EP2352859B1 - Procédé et installation de décapage - Google Patents

Procédé et installation de décapage Download PDF

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Publication number
EP2352859B1
EP2352859B1 EP09796936.4A EP09796936A EP2352859B1 EP 2352859 B1 EP2352859 B1 EP 2352859B1 EP 09796936 A EP09796936 A EP 09796936A EP 2352859 B1 EP2352859 B1 EP 2352859B1
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EP
European Patent Office
Prior art keywords
pickling
permeate
solution
sedimentation
container
Prior art date
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Not-in-force
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EP09796936.4A
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German (de)
English (en)
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EP2352859A2 (fr
Inventor
Thomas König
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Konig Thomas
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Konig Thomas
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Priority claimed from DE102008063729A external-priority patent/DE102008063729A1/de
Priority claimed from DE200810062970 external-priority patent/DE102008062970A1/de
Application filed by Konig Thomas filed Critical Konig Thomas
Publication of EP2352859A2 publication Critical patent/EP2352859A2/fr
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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
    • 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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/36—Alkaline compositions for etching aluminium or alloys thereof
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/027—Associated apparatus, e.g. for pretreating or after-treating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

Definitions

  • the invention relates to a pickling process for workpieces made of aluminum or aluminum alloys and a pickling plant suitable for such a pickling process.
  • the surface pretreatment by pickling takes place predominantly in alkaline baths, for example in sodium hydroxide solution.
  • the aluminum reacts on the surface of the workpiece with the sodium hydroxide solution according to the formula: 2Al + 6H 2 O + 2NaOH ⁇ 2NaAl (OH) 4 + 3H 2 ⁇
  • the aluminum goes into solution, which does not precipitate as Al (OH) 3 in the presence of complexing agents and free NaOH.
  • a certain concentration of aluminum in the pickling solution is helpful to slow down the pickling process, as it can provide a high quality and matte finish.
  • Such a long-term stain is in equilibrium if the proportion of the aluminum going into solution corresponds approximately to the mass fraction which is removed from the pickling bath by the workpieces during removal - ie in this state of equilibrium the aluminum content of the pickling bath remains approximately constant.
  • a Equilibrium state for example, at an aluminum concentration of about 140 to 180 g / l aluminum.
  • the pickling quality is adversely affected by the fact that different heavy metals, silicates, etc. accumulate in the pickling solution - depending on the alloy content of the various workpieces.
  • an increased content of zinc has a particularly negative effect, since the zinc precipitates at the grain boundaries and forms so-called "zinc flowers", which adversely affect the surface quality.
  • pickling additives are added to the pickling solution.
  • the flow behavior of the pickling solution can be improved by the workpiece so that less pickling solution is removed when transferring the workpieces from the pickling solution in a subsequent rinse.
  • Other pickling additives for example sulfides, form metal sulfides which are sparingly soluble with the heavy metals and precipitate out as sludge in the bath.
  • complexing agents such as gluconate, sorbitol or other derivatives from sugar chemistry are added in such pickling baths, can be prevented by the precipitation of aluminum hydroxide.
  • the alkaline pickling solution insoluble elements such as copper, silicon, etc., remain in the mud.
  • the sludge obtained in the pickling bath which is colored black due to the alloy constituents (for example Si, Zn, Mn and Cu compounds), is withdrawn from the plant at regular intervals, for example twice a year, and disposed of.
  • the alkaline pickling is also removed in order to prevent an excessive increase in the Al concentration and to compensate for losses caused by carry-over (NaOH, additives).
  • a treatment method for a pickling solution is described with the aim of keeping the aluminum concentration in the pickling solution within a predetermined range.
  • a subset of the pickling solution in centrifuges is partially freed of solids and then cooled to precipitate aluminum hydroxide and corresponding alloying ingredients.
  • the remaining clear phase is freed of solids in a further process step and fed to a tank in which the concentration of sodium aluminate can be adjusted by adding an aluminum hydroxide-rich filter cake obtained during the filtration.
  • Aluminum hydroxide is thus precipitated in both of the above-described known processes, with alloy constituents, such as, for example, zinc, being precipitated.
  • a precipitation of the heavy metals would result in this process, that the precipitated in the bath and subsequently obtained by solids separation aluminum hydroxide would be contaminated with heavy metals - the desired utilization of Aluminimhydroxids would be severely limited.
  • Pickling additives are not mandatory in this process because precipitation of aluminum hydroxide is desired.
  • the aluminum then precipitates at low concentrations as aluminum hydroxide - as stated - such a low aluminum content in the pickling bath, however, deteriorates the surface quality, so that the cost savings by the accumulation of aluminum hydroxide and / or sodium hydroxide at the expense of surface quality.
  • the DE 40 15 141 A1 discloses a process in which a pre-treatment bath - ie a pickling bath - continuously fresh pickling liquid is supplied and a corresponding amount of "spent" pickling liquid withdrawn and fed either a supply or a further processing.
  • the invention has for its object to provide a pickling bath and a pickling plant, which allow a long-term pickling with minimal effort.
  • a continuous and discontinuous preparation and concentration adjustment of a pickling solution of a pickling bath are provided in the pickling process for workpieces made of aluminum or aluminum alloys.
  • a subset of the pickling solution is withdrawn continuously or in sections from the pickling bath, and solids are separated from the withdrawn subset by means of a solids separation / solids separation.
  • composition of the remaining, low-solids permeate taken up in a receiver tank and the actual composition of the pickling solution of the pickle bath are analyzed and a permeate target composition adjusted by adding pickling solution and additives depending on the result of this analysis. From this permeate in the feed tank then permeate is fed back into the pickling bath to keep the pickling solution contained therein to a predetermined target composition. Due to the quasi-continuous extraction of solids from the pickling solution and precipitation of the heavy metals outside the pickling bath, a seepage of the sludge at the bottom of the pickling bath is reliably prevented, so that a long-term pickling with high efficiency is made possible.
  • the pickling plant according to the invention for carrying out the pickling process according to the invention is correspondingly carried out with a pickling bath which has a process for discharging a partial amount of a pickling solution from the pickling bath.
  • the pickling plant also has a solids separation in which the heavy metals described in the form of solids removed from the stripped pickling solution become.
  • the low-solids permeate is temporarily stored in a storage tank.
  • the pickling plant also has an analysis for analyzing the composition of the low-solids permeate received in the receiving container.
  • This analysis can also be used to record the composition of the pickling solution of the pickling bath.
  • pickling solution for example sodium hydroxide solution
  • additives are then supplied by means of a metering unit in order to adjust a composition of the permeate in the storage container which is dependent on the actual composition of the pickling solution.
  • the pickling solution is frequently fed to a special chemistry in which all the necessary pickling additives are contained.
  • Such a procedure has the disadvantage that even if there is a shortage with a single pickling additive, the special chemistry consisting of a multiplicity of pickle additives is metered in, so that the other pickling additives are rather overdosed.
  • a targeted adjustment by addition of the individual pickling additives and sodium hydroxide solution, so that such overdose is avoided.
  • the permeate taken up with a defined target composition is passed from the feed tank into the pickling bath in order to keep the pickling solution at a predetermined desired composition and to compensate for volume losses or to keep the Al content constant.
  • Volume losses can also be compensated by a downstream EO stain, floor sink or 1st sink.
  • This bath can be integrated into the process according to the invention, wherein the filling of the sedimentation tank does not have to take place directly from the pickling bath 1. In this case, solid is separated, the concentration determined, metered accordingly and filled the pickling bath.
  • the separation of solids takes place by means of a membrane filtration and subsequent sedimentation in the sedimentation tank.
  • a membrane filtration and subsequent sedimentation in the sedimentation tank.
  • suitable solid separation processes can be used with which heavy metals in the form of solids can be separated from an alkaline or acid pickling solution.
  • the solids separation contains a dynamic filtration, preferably a micro- or ultrafiltration.
  • the retentate produced during the filtration can be circulated through the filter in a variant according to the invention in the batch mode until the retentate has reached the desired concentration (for example 10 times).
  • the sub-quantity withdrawn from the pickling bath can be added to the circulated volume flow.
  • a continuous procedure feed and bleed
  • the concentration preferably takes place in the sedimentation tank - as soon as the desired concentration is reached, the membrane filtration is terminated, so that flocculation and sedimentation of the undissolved heavy metal compounds takes place in the form of solids in the sedimentation tank.
  • this sedimentation clear phase is subtracted in a variant of the pickling process according to the invention and fed to the storage container.
  • the solids concentration of this clear phase corresponds approximately to the concentration of the permeate from the first filter operation.
  • the turbidity phase (sediment) obtained during the sedimentation is withdrawn from the sedimentation tank and fed to a solids separator, for example a static filter, and the filtrate, which has largely been freed of solids, is then fed to the feed tank.
  • This filtrate also has about the same solids concentration of the aforementioned permeate and the aforementioned clear phase.
  • the accumulating on the static filter cake, which has a high content of heavy metals, is preferably disposed of as waste. Through this downstream filter, the waste volume can be reduced to a minimum.
  • This addition of additives / caustic soda takes place as a function of the actual composition of the pickling solution taken up in the pickling bath and / or of the aluminate concentration in the feed / metering tank or of the desired concentration of an aluminate intended for further use.
  • This composition is determined in a preferred embodiment after removing the solids, or from the permeate.
  • the solids separation takes place approximately at the temperature of the pickling bath, so that a correspondingly high volume flow is adjustable.
  • the storage of the concentrated permeate solution takes place at a low temperature.
  • the pickling solution can also be cooled, taking advantage of the fact that the residual solubility of the sparingly soluble heavy metal compounds decreases with the temperature.
  • a partial stream is withdrawn from the feed tank and fed to a collecting tank.
  • This highly concentrated aluminate solution can then be recycled.
  • the aluminate solution can be optimized by the addition of NaOH or additives such as complexing agents for further processing.
  • the entire process and also the pickling plant can be designed as a closed system (reactor), in which case the process liquids are conducted from the feed tank to the reactor or a coating cell and not, as usual, the work piece or the "product” to the pickling solution ("Ware to chemistry ").
  • the method can also be used for pickling by spraying.
  • the use of the low solids pickling solution prevents the nozzles from clogging.
  • the solids separation can be fed in addition to or as an alternative to the pickling solution removed from the pickling solution a solution from another process stage, for example an EO pickling.
  • the pickling plant in the area of solids separation is designed with a dynamic filter and a sedimentation tank.
  • the pickling plant can be designed with a circulation pump for recycling retentate from the sedimentation to the inlet of the filter.
  • the turbidity phase can be deducted from the sedimentation after sedimentation.
  • the pickling plant can furthermore be designed with a feed pump for conveying the clear phase arising during the sedimentation from the sedimentation tank into the feed tank.
  • the pickling plant is advantageously carried out with a filter over which the sedimentation occurring in the sedimentation (sediment) is freed from solids and the concentrated filtrate is then also fed to the reservoir.
  • This storage container can be made in two parts in a development of the invention, wherein in a permeate the above-described, resulting from the dynamic filtration, sedimentation and filtration volume flows (permeate, clear phase, filtrate) are cached.
  • This permeate container is connected via a feed pump and a suitable valve device with a dosing. Permeate can be withdrawn from the permeate container via this feed pump and fed to the metering container.
  • the composition of the permeate taken up in the dosing container is then adjusted to the desired composition by adding sodium hydroxide / additives. Permeate is then withdrawn from this template thus adjusted and fed to the pickling bath to set the desired concentration. That is, in this variant, the intermediate storage of the permeate and the setting of the dosing template are carried out separately.
  • the volume of the sedimentation tank approximately corresponds to the volume of the storage container, so that the storage container can also be filled with a filling of the sedimentation container.
  • the sedimentation container can first be filled with retentate by circulation through the filter, wherein already permeate is branched off from the filter and fed directly into the feed container. After filling the sedimentation tank, the cycle to the dynamic filter is shut off and the sedimentation process begins. The resulting clear phase is fed to the feed tank, in which the metered addition of the sodium hydroxide solution (or other pickling solution) and the additives takes place in order to set a predetermined composition in the reservoir. By removing permeate from this storage tank, the concentration of the pickling solution in the pickling bath can then be kept constant, with losses and consumption of pickling solution being compensated.
  • the pickling plant according to the invention can be designed with a collecting container for receiving permeate withdrawn from the feed container. This highly concentrated, set, for example, with regard to the reuse aluminate can then be supplied from the cache of the mentioned further processing.
  • solution from another process step for example an EO pickling or a first rinse
  • This solution can also - be fed directly to the pickling bath - similar to the prior art.
  • the target aluminum concentration in the aluminate By including the EO pickle or rinse or first rinse, the target aluminum concentration in the aluminate, which is reused, can be adjusted independently of the desired concentration in the pickling bath.
  • the condition is that the aluminum concentration in the pickling bath is greater than in the stabilized for further use aluminate. This is usually the case.
  • an aluminum concentration of about 150 g / l in the aluminate solution is desired.
  • the pickling bath usually has an Al concentration of 160-180 g / l.
  • FIG. 1 shows the basic structure of a pickling plant 1, as used in a pickling process for pickling workpieces made of aluminum or aluminum alloys.
  • the actual pickling is carried out in a pickling bath 1, wherein alkaline pickling solutions can be used.
  • a pickling solution 2 sodium hydroxide solution is used to which the additives described above, for example, to prevent unwanted precipitation of aluminum hydroxide, for binding heavy metals, to improve the pickling behavior and to improve the flow behavior are added.
  • Common additives include, for example, sodium gluconate, sodium sulfide, sodium thiosulfate or sodium nitrate. Further suitable additives can be taken from the prior art described at the outset. According to the composition of the pickling solution 2 is kept constant, wherein for the pickling detrimental solid fractions are continuously or discontinuously withdrawn.
  • a partial amount of pickling solution 2 is withdrawn from the pickling bath 1, freed of solids via a solids separation / separation 4 and then fed to a feed tank 6 in which the permeate present after the solids separation by adding sodium hydroxide solution and additives by means of a metering unit 8 a predetermined composition is set, which composition is variable depending on the actual composition of the pickling solution during the pickling process.
  • a valve assembly 14 of in FIG. 1 indicated by dashed lines solid separation 4 supplied.
  • a recirculation flow 16 which is returned to the pickling bath 1.
  • the valve 14 can be variably adjusted so that the volume flow 3 can be divided flexibly (eg 100% bath circulation or other conditions, depending on the respective cycle (filling of 20, sedimentation in 20, etc.).) By suitable adjustment of the valve arrangement 14 Thus, the volume flow set via the pump 12 can be divided again.
  • the pressure and the flow rate, which is the solids separation 4 is supplied.
  • This consists in the illustrated embodiment of a dynamic filter 18 and a sedimentation 20.
  • all other Feststoffabscheideclar can be used to separate solids from the pickling solution.
  • the separation of solids can be achieved by sedimentation alone, by centrifugation or by a static filter or by combination of known solid separation processes.
  • microfiltration is used wherein a membrane 22 is used to separate the solid.
  • two operating modes are distinguished: the "cross-flow” and the "dead-end” flow control.
  • cross-flow filtration the crude solution flows along the membrane surface, with only a relatively small portion passing through the membrane 22 as permeate.
  • liquids with a high turbidity / solids content can be clarified.
  • the concentrate or retentate 26 flowing along the membrane 22 is conducted into the sedimentation tank 20 and from there returned via a circulation pump 28 and a circulation valve arrangement 30 as circulation flow 32 to the input of the dynamic filter 18 and summed to the subset 3 withdrawn via the pump 12.
  • This circulation of the retentate 26 concentrates this, so that its solids content increases continuously, since the permeate 24 is discharged into the feed tank 6.
  • the circulation valve assembly 30 and by switching off the circulation pump 28 and by switching the valve assembly 14 to circulation or switching off the pump 12
  • the circulation of the retentate 26 is interrupted, so that in the sedimentation 20, the flocculation and the sedimentation process can begin.
  • settling in the sedimentation tank 20 clear phase 34 is withdrawn via a feed pump 37 from the sedimentation tank 20 and conveyed into the reservoir 6.
  • the sedimentation present on the bottom side turbidity phase (sediment) 36 is withdrawn via the circulation pump 28 and the corresponding switched valve assembly 30 and fed to another filter, such as a static filter.
  • this static filter is designed as a chamber filter press 38, in which the solids contained in the turbidity phase 36 are retained as a filter cake.
  • This filter cake 40 is then disposed of as waste or sent for further use.
  • the freed from solids filtrate 42 then also flows into the feed tank 6.
  • a continuous flow through the sedimentation without recycling of the retentate (feed and bleed) can be selected.
  • the volume of the sedimentation tank 20 corresponds approximately to the volume of the receiver 6, so that after completion of sedimentation and deposition of the filter cake, the receiver tank 6 with permeate, i. filled with solids-free pickling solution is filled.
  • cleaning of the membrane is required to prevent a decrease in permeate performance.
  • This cleaning is in for simplicity FIG. 1 not shown.
  • the cleaning can be done, for example, during sedimentation, wherein in the so-called CIP process [Cleaning in Place] first rinsed with water (neutral), then cleaned with acid and then rinsed again with water (neutral).
  • the composition of the pickling solution 2 in the pickling bath 1 can be continuously adjusted or maintained at a desired value.
  • a comparatively small amount of analysis 46 is withdrawn from the reservoir 6 and fed to the analysis 10 via a feed pump 44. About this can then the permeate in the reservoir 6, ie the proportion of aluminum, caustic soda and additives are determined.
  • the analysis 10 is designed to be able to detect the individual components with sufficient accuracy. In this way, the actual composition of the permeate in the reservoir 6 is determined.
  • sodium hydroxide solution and additives are metered into the feed container 6 via the metering unit 8, so that a predetermined desired permeate composition is established.
  • Permeate is then withdrawn from the feed tank 6 with the preset permeate target composition via the feed pump 44 and the corresponding reversed feed valve arrangement 48.
  • This template volume flow 50 is then returned to the pickling bath 1, so that the pickling solution 2 is brought to the desired desired composition and any losses due to removal, evaporation etc. are compensated.
  • the solids content of the streams 24, 34 and 42 is substantially at the same low level near 0%.
  • the pickling unit is switched back to the mode described above under 1. to fill the feed tank 6 with permeate / aluminate.
  • the additives metered in via the dosing unit 8 can also be adapted to the individual substance separation steps described above, so that, for example, optimized filtration or sedimentation is made possible.
  • the temperature in the reservoir 6 is lower than the temperature of the pickling bath 1.
  • the pickling bath 1 for example, be operated at a temperature of 70 ° C - the temperature in the reservoir 6 may then be for example about 40 ° C.
  • the filter 18 and also in the sedimentation tank 20 is the comparatively high temperature (70 ° C), so that a higher flow through the filter 18 can be realized due to this comparatively high temperature.
  • the sedimentation tank 20 may be provided with a cooling 21 to cool the retentate 26 to aid in the precipitation of heavy metals.
  • an unused volume fraction of permeate (consisting essentially of sodium aluminates) 52 withdrawn and fed to an industrial utilization become.
  • Such sodium aluminate solutions are used for example for drinking water treatment, wastewater treatment or as a raw material for zeolite production.
  • the withdrawal also takes place in order to prevent an excessive increase in the Al content in the bath and to keep the Al concentration within a defined target range.
  • the concentration of pickling solution 2 in pickling bath 1 can be kept at a defined composition by means of the method described above, the resulting solids being separated off continuously or quasi-continuously. Due to this minimum solids content in the pickling solution 2 and the avoidance of temperature and concentration fluctuations in the pickling solution 2, the risk of stone formation or the formation of sludge in the reservoir 6 or in the pickling bath 1 is practically nonexistent. Since no sludge accumulates during operation, expensive cleaning work and the concomitant shutdown of the system can be omitted.
  • the process described above also opens up the possibility of recovering caustic soda from the pickling or permeate solution and reuse in the pickling process.
  • the permeate 24, the clear phase 34 and the filtrate 42 are introduced together into the reservoir 6.
  • the metered addition to the adjustment of the original concentration also takes place in this storage tank 6.
  • FIG. 2 an embodiment of a system according to the invention is shown, in which the storage container 6 is designed in two parts with a permeate 54 and a dosing 56. These two containers 54, 56 are connected to each other via a feed pump 58 and a feed line 60, so that the dosing 56 is filled via the feed pump 58 and the feed line 60 from the permeate 54 can be.
  • the setting of the permeate target composition is carried out by metering in caustic soda and / or other suitable additives, such as complexing agents, inhibitors, precipitants for heavy metals, optionally from additive containers 62, 64, 66, 68 via a Dosierventilan Aunt 70 and a metering 72nd be supplied.
  • suitable additives such as complexing agents, inhibitors, precipitants for heavy metals
  • additive containers 62, 64, 66, 68 optionally from additive containers 62, 64, 66, 68 via a Dosierventilan Aunt 70 and a metering 72nd be supplied.
  • the metering from the additive containers 62, 64, 66 and 68 can also take place via individual metering pumps and metering lines, so that the additive containers are each connected to the metering container 56 via their own line and metering pump. This eliminates the metering valve assembly 70th
  • FIG. 2 illustrated variant has the advantage that the filling of the permeate tank 54 and the metered addition of the original volume flow 50 from the metering 56 into the pickling bath 1 for setting the desired Beizatesszusammen applicant can be done in parallel, while in the embodiment described above, the filling and metering takes place in sections.
  • aluminate should be removed to avoid precipitation. In the illustrated embodiment, this is done via the feed valve assembly 48, deducted over the concentrated permeate / aluminate 52 from the dosing 56 and a collecting 74 is supplied - so that the aluminate concentration in the dosing 56 and / or in the pickling solution 2 is lowered.
  • the aluminate solution received in the collecting container 74 can be circulated via a circulating pump 76 and a circulating line 78.
  • a trigger valve assembly 80 aluminate can be withdrawn from the sump 74 and fed to a recycling.
  • a special feature of this variant of the method is that the concentration of the aluminate / permeate received in the dosing container can be detected via the analytics 10 and a targeted target concentration can be adjusted by suitable control of the dosing valve arrangement 70, which then - for example not with regard to the pickling process - is optimized for reuse.
  • the aluminate concentration can be deliberately adjusted to a concentration by addition of sodium hydroxide solution and additives, for example complexing agents, which ensures optimal reuse with a stabilized solution and thus is also of interest to the company which is decreasing the aluminate.
  • FIG. 2 contains yet a further embodiment of the method according to the invention or the system according to the invention.
  • pickling solution 2 is fed to the solids separation 4 and the resulting low-solids fraction (solids content almost 0%) is then fed to the one- or two-part feed tank 6, in which the desired concentration is set and from which the permeate feed is then fed to the pickling solution 2 becomes.
  • FIG. 2 shows a variant, of course, in the system diagram according to FIG. 1 is applicable and in which a solution from another upstream or downstream process stage, such as an EO stain 82 or a first sink (see above-mentioned prior art) via a feed pump 84, a Zuzhouventilan Aunt 86 and a supply line 88 downstream of the valve assembly 14th the material flow is supplied.
  • the original volume flow 50 not only consists essentially of a subset of the pickling bath 1 but can partially or completely - depending on the setting of the valve assemblies 14 and 86 and the other process step, for example, the EO pickling 82 are removed.
  • the pickling bath 1 directly from the EO pickling 82 via the feed valve arrangement 86.
  • Such a feed is in the plant scheme according to FIG. 2 indicated with the direct feed line 90.
  • the two valve assemblies 14, 86 also to a single valve assembly be summarized.
  • the supply line 88 may also open before or after one of the individual solid separation steps.
  • a heavy metal precipitation takes place within the pickling bath 1.
  • this precipitation can also take place outside the pickling bath 1.
  • the heavy metal precipitation in the sedimentation tank 20 (thickener), in which case the required amount of precipitant / sodium sulfide is first determined via process analysis 10 and then metered in from containers 92, 94. As a result, an overdose of sodium sulfide can be excluded.
  • the additive container containing the precipitant for example the additive container 66
  • the additive container containing the precipitant will then be connected to the sedimentation container 20 via the metering valve arrangement 70.
  • the permeate 24 can - as in FIG. 2 indicated - even with the bypass of the analysis 10 via a line 96 and a valve assembly 98 directly into the storage container 6 ( FIG. 1 ) or the permeate container 54 (FIG. FIG. 2 ).
  • a method for treating workpieces of aluminum or aluminum alloys and a system that can be operated by such a method.
  • a partial amount of a solution is withdrawn from a bath for the treatment of the workpieces, freed from solids and fed back to the bath at a predetermined concentration and a predetermined volume flow.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (15)

  1. Procédé de décapage pour des pièces en aluminium ou en alliages d'aluminium, qui sont amenées en vue d'un décapage à un bain de décapage (1) muni d'une solution alcaline de décapage (2), avec les étapes :
    - retrait continu ou par parties d'une quantité partielle (3) de la solution de décapage (2) du bain de décapage (1) ;
    - séparation de métaux lourds de la quantité partielle (3), un perméat (24) étant conduit à un récipient amont (6) ;
    - analyse du perméat (24 ; 46) pauvre en métaux lourds reçu dans le récipient amont (6) et de la composition réelle de la solution de décapage (2) du bain de décapage(1) ;
    - amenée de la solution de décapage (2) et d'additifs afin de régler une composition de consigne de perméat en fonction de la composition réelle de la solution de décapage (2) et de la composition du perméat (24) stocké temporairement dans le récipient amont (6) ; et
    - retour d'un modèle de perméat (50), présentant une composition définie, du récipient amont (6) jusque dans le bain de décapage (1) afin de régler une composition de consigne de la solution de décapage (2).
  2. Procédé de décapage selon la revendication 1, dans lequel la séparation de métaux lourds (4) contient une filtration (18) et une sédimentation consécutive dans un récipient de sédimentation (20).
  3. Procédé de décapage selon la revendication 1 ou 2, dans lequel une phase claire (34) résultant de la sédimentation dans le récipient de sédimentation (20) est amenée au récipient amont (6).
  4. Procédé de décapage selon la revendication 3, dans lequel le rétentat (26) résultant de la filtration est amené au récipient de sédimentation (20) et, à partir de celui-ci et dans le cycle, au filtre (18) et est ajouté à la quantité partielle (3).
  5. Procédé de décapage selon la revendication 3 ou 4, dans lequel une phase trouble (36), résultant de la sédimentation dans le récipient de sédimentation (20) et présentant une teneur élevée en métaux lourds, est retirée et amenée à un séparateur de métaux lourds, un filtre statique (38).
  6. Procédé de décapage selon la revendication 3, 4 ou 5, dans lequel le filtrat (42) est amené au récipient amont (6) et le gâteau de filtration (40) est amené à une élimination ou à un recyclage.
  7. Procédé de décapage selon l'une quelconque des revendications précédentes, dans lequel, en fonction de l'analyse, de la soude caustique est amenée au perméat (24, 34, 42) reçu dans le récipient amont (6) afin de régler la composition de perméat de consigne.
  8. Procédé de décapage selon la revendication 7, dans lequel, avant l'analyse d'une composition réelle de solution de décapage, des métaux lourds sont séparés de la solution de décapage (2).
  9. Procédé de décapage selon l'une quelconque des revendications précédentes, dans lequel une partie du perméat est retirée et conduite à un récipient collecteur (74).
  10. Procédé de décapage selon l'une quelconque des revendications précédentes, dans lequel celui-ci est mis en oeuvre dans un système fermé.
  11. Procédé de décapage selon l'une quelconque des revendications 2 à 10, dans lequel la filtration (18) contient une microfiltration ou une ultrafiltration.
  12. Installation de décapage destinée à la mise en oeuvre du procédé de décapage selon l'une quelconque des revendications précédentes, avec un bain de décapage (1), avec une évacuation destinée à évacuer une quantité partielle (3) d'une solution de décapage (2) du bain de décapage (1), avec une séparation de métaux lourds (4), avec un récipient amont (6), avec une unité d'analyse (10) destinée à analyser la composition du perméat reçu dans le récipient amont (6) et la composition réelle de la solution de décapage (2), avec une unité de dosage (8) destinée à amener des additifs/agents de décapage en fonction du résultat de l'analyse et avec un retour d'un flux volumique amont (50) dans le bain de décapage (1).
  13. Installation de décapage selon la revendication 12, dans laquelle la séparation de métaux lourds (4) a un filtre dynamique (18) et un récipient de sédimentation (20).
  14. Installation de décapage selon la revendication 13 avec une pompe de circulation (28) destinée au retour du rétentat du récipient de sédimentation (20) à l'entrée de filtre et/ou avec une pompe de transport (37) destinée à transporter une phase claire (34) hors du récipient de sédimentation (20) jusque dans le récipient amont (6).
  15. Installation de décapage selon l'une quelconque des revendications 12 à 14, avec un filtre (38) destiné à filtrer la phase trouble (36) résultant dans le récipient de sédimentation (20) et avec une conduite destinée à amener un filtrat (42), débarrassé de métaux lourds, au récipient amont (6).
EP09796936.4A 2008-11-03 2009-11-03 Procédé et installation de décapage Not-in-force EP2352859B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102008055668 2008-11-03
DE102008063729A DE102008063729A1 (de) 2008-11-03 2008-12-18 Beizverfahren und Beizanlage
DE200810062970 DE102008062970A1 (de) 2008-12-23 2008-12-23 Beizverfahren und Beizanlage
PCT/DE2009/001552 WO2010060408A2 (fr) 2008-11-03 2009-11-03 Procédé et installation de décapage

Publications (2)

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EP2352859A2 EP2352859A2 (fr) 2011-08-10
EP2352859B1 true EP2352859B1 (fr) 2018-06-27

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DE (1) DE112009003274A5 (fr)
WO (1) WO2010060408A2 (fr)

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Publication number Priority date Publication date Assignee Title
DE102012215679A1 (de) * 2012-09-04 2014-05-15 Henkel Ag & Co. Kgaa Verfahren zur korrosionsschützenden Oberflächenbehandlung von metallischen Bauteilen in Serie
DE102013108375A1 (de) 2013-01-31 2014-07-31 Thomas König Verfahren zum Aufbereiten eines Beiz- und/oder Eloxalbades und Eloxieranordnung
WO2019122979A1 (fr) * 2017-12-21 2019-06-27 Arcelormittal Procédé pour le décapage de tôles d'acier

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WO2001094510A1 (fr) * 2000-06-06 2001-12-13 Church & Dwight Company, Inc. Compositions de nettoyage recyclables

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WO2001094510A1 (fr) * 2000-06-06 2001-12-13 Church & Dwight Company, Inc. Compositions de nettoyage recyclables

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WO2010060408A4 (fr) 2010-11-25
WO2010060408A3 (fr) 2010-10-07
WO2010060408A2 (fr) 2010-06-03
DE112009003274A5 (de) 2012-09-20
EP2352859A2 (fr) 2011-08-10

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