WO2004076719A1 - Procede de phosphatation avec remise en circulation de matiere reutilisable - Google Patents

Procede de phosphatation avec remise en circulation de matiere reutilisable Download PDF

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Publication number
WO2004076719A1
WO2004076719A1 PCT/EP2004/001570 EP2004001570W WO2004076719A1 WO 2004076719 A1 WO2004076719 A1 WO 2004076719A1 EP 2004001570 W EP2004001570 W EP 2004001570W WO 2004076719 A1 WO2004076719 A1 WO 2004076719A1
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WO
WIPO (PCT)
Prior art keywords
ions
range
phosphating
regenerate
concentration
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Application number
PCT/EP2004/001570
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German (de)
English (en)
Inventor
Jan-Willem Brouwer
Peter Kuhm
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP04712493A priority Critical patent/EP1597412A1/fr
Publication of WO2004076719A1 publication Critical patent/WO2004076719A1/fr

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Classifications

    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/86—Regeneration of coating baths

Definitions

  • the invention is in the field of phosphating metal surfaces, as is carried out as a widespread corrosion protection measure in the metalworking industry such as, for example, the automotive industry and the household appliance industry, but also in part in steelworks. It relates to a method for treating the overflow of the phosphating baths and / or the rinsing water after the phosphating. The process enables the reuse of active ingredients for the preparation of supplementary solutions for phosphating baths.
  • the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers that already improve corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a significant increase in adhesion and resistance to infiltration when exposed to corrosion.
  • Such phosphating processes have long been known in the prior art.
  • the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions have comparatively low zinc ion contents of e.g. B. 0.5 to 2 g / l.
  • phosphate layers with significantly improved corrosion protection and paint adhesion properties can be formed.
  • z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions as a so-called trication process for the preparation of metal surfaces for painting, for example for the cathodic electrodeposition of car bodies, wide application.
  • a phosphating solution contains layer-forming components such as zinc and possibly other divalent metal ions as well as phosphate ions.
  • a phosphating solution contains non-layer-forming components such as alkali metal ions Dulling the free acid and especially accelerators and their degradation products.
  • the degradation products of the accelerator result from the fact that it reacts with the hydrogen formed on the metal surface by the pickling reaction.
  • the non-layer-forming components, such as alkali metal ions which accumulate over time in the phosphating bath, and in particular the degradation products of the accelerator, can only be removed from the phosphating solution by discharging and discarding part of the phosphating solution and replacing it continuously or discontinuously with new phosphating solution.
  • Phosphating solution can be discharged, for example, by operating the phosphating bath with an overflow and discarding the overflow. As a rule, however, an overflow is not necessary since the phosphated metal parts discharge a sufficient amount of phosphating solution as an adhering liquid film.
  • the phosphating solution adhering to the phosphated parts, such as automobile bodies, is rinsed off with water. Since the phosphating solution contains heavy metals and possibly other ingredients that must not be released into the environment in an uncontrolled manner, the rinsing water must be subjected to a water treatment. This must be done in a separate step before being discharged into a biological sewage treatment plant, as otherwise the functioning of the sewage treatment plant would be endangered.
  • WO 00/64817 describes a process for the treatment of phosphating bath overflow and / or rinsing water after phosphating, the phosphating being carried out with an acidic aqueous phosphating solution which contains 3 to 50 g / l phosphate ions, calculated as PO 4 3 " , 0.2 contains up to 3 g / l zinc ions, optionally further metal ions and optionally accelerators, the phosphating bath overflow and / or the rinsing water after the phosphating being passed after a membrane filtration or without an upstream membrane filtration over a weakly acidic ion exchanger.
  • the process described above can be improved by using a weakly acidic ion exchanger for treating the rinsing water after a nickel-containing phosphating, the acid groups of which are not more than 15% neutralized with alkali metal ions, and that the nickel-containing aqueous solution in the Tasks on the ion exchanger has a pH in the range of 2.5 to 6.0.
  • nickel ions are compared to zinc and manganese ions are preferably bound to the weakly acidic ion exchanger and can be recovered as a nickel-containing regenerate when it is regenerated.
  • this object is achieved by a process for the treatment of phosphating bath overflow and / or rinsing water after phosphating, the phosphating being carried out with an acidic aqueous phosphating solution which contains 3 to 50 g / l phosphate ions, calculated as PO 4 3 " , Contains 0.2 to 3 g / l zinc ions, 0.01 to 2.5 g / l nickel ions, optionally further metal ions and optionally accelerators, the phosphating bath overflow and / or the rinsing water after the phosphating being passed over a weakly acidic cation exchanger, thereby characterized in that a) the loaded cation exchanger is regenerated with phosphoric acid, nitric acid or a mixture of these acids and the acid regenerate obtained is collected, which contains nickel ions and which can contain zinc ions, manganese ions and phosphate ions and which has a ratio of total acid to free acid resulting from the regeneration conditions and a
  • step b) first determines which target ranges must be observed for selected parameters so that the regenerate can be processed at all in the sense of the present invention. In principle, this step only has to be carried out once at the beginning of the procedure according to the invention. In the course of the process, however, it may be advisable to check the target ranges and, if necessary, to adapt them to changed system conditions or procedures.
  • sub-step c) an analysis is carried out to determine whether the selected parameter or parameters in the regenerate collected are within these target ranges. If this is not the case, the regrind is not suitable for the procedure according to the invention and is therefore disposed of in step d) or sent to another treatment. However, if the values for the selected parameter or parameters in the regenerate collected in each case are in the target range, the regenerate can be set to predetermined second target values for the parameter or parameters in sub-step e) by adding one or more additional chemicals. In this way, a first supplementary solution is obtained in the form of the supplemented regrind, which has a predetermined composition. This predetermined composition does not have to be the ideal composition in order to completely supplement the phosphating solution with regard to all characteristic bath characteristics.
  • a first supplementary solution with a predetermined composition is produced in sub-step e) in a process-technically simple and harmless manner.
  • the regenerate supplemented in this way is added in sub-step f) together with at least one further supplementary solution with a predetermined composition of the phosphating solution.
  • This second supplementary solution has such a composition that, together with the regenerate added in sub-step e), it supplements the phosphating solution with regard to all relevant bath parameters.
  • the regenerate of the ion exchanger does not have to be transported to a processing point. Rather, it can be supplemented in a simple and harmless manner at the point of its creation, such as, for example, a phosphating system in the automotive industry, so that it is suitable, together with at least one additional supplementary solution, to supplement the active substance content of the phosphating solution.
  • a phosphating system in the automotive industry
  • at least one additional supplementary solution to supplement the active substance content of the phosphating solution.
  • the replenished regrind and the at least one additional replenishment solution are added to the phosphating solution together or in any order in step f).
  • the procedure according to the invention has the advantage that smaller amounts of liquid have to be adjusted. This leads to higher accuracy.
  • the one or more supplementary chemicals are preferably selected for the sub-step e) from compounds which, when mixed with the acidic regenerate collected in the sub-step a), do not lead to the formation of reaction products which are gaseous under normal conditions, such as, for example, carbon dioxide.
  • Layer-forming metal ions for the supplementary chemicals are preferably used in the form of their phosphates, since this does not introduce any potentially disruptive anions into the phosphating solution. Nitrates of the layer-forming metal ions would also be suitable to supplement nitrate-containing phosphating solutions.
  • the supplementary chemicals added to the recovered regenerate in sub-step e are preferably in the form of aqueous solutions. These are easier and less dangerous to dose than solids.
  • This solution of the supplementary chemicals preferably also contains substances which act as accelerators in the phosphating. Operation and examples of such accelerators are described below.
  • Hydroxylamine is particularly suitable for being added to the solution of the supplementary chemicals and thus to the supplemented regrind.
  • the supplemented regrind also contains, at least in part, an accelerator for the phosphating.
  • hydroxylamine acts as an alkali, which can be used as a supplementary chemical for setting the predetermined second setpoint for the ratio between total acid and free acid. If hydroxylamine is used as the alkali, then besides the desired effect of changing the ratio between total acid and free acid, there is the additional benefit that this alkali also acts as an accelerator for the phosphating. This reduces the overall chemical consumption.
  • the at least one predetermined second target value for the supplemented regenerate in sub-step e) and the predetermined composition of the at least one further one Supplementary solution in sub-step f) is preferably selected so that the volume ratio between the supplemented regenerate added to the phosphating solution in sub-step f) and the further supplementary solution (s) is in the range from 1: 4 to 1: 1. This leads to total volumes that are easy to handle.
  • the predetermined second setpoints for the supplemented regrind in sub-step e) can then be selected such that they can be adjusted by adding supplementary chemicals in the form of aqueous solutions without dangerous chemical reactions. The process according to the invention is particularly reliable under these conditions.
  • the production of the supplemented regrind in sub-step e) is preferably carried out with the aid of a computer. This can be done manually, semi-automatically or fully automatically.
  • the current values of the one or more parameters in the regenerate collected can be determined manually and entered into a computer. Alternatively, they are automatically determined by the program and stored in a computer.
  • the quantities of supplementary chemicals that have to be added in sub-step e) are then automatically derived in a computer from electronically stored correlations or algorithms. For example, a suitable Excel spreadsheet or a similar spreadsheet program can be used.
  • the quantities of supplemental chemicals determined in this way are then added to the collected regenerate either automatically or manually. Automatic addition is preferable because it requires less human labor.
  • a preferred embodiment of the method according to the invention is that
  • step c) the current values of the one or more parameters in the collected regenerate are determined manually and entered into a computer or automatically determined under program control and stored in a computer,
  • the amounts of supplementary chemicals that have to be added in sub-step e) in order to achieve the at least one second setpoint for at least one parameter selected from the ratio between total acid and free acid, the concentrations of nickel ions, zinc ions, manganese ions and phosphate ions in the supplemented regrind and the Adjust density, are automatically derived in a computer from electronically stored correlations or algorithms and
  • the first target ranges are preferably selected from in sub-step b) Ratio between total acid and free acid in the range from 2.0 to 4.5,
  • the predetermined second target values for the supplemented regenerate in sub-step e) are preferably selected from
  • the predetermined composition of the at least one further supplementary solution added to the phosphating solution in sub-step f) preferably comprises
  • the value of the free acid is determined by diluting 1 g of the sample solution with 100 ml of completely deionized water and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption is given in ml of sodium hydroxide solution per g of sample solution.
  • the free acid content is determined analogously by diluting 1 g of sample solution with 100 ml of fully deionized water and titrating with 0.1 N sodium hydroxide solution to a pH of 8.5.
  • the method according to the invention can be carried out at the point at which the regenerate is formed. It can therefore be carried out in a location that is not separated from the location of the phosphating solution by publicly accessible areas such as streets.
  • the phosphating itself and the processing method according to the invention therefore preferably take place within the same factory premises.
  • the country-specific legal regulations for the transport of waste and / or hazardous substances on public roads remain irrelevant.
  • the zinc contents are preferably in the range from 0.4 to 2 g / l and in particular from 0.5 to 1.5 g / l, as are customary for low-zinc processes.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
  • the phosphating bath can contain other components which are currently customary in phosphating baths.
  • 0.1 to 4 g / l, in particular 0.5 to 1.5 g / l, of manganese ions can also be present.
  • the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly advisable to use oxides and / or carbonates as the cation source. Because of the risk of salting up the phosphating baths, salts of acids other than phosphoric acid should preferably be avoided.
  • phosphating baths In addition to the layer-forming divalent cations, phosphating baths generally also contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • Phosphating baths that are used exclusively for the treatment of galvanized material do not necessarily have to contain a so-called accelerator.
  • accelerators which are required for the phosphating of non-galvanized steel surfaces, are also often used in technology for the phosphating of galvanized material.
  • Accelerating phosphating solutions have the additional advantage that they are suitable for both galvanized and non-galvanized materials. This is particularly important when phosphating car bodies, as these often contain both galvanized and non-galvanized surfaces.
  • accelerators are available for phosphating baths. They accelerate the formation of layers and facilitate the formation of closed phosphate layers, since they react with the hydrogen generated during the pickling reaction. This process is referred to as "depolarization". This prevents the formation of hydrogen bubbles on the metal surface which interfere with the layer formation.
  • accelerators which form either water or monovalently charged ions as by-products or degradation products. For example, the
  • Phosphating solution contain one or more of the following accelerators:

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

La présente invention concerne un procédé pour préparer un déversoir de bain de phosphatation et/ou d'eau de rinçage après phosphatation. Ce procédé consiste à retirer de l'eau usée des cations formant des couches, notamment des ions nickel, au moyen d'un échangeur d'ions. Lors de la régénération de l'échangeur d'ions, les cations sont récupérés dans un produit régénéré acide aqueux. Une analyse est conduite afin de vérifier si la composition de produit régénéré est telle qu'il est possible d'obtenir facilement une première solution complémentaire pour le bain de phosphatation par ajout de produits chimiques complémentaires. Si tel est le cas, on ajoute une quantité adéquate de produits chimiques complémentaires, afin de produire cette première solution complémentaire. Celle-ci est ensuite ajoutée à la solution de phosphatation avec une seconde solution complémentaire. Les produits chimiques complémentaires et la composition cible de la première solution complémentaire sont choisis de façon que cette première solution complémentaire puisse être produite de manière simple dans le cadre de l'installation de phosphatation.
PCT/EP2004/001570 2003-02-27 2004-02-19 Procede de phosphatation avec remise en circulation de matiere reutilisable WO2004076719A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04712493A EP1597412A1 (fr) 2003-02-27 2004-02-19 Procede de phosphatation avec remise en circulation de matiere reutilisable

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003108426 DE10308426B4 (de) 2003-02-27 2003-02-27 Verfahren zur Aufbereitung von Phosphatierbadüberlauf und/oder von Spülwasser nach der Phosphatierung
DE10308426.6 2003-02-27

Publications (1)

Publication Number Publication Date
WO2004076719A1 true WO2004076719A1 (fr) 2004-09-10

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PCT/EP2004/001570 WO2004076719A1 (fr) 2003-02-27 2004-02-19 Procede de phosphatation avec remise en circulation de matiere reutilisable

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EP (1) EP1597412A1 (fr)
DE (1) DE10308426B4 (fr)
WO (1) WO2004076719A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4226080A1 (de) * 1992-08-06 1994-02-10 Henkel Kgaa Aufbereitung wäßriger Spüllösungen aus Zinkphosphatierungsprozessen
WO2000064817A1 (fr) * 1999-04-26 2000-11-02 Henkel Kommanditgesellschaft Auf Aktien Traitement d'eaux usees lors de la phosphatation
WO2002040405A2 (fr) * 2000-11-15 2002-05-23 Henkel Kommanditgesellschaft Auf Aktien Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation
WO2002043863A2 (fr) * 2000-11-15 2002-06-06 Henkel Kommanditgesellschaft Auf Aktien Regeneration fractionnee d'un echangeur d'ions faiblement acide, charge d'ions metalliques bivalents

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3138503A1 (de) * 1981-09-28 1983-04-07 SEP Gesellschaft für technische Studien, Entwicklung, Planung mbH, 8000 München Verfahren zum kontinuierlichen regenerieren von chromatierungen fuer zink-, kadmium- und aehnliche metallbeschichtungen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4226080A1 (de) * 1992-08-06 1994-02-10 Henkel Kgaa Aufbereitung wäßriger Spüllösungen aus Zinkphosphatierungsprozessen
WO2000064817A1 (fr) * 1999-04-26 2000-11-02 Henkel Kommanditgesellschaft Auf Aktien Traitement d'eaux usees lors de la phosphatation
WO2002040405A2 (fr) * 2000-11-15 2002-05-23 Henkel Kommanditgesellschaft Auf Aktien Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation
WO2002043863A2 (fr) * 2000-11-15 2002-06-06 Henkel Kommanditgesellschaft Auf Aktien Regeneration fractionnee d'un echangeur d'ions faiblement acide, charge d'ions metalliques bivalents

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Publication number Publication date
DE10308426A1 (de) 2004-09-16
EP1597412A1 (fr) 2005-11-23
DE10308426B4 (de) 2005-03-03

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