EP2674507A2 - Installation de préparation en continu de fondants contenant du fer - Google Patents

Installation de préparation en continu de fondants contenant du fer Download PDF

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Publication number
EP2674507A2
EP2674507A2 EP13003045.5A EP13003045A EP2674507A2 EP 2674507 A2 EP2674507 A2 EP 2674507A2 EP 13003045 A EP13003045 A EP 13003045A EP 2674507 A2 EP2674507 A2 EP 2674507A2
Authority
EP
European Patent Office
Prior art keywords
iron
flux
iii
hydroxide
oxidizing agent
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Withdrawn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
EP13003045.5A
Other languages
German (de)
English (en)
Other versions
EP2674507A3 (fr
Inventor
Frank Schmelz
Dirk Schmelz
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.)
RAM Engineering and Anlagenbau GmbH
Original Assignee
RAM Engineering and Anlagenbau GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by RAM Engineering and Anlagenbau GmbH filed Critical RAM Engineering and Anlagenbau GmbH
Publication of EP2674507A2 publication Critical patent/EP2674507A2/fr
Publication of EP2674507A3 publication Critical patent/EP2674507A3/fr
Withdrawn legal-status Critical Current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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/30—Fluxes or coverings on molten baths

Definitions

  • the invention relates to a system for the continuous preparation of iron containing and used for the treatment of ferrous metal surfaces before galvanizing flux by adding an oxidizing agent, in particular hydrogen peroxide, for the conversion of iron (II) chloride in iron (III) hydroxide, and optionally by adding at least one other chemical substance.
  • an oxidizing agent in particular hydrogen peroxide
  • the workpieces to be galvanized are pretreated in several process stages before hot-dip galvanizing.
  • a degreasing step is provided to remove organic contaminants. This is followed by a pickling step for the acidic removal of oxidic impurities.
  • the workpieces then pass through a pre-treatment stage in a fluxing basin containing a flux or flux. The purpose of this bath is to protect the workpieces against corrosion on their way to the zinc bath and drying.
  • Flux solutions are aqueous salt solutions having a salt content of, for example, 300 to 500 g / l.
  • Main constituents of these salts are zinc chloride and ammonium chloride.
  • various alkali and alkaline earth metal chlorides for example KCl, NaCl, MgCl 2 , CaCl 2 ) may be present to a limited extent.
  • the flux salt is applied to the galvanizing material by immersing the workpiece in the flux solution. Even during drying, a certain pickling effect occurs due to the formation of hydroxycinic acids.
  • the dried up river salt is melted. The melting point of the river salts is well below the temperature of the zinc bath (about 450 ° C), so that the river salts can quickly develop their pickling effect.
  • the pickling effect is based on the release of hydrochloric acid, which preferably forms in the temperature range from 250 to 320 ° C of ammonium chloride. The hydrochloric acid then causes the dissolution of oxidic impurities.
  • iron During operation, iron accumulates in the flux solution, which originates from the pickling baths.
  • the pickling iron accumulates in the form of FeCl 2 , wherein the iron contents may be of the order of 100 to 160 g / l.
  • alloying constituents of the steel grades used are also brought into solution during pickling.
  • hydrochloric acid is contained in the flux bath, whereby iron and alloying elements are dissolved in small quantities from the galvanizing.
  • Iron which is introduced into the galvanizing vessel during the hot-dip galvanizing of the workpieces with the fluxing agent, reacts with elemental zinc and forms hard zinc, namely iron-zinc mixed crystals, with hard zinc precipitating in the zinc kettle as fuel.
  • hard zinc namely iron-zinc mixed crystals
  • At high iron concentrations in addition to zinc losses, there is an impairment of the quality of galvanizing.
  • the resulting Eisenhydroxidschlamm can be deposited normally.
  • the flux salt composition contains zinc chloride, alkali metal chloride, and at least one or more alkalizing ingredients and at least one or more aqueous solution (II) to ferric oxidizing components.
  • zinc oxide, alkali metal hydroxide or a metal carbonate can be used as the alkalizing component.
  • an oxidizing component in particular potassium permanganate is used.
  • the necessary for the preparation of the flux pH adjustment of the flux, the precipitation of ferric hydroxide and the setting of a certain zinc chloride / ammonium chloride ratio are thus carried out by adding the flux salt composition in one process step.
  • De-icing is carried out according to the following reaction (2): 3 FeCl 2 + KMnO 4 + 7H 2 O ⁇ 3 Fe (OH) 3 + MnO 2 + KCl + 5HCL (2)
  • the resulting hydrochloric acid is neutralized by the alkalizing component of the fluxing salt composition.
  • the known from the prior art methods for the preparation of flux solutions by deposition of iron usually require a high procedural complexity and are costly.
  • the consumption of the Oxidationsmittcls added to the flux for processing and other added in connection with the preparation of other chemical substances contributes to the high cost of treatment.
  • the object of the present invention is to provide a simple process for the treatment of iron containing flux by adding an oxidizing agent, which is characterized by low cost of treatment and makes a substantially neuric flux according to the principle of circulation from a Altmannstoff available.
  • the system according to the invention comprises at least one connectable to a Flußstoffbecken sedimentation tank for precipitating iron (III) hydroxide, at least one associated with the sedimentation filter device for settling or deposition of formed iron (III) hydroxide, at least at least one measuring device for continuous or discontinuous measurement of the iron (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux and a control device for controlling the addition of the oxidizing agent to the oxidizing agent containing and connected to the Sedimentations employcr Fluxing in dependence on the measured Eisenkonzcntration, wherein the measuring and control device is designed such that an oxidant addition preferably automatically upon reaching a predetermined upper limit of iron (II) chlori dconcentration and / or the iron (III) hydroxide concentration in the flux and only until the iron (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux reaches or falls below a lower limit. If the iron concentration in the
  • an internal and continuous Flussertonlaufweg is proposed in which the addition of the oxidizing agent and, preferably, optionally further required for the flux preparation added substances, not continuously, ie continuously, but only when the iron (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux has reached a predetermined limit.
  • This limit can be between 8 and 20 g iron / l, preferably between 10 and 15 g iron / l.
  • the lower limit value can be set to a value of less than 8 g iron / l, preferably less than 5 g iron / l.
  • the flux according to the invention does not have to be treated in an external treatment plant, but on site, in particular by continuous circulation between the system of the invention and the fluxing tank of the galvanizing, it is not necessary to replace the flux for reprocessing or to transport to an external treatment plant. This contributes to low treatment costs.
  • the inventive system corresponding means or means for measuring and / or preferably automatic adjustment of the zinc chloride / alkali metal chloride ratio and preferably automatic addition of zinc chloride and / or of A1-kalimetallchlorid, in particular of ammonium chloride.
  • the addition of zinc chloride and alkali metal chloride may be provided in the ratio of, for example, 60:40.
  • the sedimentation tank can have internal fins or an internal finned clarifier to increase the filtration area and reduce the sinking rate. As a result, a significant improvement in the precipitation of the formed iron (III) hydroxide is achieved.
  • the settling surface of the sedimentation container is preferably more than 6 m 2 , more preferably more than 8 m 2 , in particular more than 10 m 2 .
  • the rate of descent of the iron (III) hydroxide flakes in the sedimentation vessel can be reduced to less than 1 m / h, preferably less than 0.8 m / h, in particular less than 0.5 m, by adjusting the process conditions and by dimensioning the sedimentation vessel. h, be set.
  • An intensive mixing of the oxidizing agent from the oxidizing agent and optionally further required for the flux preparation reactants with the flux from the fluxing tank can be done in a static mixer from which the mixture of oxidizing agent and flux is passed to the sedimentation.
  • a static mixer it comes to the formation of iron (III) hydroxide.
  • the use of a static mixer contributes to a simple structure and a simple process control in the operation of the system according to the invention.
  • the filter unit can be designed as a (chamber) filter press, so that it is possible to strongly dehydrate the filter cake formed in the filter press.
  • the dehydration is preferably carried out until an absolute moisture content of less than 40 Gcw .-%, preferably less than 35% by weight, in particular less than 30% by weight, in each case based on the weight of the water contained in the filter cake to the total weight of filter cake.
  • At least one pump for conveying the iron (III) hydroxide-containing sludge from the sedimentation tank into the filter unit, at least one pump, in particular a membrane pump, can be provided. It is understood that the sludge discharged from the sedimentation tank must have an appropriate pumpability. With the pump, a pressure level is preferably between 4 and 20 bar, in particular between 6 and 12 bar, constructed. This ensures a high separation efficiency of the ice (III) hydroxide flakes in the filter press.
  • the system according to the invention is particularly portable, so that a continuous flux preparation can be done directly on site at a galvanizing.
  • the system can be integrated into a transportable container. This simplifies the transport of the system according to the invention to various galvanizing plants.
  • FIGS. 1 and 2 schematically a plant 1 is shown, which is designed for the continuous treatment of a flux 2, the flux 2 for the deposition of iron, an oxidizing agent, preferably hydrogen peroxide, and an alkalizing, preferably ammonia, is added.
  • an oxidizing agent preferably hydrogen peroxide
  • an alkalizing preferably ammonia
  • ammonia is used to adjust the pH of the flux 2 preferably to a value between 3.5 and 4, while hydrogen peroxide precipitates the existing in the flux 2 divalent iron as iron (III) hydroxide.
  • the flux 2 comes from a flux tank, not shown, of a refrigerator, which is connected upstream of a galvanizing boiler.
  • the precipitation of iron from flux 2 reduces the formation of hard zinc in the galvanizing boiler during hot-dip galvanizing of a workpiece and ensures very good galvanizing quality. In addition, the zinc losses are kept low.
  • two sedimentation tanks 3, 4 are provided.
  • ammonia can be done directly on the flux tank by hand. During a first manual measurement, before commissioning, the pH value and redox value are determined at the fluxing pool. Thereafter, ammonia is added to the flux pool. This process is usually repeated every 14 days and is done by the galvanizer itself. It goes without saying that an automatic measurement and addition of ammonia can also be provided here.
  • the flux 2 is first sucked in via a suction line 6 from the flux basin.
  • the pump 5 sucks the flux 2 via a suction container 6a, which is provided for a height compensation and ensures that it does not come to a chuck sectionen idling.
  • the oxidizing agent is removed with a further pump 7 an oxidizer 8 and added to the flux 2 via a supply line 9, which opens into the suction line 6.
  • the oxidizing agent container 8 can be filled manually by means of an opening which can be closed with a cover 8a.
  • ammonia for pH adjustment is in the FIGS. 1 and 2 not shown.
  • a static mixer 10 there is an intensive mixing of the flux 2 with the oxidizing agent and the slight flocculation of iron (III) hydroxide.
  • the residence time in the static mixer 10 is between 0.01 to 0.5 m / sec., Preferably 0.02 m / sec., As it comes to a temperature increase of the flux 2 by the reaction.
  • a temperature measurement can be provided after the static mixer, which shuts off the addition of the oxidizing agent at temperature exceeding, that is at temperatures of more than 80 ° C, preferably from 85 to 90 ° C.
  • the pipes are cooled.
  • the flux 2 mixed with the oxidizing agent is transferred via discharge lines 11 into the sedimentation tanks 3, 4.
  • the second sedimentation tank 4 is preferably used only for larger amounts of flux to be processed.
  • the sedimentation container 3, 4 have internal Lamellensuber 12, 13, which are provided to increase the filtration area and to reduce the settling speed of the precipitated iron (III) hydroxide.
  • the low-iron processed flux 2 passes into a return line 14a and is fed back to the flux basin.
  • iron (III) hydroxide-containing sludge Via a suction line 15 iron (III) hydroxide-containing sludge is sucked from the bottom of the sedimentation 3, 4 with a diaphragm pump 16 and conveyed into a chamber filter press 17 at a pressure of 6 to 12 bar.
  • the chamber filter press 17 the formed iron (III) hydroxide flakes separated by filtration from the flux 2, wherein the water content of the filter cake formed is preferably reduced to less than 10 wt.%.
  • the filtrate drain line 18 is designed as a closed pipeline, with hoses leading from the membrane plates of the chamber filter press 17 into the pipeline so that an undesired escape of filtrate can not take place.
  • the filtrate is sucked in with a third pump 20 and conveyed via return lines 21 into the sedimentation sheets 3, 4.
  • the system 1 shown may comprise at least one measuring device 14b for the continuous or discontinuous measurement of the ice chloride (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux and also a regulating device (not shown) for controlling the addition of the oxidizing agent to the flux 2 depending on the measured concentrations.
  • the measuring device 14b and the control device are designed such that an oxidizing agent addition preferably takes place automatically when a predetermined upper limit of the iron (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux 2 and only until the iron (II) chloride concentration and / or the iron (III) hydroxide concentration in the flux 2 reaches or falls below a lower limit. If the upper limit is reached again by introducing iron, an additional oxidant can be added automatically or manually controlled. It is understood that the same can also apply to the addition of an alkalizing constituent.
  • the reduction of the ferrous chloride concentration in the return line 14a is measured via a redox measurement.
  • the metering pump 7 is switched on or off.
  • the system 1 can be arranged in a frame or container 23, so that cin transport and a change of location are possible in a simple manner.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
EP13003045.5A 2012-06-15 2013-06-14 Installation de préparation en continu de fondants contenant du fer Withdrawn EP2674507A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012011777 2012-06-15
DE102012013588A DE102012013588A1 (de) 2012-06-15 2012-07-10 Anlage zur koninuierlichen Aufbereitung von Eisen enthaltendem Flussmittel

Publications (2)

Publication Number Publication Date
EP2674507A2 true EP2674507A2 (fr) 2013-12-18
EP2674507A3 EP2674507A3 (fr) 2016-04-27

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EP13003045.5A Withdrawn EP2674507A3 (fr) 2012-06-15 2013-06-14 Installation de préparation en continu de fondants contenant du fer

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EP (1) EP2674507A3 (fr)
DE (1) DE102012013588A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4656762A1 (fr) * 2024-05-29 2025-12-03 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé et dispositif pour le traitement des compositions de bain dans les installations de galvanisation à chaud

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT17231U1 (de) * 2020-09-24 2021-09-15 Koerner Chemieanlagenbau Ges M B H Vorrichtung und Verfahren zur Aufbereitung des Fluxbades einer Feuerverzinkungsanlage

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH569796A5 (fr) * 1970-06-16 1975-11-28 Didier Werke Ag
FR2277910A1 (fr) * 1974-07-09 1976-02-06 Degremont Sa Procede pour l'elimination en continu des sels de fer polluant les bains de galvanisation
DE2805204C3 (de) * 1978-02-08 1980-10-02 Passavant-Werke Michelbacher Huette, 6209 Aarbergen Verfahren und Vorrichtung zum Filtrieren von Schlamm o.dgl. Filtergut in einer Filterpresse
FR2520007B1 (fr) * 1982-01-15 1990-11-02 Asturienne Mines Comp Royale Procede de regeneration en continu de bains de fluxage dans la galvanisation au trempe de pieces en acier
DE3814372A1 (de) * 1988-04-28 1989-11-09 Deca Chemie Gmbh Verfahren zum wirtschaftlichen betreiben einer heissmetallisierungsanlage
BE1006337A3 (fr) * 1992-11-06 1994-07-26 Mechim Engineering Sa Procede pour entretenir un bain de fluxage d'une ligne de galvanisation.
AT402075B (de) * 1995-08-17 1997-01-27 Koerner Chemieanlagen Verfahren und anlage zur aufbereitung von zur stahl-vorbehandlung eingesetztem flussmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4656762A1 (fr) * 2024-05-29 2025-12-03 Seppeler Holding und Verwaltungs GmbH & Co. KG Procédé et dispositif pour le traitement des compositions de bain dans les installations de galvanisation à chaud

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Publication number Publication date
EP2674507A3 (fr) 2016-04-27
DE102012013588A1 (de) 2013-12-19

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