EP0519987B1 - Procede et dispositif de regeneration de reactifs alcalins d'attaque micrographique de l'aluminium - Google Patents

Procede et dispositif de regeneration de reactifs alcalins d'attaque micrographique de l'aluminium Download PDF

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Publication number
EP0519987B1
EP0519987B1 EP91906096A EP91906096A EP0519987B1 EP 0519987 B1 EP0519987 B1 EP 0519987B1 EP 91906096 A EP91906096 A EP 91906096A EP 91906096 A EP91906096 A EP 91906096A EP 0519987 B1 EP0519987 B1 EP 0519987B1
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EP
European Patent Office
Prior art keywords
pickling
reactor
solution
bath
section
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EP91906096A
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German (de)
English (en)
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EP0519987A1 (fr
Inventor
Dieter Brodalla
Roland Fransson
Herbert Breunig
Michael Ferner
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Josef Gartner and Co
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Josef Gartner and Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • aluminum surfaces are to be finished (for example by anodizing or plating), it is generally necessary to subject these surfaces to a pickling treatment beforehand, both acidic and alkaline pickling solutions being able to be used.
  • alkaline pickling solutions the aluminum is immersed in a heated bath, for example containing sodium hydroxide solution, and left in it for a certain time.
  • the pickling process consists of the alkali dissolving the metal surface, with aluminum dissolving to a small extent with the evolution of hydrogen.
  • the overall gross equation is as follows: Al + NaOH + H2O ⁇ NaAlO2 + 3/2 H2 (1) Since aluminum dissolves to a certain extent, the bath is constantly enriched with aluminate during operation.
  • DE-PS 43 977 describes a process for the preparation of alumina hydrate and alkali aluminate, in which aluminum hydroxide is precipitated from essentially pure alkali aluminate solutions by seeding. This procedure was later improved by further developments, although the further developments essentially used pure aluminate solutions.
  • EP-A1 157 190 describes a process for the precipitation of aluminum hydroxide from pickling baths which, in addition to aluminate, also contain additives in the form of gluconate and carbonate. In this process, however, the aluminum hydroxide precipitates directly in the pickling bath. Such a way of working is disadvantageous for various reasons. First of all, it cannot be prevented that precipitated aluminum hydroxide settles on the aluminum pieces to be pickled, which leads to undesirable staining on the aluminum surface. It is also necessary to continuously filter out the precipitated aluminum hydroxide from the bath pickling solution either continuously or in batches. US-A-4,826,605 shows the precipitation of aluminum hydroxide from pickling solutions by adding acid and subsequent oxidation with ozone.
  • the pickling solution in the pickling bath must be undersaturated or metastably oversaturated, for which purpose the concentrations of aluminate, alkali and gluconate in the pickling bath and the temperature are used as control parameters.
  • An operating mode with slightly metastable supersaturation is preferred.
  • the aluminate concentration (given as equivalent aluminum) is 30 to 60 g / l, preferably 30 to 45 g / l.
  • the concentration of complexing agent, given as equivalent gluconate is 0.1 to 5 g / l, preferably 0.5 to 2 g / l.
  • the alkali hydroxide concentration is in the range from 30 to 60 g / l equivalent sodium hydroxide, preferably in the range from 45 to 55 g / l.
  • Alkali hydroxide concentration means the free concentration of MeOH, where Me is an alkali metal.
  • the pickling solutions used according to the invention primarily contain alkali hydroxide (e.g. NaOH, KOH or mixtures thereof), aluminum (as aluminate) and complexing agents.
  • Additives such as nitrate and / or nitrite are also added to improve the decorative surface finish.
  • the nitrate concentrations are preferably in the range from 5 to 30 g / l, particularly preferably in the range from 20 to 25 g / l.
  • Preferred nitrite concentrations are 5 to 30 g / l, particularly preferably 10 to 25 g / l.
  • Other additives that can be used are alkali salts of inorganic acids in the concentration range from 1 to 100 g /, as in e.g. Chloride, chlorate, carbonate and thiosulfate.
  • the pickling solution is transferred from the pickling bath into a reactor section consisting of at least one reactor using the first transfer section.
  • the pickling solution transferred into the reactor section is referred to below as the "reactor solution”.
  • the reactor section aluminum precipitates as aluminum hydroxide by creating conditions in which the reactor solution is unstably supersaturated.
  • a jump in temperature between the pickling bath and the reactor section serves this purpose.
  • the pickling solution is in the pickling bath at a temperature of 40 to 90 ° C, which is why the reactor line must be kept at a low temperature.
  • the precipitation process in the reactor section is promoted and accelerated by inoculation.
  • "Inoculation” is understood below to mean the presence of crystal nuclei. It is generally only necessary to introduce germs from the outside when starting up the system; if the plant has been in operation for a certain time (approximately 24 to 72 hours), a sufficient nucleus density in the sense of a steady state equilibrium arises in the reactor solution.
  • the crystalline aluminum hydroxide formed by the precipitation also acts as a germ, ie the process has a self-initiating effect. However, the process can also be operated in such a way that germs are continuously introduced from the outside if the germ density is not sufficient in the equilibrium state.
  • a suitable vaccine to be introduced from the outside is crystalline aluminum hydroxide phases, preferably gibbsite. It was observed that when gibbsite was used as the vaccine, the aluminum hydroxide essentially also precipitated as gibbsite.
  • the reactor section is preferably stirred intensively, and in the case of a reactor section consisting of several reactors, it may be advantageous to stir only the first reactor and to operate the downstream reactor (s) without stirring.
  • the first reactor is referred to below as the reaction vessel and the second or further reactor as the sedimentation vessel.
  • the base obtained in the process when the aluminum hydroxide precipitates can be obtained by stripping off the aqueous, highly alkaline solution which is formed in the sedimentation tank above the sediment / liquid phase boundary. It is preferred to return this alkali solution to the pickling bath and to continue using it for pickling aluminum (recycling).
  • the stripped alkaline solution must contain no or as few crystallization nuclei as possible, because this could lead to undesired crystal growth of aluminum hydroxide in the pickling bath.
  • the alkaline solution is therefore preferably drawn off from the surface of the liquid in the sedimentation container and filtered before being returned to the pickling bath.
  • further sedimentation containers can also be used behind the (first) sedimentation container. A combination of both measures (filtering + further sedimentation containers) is also possible.
  • the reaction vessel can be designed in one, two or more stages. A multi-stage procedure is required if post-reactions occur.
  • a device (system) according to the invention has a pickling bath in which pickling solution can be heated or optionally cooled to the temperatures according to claim 1.
  • a first transfer line leads from the pickling bath to a reactor line consisting of at least one reactor.
  • the first transfer line is e.g. represents a pipeline and is preferably insulated against heat loss and / or heatable.
  • the transition from the transfer line to the reactor line is preferably carried out in such a way that the transfer tube does not dip into the liquid level of the reactor line (bodyless transfer).
  • the transfer path therefore preferably ends directly above a funnel-like insertion element which is attached above the liquid level of the first reactor.
  • the reactor section consists of at least one reactor, an arrangement of a first stirred reactor (reaction vessel) and a subsequent unstirred sedimentation vessel being preferred.
  • a further stirred reaction container can be arranged between the (first) reaction container and the sedimentation container.
  • the volume of the reaction container is preferably one third to half of the volume of the pickling bath.
  • the reactor volume represents an additional control parameter for the process because it can influence the residence time of the reactor solution in the reactor. A stay of 36 to 60 hours is preferred.
  • the reactor volume stabilizes the temperature of the reactor contents.
  • the reaction vessel has a stirring device with which the reactor contents can be stirred intensively. A tall and as slim as possible shape of the reaction container is preferred because this enables easier and more effective stirring and also improves the subsequent sedimentation.
  • a second transfer line leads from the reaction tank to the sedimentation tank, the second transfer line in the sedimentation tank preferably ending via a lateral wall opening at a height just above the sediment / liquid phase boundary.
  • the sedimentation container has a volume similar to that of the reaction container and can have a third transfer section with which the clear alkali solution standing above the sediment can be drawn off as close as possible to the liquid surface of the sediment container.
  • This transmission path is preferably led back to the pickling bath (recycling), a filter being able to be interposed.
  • the liquid is removed from the reaction container 20 with the aid of a second transfer section 23.
  • the second transfer section 23 opens into a sedimentation container 30 through a lateral wall duct just above the phase boundary 34, which is formed by the liquid 32 and the sediment 31.
  • the content of the sedimentation container 30 has a liquid level 33, in the immediate height or at most just below it a third transfer section 35 is arranged for discharging the clear liquid 32.
  • the third transfer section 35 leads back to the pickling bath 10, a filter 36 and preferably a measuring section 37 being able to be interposed.
  • a removal point for aluminum hydroxide is designated 38.
  • the pickling bath 10 has a volume of approximately 12 cubic meters and the reaction or sedimentation container 30 each has a volume of approximately 8 cubic meters.
  • An example of the application of the method according to the invention are the measured value logs for the operating time of the plant for the period from March 1 to March 7, 1990, in which reactor I means reaction vessel 20 and reactor II sedimentation vessel 30.
  • concentrations of NaOH and aluminum in the pickling bath are 43.4 to 56.0 g / l and 33.2 to 40.5 g / l, that of gluconate 0.9 to 1.2 g / l. Although relatively little complexing agent is present, no precipitation of aluminum hydroxide in the pickling bath was observed.

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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)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (17)

  1. Procédé de régénération de réactifs alcalins d'attaque micrographique de l'aluminium pour la récupération d'hydroxyde d'aluminium, dans lequel on transfère un réactif d'attaque micrographique contenant un hydroxyde alcalin, un aluminate ainsi qu'un agent complexant et d'autres additifs, au moyen d'un premier système de transfert, à partir d'un bain de décapage, à un système de réacteurs formé d'au moins un réacteur, où l'aluminium précipite sans addition d'acide, sous la forme d'hydroxyde d'aluminium,
    caractérisé en ce qu'on utilise, comme agent complexant, un gluconate, le sorbitol ou d'autres dérivés complexants d'un sucre, les phosphonates, ainsi que les acrylates polymères ou oligomères, et que
    a) le réactif d'attaque micrographique dans le bain de décapage est à une température plus élevée que dans le système de réacteurs, et qu'on ajuste
    b) la concentration de l'aluminate, de l'alcali et de l'agent complexant,
    c) la température du réactif d'attaque micrographique dans le bain de décapage, et
    d) la diminution de la température du réactif d'attaque micrographique, entre le bain de décapage et le système de réacteurs, d'une manière telle que
    e) le réactif d'attaque micrographique dans le bain de décapage est sous-saturé ou sursaturé de façon métastable par rapport à la précipitation d'hydroxyde d'aluminium, mais sursaturé de façon instable dans le système de réacteurs,
    f) les composants du réactif d'attaque micrographique dans le bain de décapage étant présents aux concentrations suivantes : aluminate, compté en Al 30 à 60 g/l hydroxyde alcalin, compte en equivalent d'hydroxyde de sodium 30 à 60 g/l agent complexant, compté en équivalent gluconate 0,1 à 5 g/l,
    g) la température du réactif d'attaque micrographique étant comprise entre 40 et 90°C, et la diminution de la température du réactif d'attaque micrographique entre le bain de décapage et le système de réacteurs étant de 5 à 70°C.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on fait germer le réactif d'attaque micrographique dans le système de réacteurs.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on effectue la germination à une densité élevée de germes sous agitation énergique.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on effectue la germination avec de la gibbsite.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on effectue le transfert du réactif d'attaque micrographique au système de réacteurs sous la forme d'une introduction à l'état dissous.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on fait germer le réactif d'attaque micrographique transféré dans le premier système de transfert.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que le premier système de transfert entre le bain de décapage et le système de réacteurs est isolé thermiquement et a une configuration telle qu'il peut être chauffé.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on le met en oeuvre en continu.
  9. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on recycle dans le bain de décapage la base obtenue par la précipitation de l'hydroxyde d'aluminium.
  10. Procédé selon la revendication 9, caractérisé en ce qu'on filtre la solution alcaline avant le recyclage dans le bain de décapage.
  11. Dispositif pour la mise en oeuvre du procédé selon les revendications précédentes, comportant
    a) un bain de décapage (10) recevant un réactif d'attaque micrographique,
    b) un premier système de transfert (12) pour le transfert du réactif d'attaque micrographique à un système de réacteurs comportant au moins un réacteur (20, 30),
    caractérisé par
    c) un dispositif de chauffage et/ou de refroidissement (11) au moyen duquel le réactif d'attaque micrographique dans le bain de décapage (10) peut être chauffé à une température comprise entre 40 et 90°C, de sorte qu'il est à une température supérieure de 5 à 70°C à sa température dans le système de réacteurs.
  12. Dispositif selon la revendication 11, caractérisé en ce que le premier système de transfert (12) est isolé contre les pertes de chaleur et/ou est conçu de façon à pouvoir être chauffé.
  13. Dispositif selon les revendications 11 et 12, caractérisé par un dispositif d'admission (21) en forme d'entonnoir permettant un transfert du réactif d'attaque micrographique sans solides au système de réacteurs.
  14. Dispositif selon les revendications 11 à 13, caractérisé en ce qu'au moins le premier réacteur a la forme d'un réacteur à agitation (20) grâce à un agitateur (22) disposé dans celui-ci.
  15. Dispositif selon les revendications 11 à 14, caractérisé par au moins un récipient pour sédimentation (30) relié au réacteur (20) au moyen d'un deuxième système de transfert (23).
  16. Dispositif selon les revendications 11 à 15, caractérisé par un troisième système de transfert (35) menant d'au moins un récipient pour sédimentation (30) au bain de décapage (10).
  17. Dispositif selon les revendications 11 à 16, caractérisé par un filtre (36) incorporé dans le troisième système de transfert (35).
EP91906096A 1990-03-15 1991-03-15 Procede et dispositif de regeneration de reactifs alcalins d'attaque micrographique de l'aluminium Expired - Lifetime EP0519987B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4008379 1990-03-15
DE4008379A DE4008379A1 (de) 1990-03-15 1990-03-15 Verfahren und anlage zum regenerieren von alkalihaltigen aluminiumbeizloesungen
PCT/EP1991/000491 WO1991014019A2 (fr) 1990-03-15 1991-03-15 Procede et dispositif de regeneration de reactifs alcalins d'attaque micrographique de l'aluminium

Publications (2)

Publication Number Publication Date
EP0519987A1 EP0519987A1 (fr) 1992-12-30
EP0519987B1 true EP0519987B1 (fr) 1994-12-07

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EP (1) EP0519987B1 (fr)
JP (1) JPH05505852A (fr)
AT (1) ATE115197T1 (fr)
DE (2) DE4008379A1 (fr)
WO (1) WO1991014019A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656489A (en) * 1992-07-22 1997-08-12 E. I. Du Pont De Nemours And Company Method for the remediation of organoleads especially tetraethyllead (TEL) in contaminated natural media
DE102008001577A1 (de) * 2008-05-06 2009-11-12 Wacker Chemie Ag Verfahren zur Hydrolyse von festen Metallsalzen mit wässrigen Salzlösungen
EP2352859B1 (fr) * 2008-11-03 2018-06-27 Thomas König Procédé et installation de décapage

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE43977C (de) * 1892-01-31 1888-08-03 Dr. K. J. BAYER in Dorf Tentelewa bei St. Petersburg Verfahren zur darstellung von thonerdehydrat und alkalialuminat
US2975041A (en) * 1956-08-06 1961-03-14 Purex Corp Ltd Method for etching aluminum and aluminum alloy bodies
FR2167243A1 (en) * 1972-01-11 1973-08-24 Maltret Georges Regenerating etch bath - for etching aluminium prior to anodising
US3909405A (en) * 1972-04-07 1975-09-30 Dai Doh Plant Engineering Corp Method for treating alkaline waste streams containing aluminum dissolved therein
DE2433141A1 (de) * 1974-07-10 1976-01-29 Kannegiesser H Kg Rotationskoerper zur herstellung und/ oder behandlung von bahnen, stuecken, folien und verbundmaterialien
US4136026A (en) * 1977-11-23 1979-01-23 Aluminum Company Of America Caustic solution having controlled dissolved aluminum content
JPS5810895B2 (ja) * 1979-07-16 1983-02-28 東京計装株式会社 デ−タ収集回路
EP0157190B1 (fr) * 1984-03-16 1990-07-18 Prof. Dr. E. Plattner Procédé de décapage d'aluminium
US4826605A (en) * 1986-11-03 1989-05-02 Caspian International, Inc. Process for depleted chemical milling solutions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Bd. 84, 1979, Seite 301, Zusammenfassung Nr. 110 145t, Columbus, Ohio, US; & JP-A-50 142 433 *

Also Published As

Publication number Publication date
WO1991014019A2 (fr) 1991-09-19
ATE115197T1 (de) 1994-12-15
DE4008379C2 (fr) 1992-01-16
WO1991014019A3 (fr) 1991-10-31
JPH05505852A (ja) 1993-08-26
DE59103815D1 (de) 1995-01-19
DE4008379A1 (de) 1991-09-19
EP0519987A1 (fr) 1992-12-30

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