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EP0832315B1 - Procede de demetallisation de bains tres acides et mise en oeuvre de ce procede pour le polissage electrolytique de surfaces en acier special - Google Patents

Procede de demetallisation de bains tres acides et mise en oeuvre de ce procede pour le polissage electrolytique de surfaces en acier special Download PDF

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Publication number
EP0832315B1
EP0832315B1 EP96921930A EP96921930A EP0832315B1 EP 0832315 B1 EP0832315 B1 EP 0832315B1 EP 96921930 A EP96921930 A EP 96921930A EP 96921930 A EP96921930 A EP 96921930A EP 0832315 B1 EP0832315 B1 EP 0832315B1
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EP
European Patent Office
Prior art keywords
electrolyte
electropolishing
ions
weight
phosphoric acid
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.)
Expired - Lifetime
Application number
EP96921930A
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German (de)
English (en)
Other versions
EP0832315A1 (fr
Inventor
Razmik Abedian
Olaf BÖHME
Siegfried Piesslinger-Schweiger
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.)
Poligrat GmbH
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Poligrat GmbH
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Publication of EP0832315A1 publication Critical patent/EP0832315A1/fr
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Publication of EP0832315B1 publication Critical patent/EP0832315B1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
    • C25F7/02—Regeneration of process liquids

Definitions

  • the invention relates to a method for demetallizing highly acidic baths based on phosphoric and sulfuric acid.
  • the invention further relates to the use of a demetallization process when electropolishing stainless steel surfaces (Stainless steel).
  • Electropolishing or electrolytic polishing is a process electrochemical metalworking, in which the Polishing metal is usually connected as an anode in a circuit becomes.
  • the electrolyte consists of an acid or an acid mixture. From the metal to be polished outstanding bumps (tips, Burrs) superficially dissolved and thus polished the metal. So the previously matt metal is smoothed and shiny.
  • As an electrolyte is used for stainless steels and carbon steels mostly phosphoric acid-sulfuric acid mixtures with additives of catalysts, inhibitors and the like.
  • the objects to be polished are the on the corresponding support and contact elements or devices hanging or in baskets or the like, in the electrolyte, d. H. the polishing bath, sunk and after a certain polishing time out of this. After this Drain the bath liquid from the polished surfaces the treated objects are then in rinsing baths dipped to remove the electrolyte.
  • Electropolishing processes currently used for processing of stainless steels predominantly low-water mixtures of concentrated phosphoric acid and sulfuric acid as the electrolyte.
  • the optimal working range in the metal content more common Electrolytes are usually between 35 g / l and 70 g / l (2 - 4% by weight).
  • the electrolytes are up to the state of the art to a metal content of approx. 100 g / l, this corresponds to approx. 6% by weight, workable. With a higher metal content the decreases Polish quality drastically.
  • the enriched electrolyte is removed either continuously on the carryover of the surface of the machined workpieces the electropolishing bath in the subsequent rinsing process, or by direct withdrawal.
  • the removed electrolyte is either over a suitable wastewater treatment plant or directly processed that the resulting wastewater to the sewers can be released while the solids because of their content heavy metals are generally disposed of as hazardous waste have to.
  • the invention is based on the idea that one with metal ions selectively enriched electrolytes the metal ions must withdraw if an electropolishing electrolyte without partial exchange be kept permanently functional by electrolyte should.
  • Ordinary filtration processes (see DE-33 43 396 A1) are out of the question here, since in the course of a filtration yes only solid separated, not the concentration of metallic Ions is lowered.
  • the state of the art membranes used in electrodialysis for example, compared to highly concentrated acid mixtures resistant.
  • the aim of the present invention is thus a method that direct separation of metal ions including iron from the with the metal ions enriched electrolytes without that the electrolytes must be diluted significantly.
  • the Concentration of the metal ions in the depleted electrolyte should ideally be adjusted so that the metal concentration the optimal working area is reached.
  • those concentrated with metal ions are concentrated Mixtures based on phosphoric acid and sulfuric acid electrochemically demetallized.
  • the separation of the metal ions of the electrolyte takes place by means of the generated in situ Diaphragm.
  • the Suitable material can easily be found on the basis of simple experiments find.
  • An electrolysis cell is used to carry out the method (Fig.1), their anodic and cathodic area are separated from each other by a porous partition.
  • a porous partition When putting on of direct current to the electrolyte to be demetallized filled cell is formed by migration of the sulfate ions in the anolytes on the side of the catholyte one of sulfate ions depleted diffusion layer with high phosphoric acid content from, which complicates the passage of the metal ions and as Separation medium works.
  • the higher the content of phosphoric acid in the mixture the lower the exchange of metal ions in principle through the diaphragm.
  • the dissolved iron originally mainly lies in Form of readily soluble Fe (III) ions before. These are in the cathode compartment reduced to much less soluble Fe (II) ions and then fall in when the solubility limit is reached Form of iron (II) sulfate (mostly as cathode sludge). This is easy through appropriate processes such as sedimentation, Separate filtration, centrifugation etc. from the electrolyte. At the same time, nickel and chrome are also deposited. Advantageous it has also been shown that impurities in the electrolyte, those that got into them during electropolishing, largely bound to the sludge and also separated. In order to will be an accumulation of these substances at higher concentration could interfere with the electropolishing process.
  • the iron content of the electrolyte is in the Usually around 2.5% by weight and thus in the ideal working range. After adding the sulfuric acid consumed by the precipitation and setting the correct density is the cleaned electrolyte usable again.
  • the process works in a very wide mixing range of Phosphoric acid and sulfuric acid and is effective as soon as the metal content is over 40 g / l.
  • a device for the recovery of entrained electrolytes and cleaned Water from the rinse water e.g. an evaporator in Connection with a suitable rinsing water supply is a waste water-free one Operation of electropolishing systems possible (Fig. 2).
  • the sludge from the process contains the separated sludge Metals in high concentration. He can after appropriate treatment may be used for further use. With that created the conditions to avoid the generation of hazardous waste, which places a heavy burden on the landfills and high disposal costs caused.
  • the invention in another aspect, relates to a method for demetallizing mixtures which are essentially phosphoric acid and contain sulfuric acid, the one enriched with metal ions Mixture is transferred to an electrolytic cell the Fe (III) ions are reduced to Fe (II) ions and these are then Form of Fe (II) sulfate can be precipitated.
  • a regeneration of highly acidic electropolishing baths can be achieved.
  • polishing stainless steel works with a current density of 5 - 50 A / dm 2 , preferably about 10 - 25 A / dm 2 , at about 40 - 80 ° C and a polishing time of approx. 15 min.
  • the method of the invention can be in terms of actual electropolishing subsequent process stages optimize.
  • electropolishing subsequent rinsing so that the rinse water using a cascade rinse with rinsing water regeneration (Evaporator) in a closed circuit.
  • the electrolyte recovered from the rinse water can then be used again be fed into the process.
  • the metal salts separated from the electrolyte during filtration contain the heavy metals in high concentration. she can, for example, be fed directly to an smelting process become. Through a treatment downstream of the filtration such as e.g. B. Rinsing with ice water can the metal salts as far from adhering acid residues are cleaned that a safe Handling is possible.
  • the method according to the invention is known per se Arrangement for electrolytic polishing with a separate one electrochemical cell including the diaphragm and agent performed for filtering the electrolysis bath. Usually include these means feeds and discharges, which are constant or discontinuous return of the electrolyte solution in the polishing process enable.
  • FIG. 1 shows a schematic structure of a demetallization device and illustrates the essential electrochemical Reactions.
  • FIG. 2 shows a process flow diagram of a wastewater-free Electropolishing system which uses the method according to the invention.
  • FIG. 1 shows a demetallization device as it is used externally but also integrated in an electropolishing process can be.
  • the electrolyte is fed through suitable leads into the electrolytic cell continuously or discontinuously performed and subjected to electrolysis there.
  • Fe (III) ions are reduced to Fe (II) ions and if exceeded a certain limit concentration (which by the Ion product is determined) precipitated as iron sulfate.
  • Electropolishing baths generally have high sulfate concentrations, the Fe (II) is precipitated practically quantitatively as sulfate.
  • the slurry or suspension from the electrolytic cell is then fed to a filter in which essentially that Iron sulfate is deposited.
  • the process flow diagram shown in FIG. 2 illustrates the particular advantages of the procedure according to the invention. Because both the electrolyte and the rinse water can be reused can, works optimally a system according to the invention practically wastewater-free. Workpieces that are electropolished have been subjected to, in a rinse stage (economy sink) in essentially rinsed with water. The waste water from the economy sink can then an evaporator can be fed to the electrolyte by distillation separates from the rinse water so that both can be reused separately can be. When the electrolyte is electropolished has reached a certain metal concentration in the Readjust the electropolishing effect. To prevent this condition or to regenerate the electropolishing ability Electrolyte from the electrolysis bath continuously or discontinuously a separate demetallization fed.
  • demetallization is electrochemical Fe (III) reduced to Fe (II) and the iron content essentially precipitated as Fe (II) sulfate.
  • a sludge is obtained which is another external one Refurbishment can be supplied.
  • a regenerated Get electrolyte in the electropolishing process is returned.
  • the external one shown here in Fig.2 Refurbishment is not essential to over a long period Period a continuous wastewater-free electropolishing system keep in operation. But it has certain advantages because acid components were also recovered from this external treatment which can then flow back into the electropolishing stage.
  • An electrolysis cell was used which could hold a volume of approximately 10 liters.
  • a porous ceramic plate with a pore size of approximately 1.0 ⁇ m was used as the separating material.
  • the separate electrolysis was carried out batchwise, with only the cathode space being filled with electrolyte after the filtrate had been returned from the cathode space of the electrolysis cell to the electropolishing device.
  • the temperature was set to 60 ° C and the voltage was 3 V. Carbon pins and stainless steel sheets were used as electrodes.
  • Electrolyte 1 85% phosphoric acid 60.0% by weight 96% sulfuric acid 36.0% by weight Morpholinomethane diphosphoric acid 1.0% by weight Diethanolamine 0.5% by weight water 2.5% by weight
  • Electrolyte 2 85% phosphoric acid 54.0% by weight 96% sulfuric acid 43.0% by weight Morpholine 1.0% by weight Diisopropanolamine 0.5% by weight water 1.5% by weight
  • Electrolyte 3 85% phosphoric acid 56.0% by weight 96% sulfuric acid 40.0% by weight Nicotinic acid 1.5% by weight Diisopropanolamine 0.5% by weight water 2.0% by weight
  • the electrolyte was in the bypass flow during the entire operating time fed to the electrolysis cell described above and filtered, so that the total bath volume depending on the bath load every 3 up to 14 days.
  • the through the sludge discharge Losses of chemicals caused have been added. It revealed a steady state of the electrolyte with a total content on metals (mainly iron, chromium and nickel) of 2.5 up to 4% by weight.
  • the electrolyte remained functional and that The results achieved corresponded to the quality expectations the current state of the art. After reaching the stationary The state of the electrolyte became the whole when electropolishing Amount of metal removed immediately during electrolysis precipitated as metal salt sludge and via the filter circuit in concentrated form removed from the electrolyte.
  • Electrolytic solution of different composition demetallized was also consumed.
  • the electrolytic cell corresponded to the above information. It was found that with a wide variety of compositions the as typical examples of electropolishing solutions are considered can, successful demetallization is achieved and that the electropolishing solutions have been successfully regenerated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • ing And Chemical Polishing (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (4)

  1. Procédé pour démétalliser des mélanges qui contiennent essentiellement de l'acide phosphorique et de l'acide sulfurique en introduisant le mélange dans une cellule d'électrolyse comprenant une paroi de séparation en un matériau présentant une largeur de pores comprise entre 0,5 pm et 10 µm et telle que lors de l'application d'un courant continu in situ un diaphragme perméable se forme qui rend plus difficile la traversée d'ions métalliques, entre la zone anodique et cathodique de la cellule d'électrolyse, et dans lequel les ions Fe(III) présents dans le mélange sont réduits en ions Fe(II) et sont précipités sous forme de FeSO4 lorsque la limite de solubilité est atteinte et les précipités sont séparés.
  2. Utilisation d'un procédé selon la revendication 1 pour le polissage électrolytique de surfaces en acier spécial, lors de laquelle
    un mélange acide sulfurique / acide phosphorique est utilisé comme électrolyte,
    l'électrolyte est soumis séparément de façon continue ou discontinue à une électrolyse lors de laquelle les ions Fe(III) sont réduits en ions Fe(II) et
    les précipités apparaissant sont séparés par filtration et le filtrat est ramené dans l'électrolyte.
  3. Utilisation selon la revendication 2,
    caractérisée en ce que l'eau de rinçage est mise en circulation en circuit fermé dans le processus de rinçage qui suit immédiatement le polissage électrolytique.
  4. Utilisation selon la revendication 3,
    caractérisée en ce que l'électrolyte récupéré du circuit fermé d'eau de rinçage est recyclé.
EP96921930A 1995-06-09 1996-06-04 Procede de demetallisation de bains tres acides et mise en oeuvre de ce procede pour le polissage electrolytique de surfaces en acier special Expired - Lifetime EP0832315B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19521132A DE19521132C1 (de) 1995-06-09 1995-06-09 Verfahren zum Entmetallisieren von hochsauren Bädern und Verwendung dieses Verfahrens beim Elektropolieren von Edelstahloberflächen
DE19521132 1995-06-09
PCT/EP1996/002439 WO1996041905A1 (fr) 1995-06-09 1996-06-04 Procede de demetallisation de bains tres acides et mise en oeuvre de ce procede pour le polissage electrolytique de surfaces en acier special

Publications (2)

Publication Number Publication Date
EP0832315A1 EP0832315A1 (fr) 1998-04-01
EP0832315B1 true EP0832315B1 (fr) 1999-03-24

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EP96921930A Expired - Lifetime EP0832315B1 (fr) 1995-06-09 1996-06-04 Procede de demetallisation de bains tres acides et mise en oeuvre de ce procede pour le polissage electrolytique de surfaces en acier special

Country Status (11)

Country Link
US (1) US5882500A (fr)
EP (1) EP0832315B1 (fr)
JP (1) JP2000512685A (fr)
AT (1) ATE178106T1 (fr)
AU (1) AU6300596A (fr)
CA (1) CA2226367A1 (fr)
CZ (1) CZ396197A3 (fr)
DE (2) DE19521132C1 (fr)
ES (1) ES2129268T3 (fr)
TW (1) TW358831B (fr)
WO (1) WO1996041905A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0931860A1 (fr) * 1997-12-31 1999-07-28 Otomec S.r.l. Appareillage pour le traitement électrolytique de fils ferreux et non ferreux
US6428683B1 (en) * 2000-12-15 2002-08-06 United Technologies Corporation Feedback controlled airfoil stripping system with integrated water management and acid recycling system
CN103361660A (zh) * 2012-03-27 2013-10-23 中国科学院大连化学物理研究所 一种质子交换膜燃料电池不锈钢双极板前处理方法
US9057272B2 (en) * 2012-06-29 2015-06-16 United Technologies Corporation Protective polishing mask
WO2016030506A1 (fr) 2014-08-29 2016-03-03 Poligrat Gmbh Électrolyte permettant de polir des aciers inoxydables, contenant un acide pyridine-carboxylique
US20170088971A1 (en) * 2015-09-30 2017-03-30 Macdermid Acumen, Inc. Treatment of Etch Baths

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3206538C2 (de) * 1982-02-24 1984-04-12 Keramchemie GmbH, 5433 Siershahn Verfahren zur elektrolytischen Regenerierung von verbrauchter Schwefelsäure-Beizflüssigkeit
DE3343396A1 (de) * 1983-11-30 1985-06-05 Kraftwerk Union AG, 4330 Mülheim Verfahren zum dekontaminieren metallischer komponenten einer kerntechnischen anlage
DE4218915A1 (de) * 1992-06-10 1993-12-16 Heraeus Elektrochemie Verfahren und Vorrichtung zur Regenerierung einer Metallionen und Schwefelsäure enthaltenden wäßrigen Lösung sowie Verwendung

Also Published As

Publication number Publication date
DE19521132C1 (de) 1996-10-17
US5882500A (en) 1999-03-16
JP2000512685A (ja) 2000-09-26
ATE178106T1 (de) 1999-04-15
DE59601506D1 (de) 1999-04-29
AU6300596A (en) 1997-01-09
ES2129268T3 (es) 1999-06-01
CA2226367A1 (fr) 1996-12-27
CZ396197A3 (cs) 1998-06-17
EP0832315A1 (fr) 1998-04-01
TW358831B (en) 1999-05-21
WO1996041905A1 (fr) 1996-12-27

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