cascade should be continuously in a suitable system, e.g. B. be concentrated in an electrodialysis system.
  • the low salt water should then be returned to the last cascade. A certain amount of fresh water must also be added to this cascade, which avoids the concentration of the neutral salts in the circuit.
  • the metal dissolution in the process solution results in an increase in the density of the iron chloride solution.
  • the change in density is recorded in a density controller and automatically corrected with rinsing water from the last cascade rinsing section.
  • the amount of rinse water supplied to the pickling bath 3 should correspond to the volume of the fresh water supplied to the last cascade. It is therefore possible to achieve a complete regeneration of the pickling medium without producing wastewater and to return both the iron (III) chloride solution used during pickling and the water back into the pickling process.
  • the iron (III) chloride solution formed during the regeneration and density correction is collected in a collection container and represents an economic good that is widely used in the production of molded parts and printed circuit boards due to the concentration of 40 to 45% that is customary in the market and a normally sufficient degree of purity as a precipitating and conditioning agent during water and wastewater treatment.
  • the regeneration system consists of an electrolytic cell block, which in turn consists of several electrolytic cells 101 arranged one behind the other.
  • Each electrolytic cell 101 has two mutually parallel plate-shaped electrodes 102, 102 (anode 102, cathode 103) in a cell trough.
  • a membrane 104 parallel to the electrodes 102, 103 is arranged between adjacent electrodes 102, 103.
  • the cell troughs are each made up of four profile plates 106, the electrodes 102, 103 and membranes 104, between the electrolyte space halves 105, which are accommodated.
  • the profile plates 106 of the cell troughs are clamped together in a pressure-tight manner in a block frame 107 with two parallel block end plates 108, 109 arranged on the end face (cf. FIGS. 2, 3).
  • the profile plates 106 consist of injection molded parts. In their corner areas, they and also the anodes 102 are provided with electrolyte feed and drain holes 110 perpendicular to the profile plates 106.
  • the profile plates 106 have integrated membrane support grids 111. To hold the membranes 104, the corresponding profile plates 106 are provided with clamping ribs 112 and associated clamping grooves 113.
  • the profile plates 106 are also provided with receiving grooves 114 for the sealing cords or O-rings 115.
  • the measure of holding the profile plates 106 in pairs with the associated membranes 104 with the aid of catches is not shown in detail.
  • the profile plates 106 are provided with upper and lower guide recesses 116 for horizontal traverses 117 of the block frame 107.
  • the block end plates 108, 109 are made of steel. They are held together with the aid of tie rods 118. However, they could also be clamped together using at least one hydraulic cylinder piston arrangement.
  • the one block end plate namely the block end plate 108 to be seen on the left in FIGS. 2 and 3 and the block end plate 108 shown in FIG. 4, is fixedly arranged in the block frame 107.
  • the other block end plate 109 on the other hand, can be moved in parallel after removing the tie rods 118. In this way, additional cells can be used added cells or excess cells are removed.
  • the fixed block end plate 108 is provided with electrolyte feed and drain pipe 119.
  • the basic structure of the device for chemical metalworking shown schematically in FIG. 7, in particular for pickling or etching metallic raw products and semi-finished and finished products, initially consists of a metalworking station 201 and a rinsing station 202.
  • the objects to be processed are drawn in the direction of the drawing Arrow 203 first transferred to the metal processing station 201 and then to the rinsing station 202.
  • the metal processing station 1 has a processing container 204 which is filled with an iron (III) chloride solution 205.
  • This iron (III) chloride solution 205 is circulated via a regeneration system 206 connected to the processing tank 204.
  • the structure and mode of operation of such a regeneration system 206 have been described.
  • the rinsing station 202 has a rinsing container 208 filled with rinsing water 207 with a fresh water supply line 209.
  • a flushing water concentration unit 210 is assigned to the flushing station 202.
  • This rinse water concentration unit 210 has a rinse water inlet line 211 which is led out of the rinse tank 208.
  • the rinse water 207 is concentrated in the rinse water concentration unit 210; the concentrate is over a concentrate outlet line 212 is dispensed.
  • the fraction depleted in salts flows out via an eluate outlet line 213.
  • This eluate outlet line 213 is returned to the rinsing tank 208, while the concentrate outlet line 212 is led into the processing tank 205.
  • the rinse water concentration unit 210 consists of an electrodialysis machine.
  • the concentrate outlet line 212 is additionally fed into the rinsing tank 207 via an intermediate metering element 214 and a branch line 215, and the processing tank 205 is equipped with a sensor 216 of a density control device 217 that measures the density of the iron (III) chloride solution equipped to which said metering element 214 is connected as an actuator.
  • the concentrate not required for density control is returned to the rinsing tank 207 via the branch line 215.
  • the flushing station 202 is designed as a multi-stage flushing cascade.
  • the rinsing water inlet line 211 is led out of the first cascade 202a, while the branch line 215 opens into this first cascade 202a.
  • the fresh water supply line 209 and the eluate outlet lines 213 are introduced into the last cascade 202c.
  • the fresh water line 209 can also be connected to an actuator 219 controlled by a rinse water level sensor 218, so that practically an automatic drain of the rinse station 202 is ensured.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP19920105107 1991-03-29 1992-03-25 Apparatus for chemical treatment of metal Withdrawn EP0506000A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4110423 1991-03-29
DE19914110423 DE4110423A1 (de) 1991-03-29 1991-03-29 Vorrichtung zur chemischen metallbearbeitung

Publications (2)

Publication Number Publication Date
EP0506000A2 true EP0506000A2 (fr) 1992-09-30
EP0506000A3 EP0506000A3 (en) 1993-02-24

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EP19920105107 Withdrawn EP0506000A3 (en) 1991-03-29 1992-03-25 Apparatus for chemical treatment of metal

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EP (1) EP0506000A3 (fr)
DE (1) DE4110423A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995024518A1 (fr) * 1994-03-07 1995-09-14 Mib Metallurgie Und Oberflächentechnik Und Innovation In Berlin Gmbh & Co. Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation
DE4419683A1 (de) * 1994-06-06 1995-12-07 Eilenburger Elektrolyse & Umwelttechnik Gmbh Bipolare Filterpressenzelle für anodische Oxidationen am Platin
RU2157423C1 (ru) * 1999-09-17 2000-10-10 Московский государственный вечерний металлургический институт Линия травления окисленных металлических материалов
WO2001064970A3 (fr) * 2000-03-01 2001-12-20 Sms Demag Ag Procede et installation de revetement par trempe de bandes metalliques
RU2211883C1 (ru) * 2002-01-08 2003-09-10 Открытое акционерное общество "Магнитогорский металлургический комбинат" Способ травления тонколистовой стали в пачках
FR2839984A1 (fr) * 2002-05-23 2003-11-28 Afelec Traitement electrochimique des bains de decapage uses
CN111394729A (zh) * 2020-04-26 2020-07-10 江苏地一环保科技有限公司 电解装置及其印制板酸性蚀刻废液再生及铜回收设备

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006012296A1 (de) * 2006-03-15 2007-09-20 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Recycling-Ätzverfahren für die Feinstleiterplattentechnik

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Publication number Priority date Publication date Assignee Title
DE2434305C2 (de) * 1974-07-17 1983-09-29 Hans Höllmüller Maschinenbau GmbH & Co, 7033 Herrenberg Ätzanlage
FR2314900A1 (fr) * 1975-06-18 1977-01-14 Niso Ste Civile Etud Rech Procede et installation de traitement des solutions de decapage de metaux
US4468305A (en) * 1979-05-08 1984-08-28 The Electricity Council Method for the electrolytic regeneration of etchants for metals
FR2457331A1 (fr) * 1979-05-23 1980-12-19 Minemet Rech Sa Procede ameliore pour le decapage d'objets metalliques
EP0346510A1 (fr) * 1988-06-15 1989-12-20 Chema Chemiemaschinen Gmbh Décapage de produits semi-finis

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995024518A1 (fr) * 1994-03-07 1995-09-14 Mib Metallurgie Und Oberflächentechnik Und Innovation In Berlin Gmbh & Co. Procede electrolytique de regeneration d'une solution de sulfate ou de chlorure ferrique, utile notamment pour le mordançage d'acier par pulverisation
DE4419683A1 (de) * 1994-06-06 1995-12-07 Eilenburger Elektrolyse & Umwelttechnik Gmbh Bipolare Filterpressenzelle für anodische Oxidationen am Platin
DE4419683C2 (de) * 1994-06-06 2000-05-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Bipolare Filterpressenzelle für anodische Oxidationen an Platin
RU2157423C1 (ru) * 1999-09-17 2000-10-10 Московский государственный вечерний металлургический институт Линия травления окисленных металлических материалов
WO2001064970A3 (fr) * 2000-03-01 2001-12-20 Sms Demag Ag Procede et installation de revetement par trempe de bandes metalliques
US6811827B2 (en) 2000-03-01 2004-11-02 Sms Demag Ag Method and installation for hot dip coating metal strips
KR100746297B1 (ko) * 2000-03-01 2007-08-03 에스엠에스 데마그 악티엔게젤샤프트 금속 스트립의 고온 침지 코팅 방법 및 장치
RU2211883C1 (ru) * 2002-01-08 2003-09-10 Открытое акционерное общество "Магнитогорский металлургический комбинат" Способ травления тонколистовой стали в пачках
FR2839984A1 (fr) * 2002-05-23 2003-11-28 Afelec Traitement electrochimique des bains de decapage uses
CN111394729A (zh) * 2020-04-26 2020-07-10 江苏地一环保科技有限公司 电解装置及其印制板酸性蚀刻废液再生及铜回收设备

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DE4110423A1 (de) 1992-10-01

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