EP1337471A2 - Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation - Google Patents

Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation

Info

Publication number
EP1337471A2
EP1337471A2 EP01996515A EP01996515A EP1337471A2 EP 1337471 A2 EP1337471 A2 EP 1337471A2 EP 01996515 A EP01996515 A EP 01996515A EP 01996515 A EP01996515 A EP 01996515A EP 1337471 A2 EP1337471 A2 EP 1337471A2
Authority
EP
European Patent Office
Prior art keywords
phosphating
ion exchanger
ions
nickel
solution
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Withdrawn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
EP01996515A
Other languages
German (de)
English (en)
Inventor
Klaus Lepa
Jens KRÖMER
Patrick Droniou
Jan-Willem Brouwer
Peter Kuhm
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1337471A2 publication Critical patent/EP1337471A2/fr
Withdrawn legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/07—Processes using organic exchangers in the weakly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange

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 with nickel-containing phosphating solutions. The method allows in preferred
  • Embodiments the return of bath ingredients in the phosphating bath, the reuse of active ingredients for the preparation of supplementary solutions for phosphating baths and the use of the solution depleted in metal ions as rinsing water.
  • the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves 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 / 1.
  • An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 12 and can take values up to 30.
  • 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 method for the preparation of metal surfaces for painting, for example for the cathodic electrocoating of car bodies, wide application.
  • a phosphating solution contains layer-forming components such as e.g. Zinc and possibly other divalent metal ions and phosphate ions.
  • a phosphating solution contains non-layer-forming components such as alkali metal ions to blunt the free acid and in particular 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, otherwise the functioning of the sewage treatment plant would be endangered.
  • German patent application DE 198 13 058 describes a process for the treatment of phosphating bath overflow and / or rinsing water after phosphating, the phosphating bath overflow and / or the rinsing water being subjected to nanofiltration.
  • the concentrate of the nanofiltration can be returned to the phosphating bath.
  • the filtrate from the nanofiltration represents waste water, which may have to be treated further before being discharged into a biological sewage treatment plant.
  • the German patent application DE 198 54431 describes a method for saving rinsing water in the phosphating.
  • the phosphating bath overflow and / or the rinse water after the phosphating is subjected to a treatment process such as a reverse osmosis, an unspecified ion exchange process, a nanofiltration, an electrodialysis and / or heavy metal precipitation and the water phase depleted of metal ions is used as rinsing water for rinsing the phosphating metal parts is used after cleaning.
  • DE-A-42 26 080 discloses the treatment of rinse water after phosphating by ion exchange processes. Strongly acidic cation exchange resins based on sulfonic acid groups are used.
  • regenerate cannot be used to supplement the phosphating solution, since in addition to the layer-forming cations it also contains non-layer-forming cations, which would lead to excessive salting of the phosphating solution.
  • DE 199 18 713 describes an improved method for treating phosphating bath overflow and / or rinsing water after phosphating. It should at least be ensured that ultimately there is a waste water to be disposed of, the content of zinc and / or nickel ions of which is below the permissible waste water limit values. Instead of being disposed of by a sewage treatment plant, however, the wastewater should also be able to be used to rinse the metal parts to be phosphated after degreasing them. The process should preferably be able to be operated in such a way that layer-forming components of the phosphating bath, in particular zinc and / or nickel ions, can be recovered and used again for phosphating purposes.
  • Lewatit R TP 207 or TP 208 is Lewatit R TP 207 or TP 208 from Bayer AG.
  • Lewatit * - selective exchanger properties and application of Lewatit TP 207
  • Lewatit TP 207 is used in the majority of cases after pre-loading (conditioning) with alkali or alkaline earth ions.
  • the decomplexing pH for nickel is given as 2.1. This pH value indicates the hydrogen ion concentration at which the metal ion is being desorbed again by the Lewatit TP 207.
  • the company letter further states that the maximum exchange capacity is generally reached when the pH of the loading solution is at least 2 units above the decomplexing pH. According to this information, nickel is only sufficiently bound at a pH above 4.1. Consequently, the ion exchanger in the monosodium form is used in the exemplary embodiments of DE-A-199 18 713, already cited. According to the Bayer AG company publication mentioned above, the outflow of the ion exchanger in the mono-sodium form has a pH value between 6 and 9.
  • Japanese patent application JP 62287100 (cited from Derwent abstract 1988-025811) describes the binding of nickel ions from phosphoric acid solution to an ion exchanger, the acidic groups of which are 25 to 75% neutralized with sodium ions.
  • Japanese patent application JP 63057799 A2 (cited from Patent Abstracts of Japan) discloses that nickel from a plating solution can also be bound to the H form of an ion exchanger with chelating iminodiacetic acid groups (which are weakly acidic groups). This is not transferable to the problem of the present invention, since plating solutions have much higher metal ion contents than phosphating bath overflow diluted with rinsing water or rinsing water after phosphating.
  • the nickel contents of the latter solutions are generally in the range between 5 and 100, in particular between 10 and 50 ppm. These solutions must be processed so that the nickel content of the processed solutions is below 1 ppm.
  • this method has the disadvantage that when the ion exchanger is used to treat the phosphating bath waste water, waste water salted by sodium salts is formed which can only be reused to a limited extent.
  • waste water salted by sodium salts is formed which can only be reused to a limited extent.
  • residual sodium in the ion exchanger is also eluted.
  • the nickel-containing resource solution is therefore contaminated with sodium ions and can therefore only be used to a limited extent.
  • the object of the present invention is to avoid the disadvantages mentioned above.
  • weakly acidic ion exchangers of the Lewatit R TP 207 type also have a pH of not more than 4 nickel from dilute solutions (nickel contents between 5 and 100, especially between 10 and 50 ppm) bind sufficiently and in particular selectively to manganese and partially zinc.
  • the invention accordingly relates to a process for the preparation of a nickel-containing aqueous solution consisting of a phosphating bath overflow and / or rinsing water after the 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 accelerator, the phosphating bath overflow and / or the rinsing water after the phosphating being passed over a weakly acidic ion exchanger, characterized in that the acid groups of the ion exchanger are neutralized to no more than 15% with alkali metal ions and in that the nickel-containing aqueous solution has a pH in the range from 2.5 to 6.0, preferably from 3 to 4, when it is applied to the ion exchanger. 1.
  • a weakly acidic ion exchanger should therefore be used, the acid groups of which are not more than 10% neutralized with alkali metal ions.
  • the acid groups of the ion exchanger are neutralized to no more than 5%, preferably not more than 3% and in particular not more than 1% with alkali metal ions.
  • the ion exchanger contains no alkali metal ions at all. Since equilibrium processes play a role in the regeneration of a loaded ion exchanger, this desired ideal state of the ion exchanger cannot always be achieved.
  • BV bed volume
  • the bed volume of weakly acidic ion exchangers tends to depend on the degree of neutralization of the acid groups. If, for example, the di-sodium form of a weakly acidic ion exchanger with iminodiacetic acid groups, for example Lewatit R TP 207, with a bed volume of 500 ml is washed with acid to such an extent that the sodium ions are removed as much as possible, the bed volume shrinks to 400 ml.
  • the bed volume of the mono-sodium form is 450 ml.
  • Such an ion exchanger is in the state to be used according to the invention if the bed volume of the ion exchanger, which is 500 ml in the di-sodium form, is not above 415 ml.
  • 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 baths contain 0.01 to 2.5 g / l, preferably 0.3 to 2.0 g / l, of nickel ions.
  • the phosphating solution as is customary for trication processes, can contain 0.1 to 4 g / l, in particular 0.5 to 1.5 g / l, of manganese ions.
  • the phosphating solution can also contain as further metal ions: 0.2 to 2.5 g / l magnesium (II), 0.2 to 2.5 g / l calcium (II), 0.002 to 0.2 g / l copper (II), 0.1 to 2 g / l cobalt (II).
  • the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly useful 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 called "depolarization". The formation of hydrogen bubbles on the metal surface, which the Disrupt layer formation is prevented. If a membrane process (reverse osmosis or nanofiltration) is used in the process according to the invention before the ion exchange, accelerators are preferred whose by-products or degradation products (reaction products with hydrogen) can penetrate the membrane. This ensures that these by-products and degradation products of the accelerator do not accumulate in the phosphating bath, but are at least partially discharged from the system via the filtrate of the membrane filtration.
  • Degradation products form either water or monovalently charged ions, which is a
  • Phosphating solution contain one or more of the following accelerators:
  • chlorine ions form chloride ions, nitrite ions nitrate ions and ammonium ions, ammonium ions from nitrate ions, ammonium ions from hydroxylamine and water from hydrogen peroxide.
  • the anions or ammonium ions formed can pass through a nanofiltration membrane, so that in the process according to the invention they are at least partially discharged from the phosphating bath overflow or from the rinsing water after the phosphating.
  • hydrogen peroxide can advantageously be used as the accelerator. This can be used as such or in the form of compounds which form hydrogen peroxide under the conditions of the phosphating bath.
  • polyvalent ions should preferably not be formed as by-products in this case, since they are present in Return of the concentrate of the nanofiltration in the phosphating bath would be enriched. Therefore, alkali metal peroxides are particularly suitable as an alternative to hydrogen peroxide.
  • An accelerator which is also preferably to be used in the process according to the invention is hydroxylamine. If this is added to the phosphating bath in free form or in the form of hydroxylammonium phosphates, hydroxylammonium nitrate and / or hydroxylammonium chloride, only degradation or by-products are also produced which can penetrate a nanofiltration membrane.
  • the process according to the invention can be operated in such a way that the phosphating bath overflow and / or the rinsing water after the phosphating is carried out directly (if appropriate after removing sludge and / or organic constituents, for example by sieve or bag filtration or filtration via a particle bed such as For example, a sand filter can be carried out) via the weakly acidic ion exchanger.
  • the phosphating bath over and / or the rinsing water after the phosphating (likewise if appropriate after the removal of sludge and / or organic constituents) can be subjected to membrane filtration in the form of ultrafiltration, nanofiltration or reverse osmosis.
  • the aqueous solution is then passed over the weakly acidic ion exchanger.
  • the weakly acidic ion exchanger selectively removes metal ions, which are valuable substances from a phosphating solution, from the aqueous solution.
  • this increases the certainty that the wastewater limit values for these cations are observed.
  • these cations can be used again for the purposes of phosphating after regeneration of the ion exchanger.
  • membrane types are available for ultrafiltration, nanofiltration or reverse osmosis. Since phosphating baths and also the corresponding rinsing water react acidic, the membrane used should be acid-stable.
  • suitable inorganic membranes such as B. ceramic membranes.
  • Organic polymer membranes can also be used.
  • Polyamide membrane suitable as a nanofiltration membrane
  • the process is preferably operated in such a way that the retentate of the membrane filtration is returned to the phosphating solution.
  • part of the layer-forming cations present in the overflow of the phosphating bath or in the rinsing water is already returned to the phosphating solution. This leads to a more economical way of operating the phosphating bath, since fewer ingredients have to be added again.
  • the phosphating bath overflow and / or the rinsing water after the phosphating is passed directly to the ion exchanger or whether one of the membrane filtration processes mentioned is used beforehand, it is preferred to use the phosphating bath overflow and / or the rinsing water after the phosphating of sludge and / or free organic ingredients. This prevents the filtration membranes or the ion exchanger from blocking. Sludge can be removed, for example, by bag filtration.
  • the filter Lofclear 523 D from Loeffler GmbH is suitable as a filter here. It removes 95% of the particles smaller than 1.5 ⁇ m and 99.9% of the particles smaller than 5.5 ⁇ m.
  • Organic constituents in the phosphating bath can be removed by activated carbon or by synthetic resins.
  • the type Lofsorb LA 40 E-3-01 from Loeffler GmbH is suitable as activated carbon.
  • Lewatit VP 0C 1066 or Dowex OPTL 285, for example, can be used as organic resins to remove organic constituents.
  • a weakly acidic ion exchanger is preferably a type which is selective for nickel and / or zinc ions.
  • the weakly acidic ion exchanger preferably binds nickel ions more strongly than zinc ions under the operating conditions. This means that nickel ions from the applied solution can displace zinc ions from the ion exchanger. Monovalent cations should be bound as little as possible.
  • Those weakly acidic ion exchangers which carry chelating iminodiacetic acid groups are particularly suitable for this.
  • a suitable product is Lewatit R TP 207 or TP 208 from Bayer.
  • Other suitable ion exchangers are IRC 718/748 from Rohm & Haas and S-930 from Purolite.
  • the process is preferably operated in such a way that the weakly acidic ion exchanger is regenerated after loading with a strong acid.
  • the selectively bound nickel ions, optionally together with remaining zinc ions, are eluted here and can be used again for the purposes of phosphating.
  • these cations do not have to be disposed of as sludge containing heavy metals, but can be used again for phosphating, if appropriate after suitable treatment. This saves resources.
  • Phosphoric acid is particularly suitable.
  • the phosphoric acid can, based on the total amount of acid, contain up to a total of 10 mol% of nitric acid, hydrochloric acid and / or hydrofluoric acid.
  • the ion exchanger is washed after the regeneration with a strong acid with water or with an amount of alkali that does not exceed 0.5 bed volumes of 4 -% sodium hydroxide solution. This rinsing process is carried out until the pH of the rinsing solution flowing out of the ion exchanger is between 2.1 and 4.5, preferably between 3.0 and 4.1.
  • a rinse water is used, the temperature of which is in the range between approximately 5 and approximately 50 ° C. and in particular between approximately 15 and approximately 45 ° C. You can completely do without sodium hydroxide for rinsing. However, this requires a correspondingly long rinse with water.
  • the rinsing process can be shortened if you add an amount of lye to the rinsing water that corresponds to a maximum of 0.5 bed volumes of 4% sodium hydroxide solution. With this amount of lye, the remaining acid in the free volume between the exchange particles is neutralized, but not the acid groups of the exchanger itself. This means that with this small amount of lye, hardly any sodium ions bind to the ion exchanger. Rather, these are predominantly present as dissolved salts in the water phase between the exchanger particles and are therefore quickly displaced onto the exchanger when the solution to be treated is added.
  • the procedure is preferably to discharge a concentrate fraction which contains at least 0.5% by weight of nickel ions and to use this immediately or after supplementing it with other active ingredients to supplement a phosphating solution. It is particularly preferred to supplement the regenerate with further zinc and / or nickel ions and with other active ingredients of a phosphating solution in such a way that a conventional supplementary solution for a phosphating bath is formed. This supplementary solution can then be used as usual to supplement the phosphating bath.
  • the solution depleted in cations which leaves the weakly acidic cation exchanger in its loading phase, can, depending on the ingredients, be fed to a simplified wastewater treatment or directly into a biological sewage treatment plant can be started.
  • this solution it is more economical to use this solution as rinse water for the metal parts to be phosphated after they have been degreased.
  • This embodiment of the method according to the invention has the additional advantage that flushing water is saved.
  • the outlet from the ion exchanger can be used directly for rinsing purposes. If the upstream membrane filtration is dispensed with, it is advisable to subject the outlet from the ion exchanger to membrane filtration before it is used as rinsing water. Nanofiltration is particularly suitable for these processes.
  • the activity of the weakly acidic cation exchanger Lewatit TP 207 (Bayer) in the H + form against a fully synthetic aqueous phosphating rinse solution was tested.
  • exchange columns were filled with 500 ml resin each (in the delivery form as disodium form. Volume shrinks to 400 ml when exchanged with acid to form the H + form) and charged with 648 bed volumes of rinsing solution and the eluate solution emerging from the columns was continuously analyzed for its residual metal content.
  • the fully synthetic rinsing solutions used contained 25 ppm nickel, 25 ppm manganese and 50 ppm zinc. Table 1 shows the loading volumes and the corresponding nickel concentrations. Table 1
  • the activity of the weakly acidic cation exchanger Lewatit TP 207 was investigated analogously to Example 1.
  • the used Phosphating rinse solutions corresponded to the information in Example 1.
  • Table 2 shows the loading volumes and the corresponding nickel concentrations. The breakthrough behavior for nickel is almost identical in both examples.
  • the activity of the weakly acidic cation exchanger Lewatit TP 207 (Bayer) in the H + form against a fully synthetic aqueous phosphating rinse solution was tested.
  • exchange columns were each filled with 500 ml resin (delivery form: Di-Na + , about 400 ml in the H + form used) and charged with 480 bed volumes of rinsing solution, and the eluate solution emerging from the columns was continuously analyzed for its residual metal content.
  • the fully synthetic rinsing solutions used contained 25 ppm nickel, 25 ppm manganese and 50 ppm zinc. Table 3 shows the loading volumes and the corresponding nickel concentrations.
  • the activity of the weakly acidic cation exchanger Lewatit TP 207 was investigated analogously to Example 3.
  • the resin was conditioned with 2.4 BV NaOH (4%) after regeneration and then rinsed with 2.0 BV deionized water (each with 4 BV / h).
  • the used Phosphating rinse solutions corresponded to the information in Example 3.
  • Table 4 shows the loading volumes and the corresponding nickel concentrations. The breakthrough behavior for nickel is very similar in both examples.
  • Example 4 shows that nickel is more firmly bound to Lewatit R TP 207 than zinc and manganese.
  • the initially high nickel contents are based on residual nickel in the test setup through a previous test cycle.
  • Manganese is only initially bound by the column, but runs freely after loading with about 500 bed volumes of solution. With this loading, the breakthrough of zinc also begins, while nickel is still almost completely bound up to about 1000 bed volumes. Above this degree of loading, nickel is becoming increasingly poorer, but is still bound significantly, while the zinc content of the emerging solution is higher than that of the applied solution. This means that not only is no further zinc bound, but that nickel in the solution displaces the zinc bound to the exchanger.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention concerne un procédé de traitement d'une solution aqueuse au nickel renfermant un excès de bain de phosphatation et/ou d'eau de rinçage après phosphatation, ladite phosphatation étant effectuée à l'aide d'une solution phosphatée aqueuse acide contenant de 3 à 50 g/l d'ions phosphates, calculés sous forme de PO4-3, de 0,2 à 3 g/l d'ions zinc, de 0,01 à 2,5 g/l d'ions nickel, éventuellement d'autres ions métalliques et éventuellement un accélérateur, et l'excès de bain de phosphatation et/ou l'eau de rinçage après phosphatation étant acheminé vers un échangeur d'ions faiblement acide. Ce procédé est caractérisé en ce que les groupes acides de l'échangeur d'ions sont neutralisés à pas plus de 15 % d'ions de métaux alcalins et que la solution aqueuse au nickel présente un pH compris entre 2,5 et 6, lors de son chargement sur l'échangeur d'ions.
EP01996515A 2000-11-15 2001-11-06 Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation Withdrawn EP1337471A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10056629A DE10056629C1 (de) 2000-11-15 2000-11-15 Verfahren zur Aufbereitung von nickelhaltigem Abwasser bei der Phosphatierung
DE10056629 2000-11-15
PCT/EP2001/012814 WO2002040405A2 (fr) 2000-11-15 2001-11-06 Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation

Publications (1)

Publication Number Publication Date
EP1337471A2 true EP1337471A2 (fr) 2003-08-27

Family

ID=7663411

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01996515A Withdrawn EP1337471A2 (fr) 2000-11-15 2001-11-06 Traitement d'eaux residuaires renfermant du nickel lors d'une phosphatation

Country Status (9)

Country Link
US (1) US20040037765A1 (fr)
EP (1) EP1337471A2 (fr)
JP (1) JP2004514055A (fr)
CN (1) CN1498193A (fr)
AU (1) AU2002219077A1 (fr)
BR (1) BR0115363A (fr)
CA (1) CA2429156A1 (fr)
DE (1) DE10056629C1 (fr)
WO (1) WO2002040405A2 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003266307A1 (en) * 2002-08-31 2004-04-30 Henkel Kommanditgesellschaft Auf Aktien Multi-stage method for reprocessing waste water from a phosphating process, using a subacid ion exchanger
DE10257074B4 (de) 2002-12-06 2018-07-26 Henkel Ag & Co. Kgaa Verfahren zum Aufbereiten von Phosphatierbadüberlauf oder Spülwasser nach einer Phosphatierung
DE10308426B4 (de) * 2003-02-27 2005-03-03 Henkel Kgaa Verfahren zur Aufbereitung von Phosphatierbadüberlauf und/oder von Spülwasser nach der Phosphatierung
DE102005043031A1 (de) * 2005-09-10 2007-03-15 Mauer, Dieter, Dr. Verfahren zum Entfernen von Phosphaten aus Acetat-gepufferten Lösungen
WO2008038740A1 (fr) * 2006-09-28 2008-04-03 Kurita Water Industries Ltd. Procédé et équipement pour récupérer l'acide phosphorique dans de l'eau contenant de l'acide phosphorique
CN101624248B (zh) * 2009-07-29 2011-08-24 深圳市天骄科技开发有限公司 镍钴锰酸锂生产废水的处理方法
CN103663774A (zh) * 2013-02-27 2014-03-26 苏州信望膜技术有限公司 利用膜分离技术处理低浓度含氨废水的方法
CN103588325A (zh) * 2013-11-22 2014-02-19 大连碧城环保科技有限公司 酸洗磷化工业废水的再生循环方法
CN103588326A (zh) * 2013-11-22 2014-02-19 大连碧城环保科技有限公司 金属磷化加工清洁生产工艺
DE102016215233A1 (de) * 2016-08-16 2018-02-22 Bayerische Motoren Werke Aktiengesellschaft Verfahren und Vorrichtung zum Entfetten eines Bauteils
CN111470717A (zh) * 2020-04-15 2020-07-31 河南恒安环保科技有限公司 一种新能源汽车电泳涂装废水处理回用方法
CN111809048A (zh) * 2020-07-19 2020-10-23 河南科技大学 一种去除硫酸钴电解中痕量镍的方法
CN112125457A (zh) * 2020-09-10 2020-12-25 黄河三角洲京博化工研究院有限公司 一种热电反渗透浓水结晶分盐的处理方法
CN114436481A (zh) * 2022-04-02 2022-05-06 山东凤鸣桓宇环保有限公司 一种磷化废水资源化回收工艺
CN114477665B (zh) * 2022-04-14 2022-07-22 山东凤鸣桓宇环保有限公司 一种涂装废水资源化处理工艺

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5910430B2 (ja) * 1976-04-19 1984-03-08 日本ペイント株式会社 リン酸塩皮膜化成処理方法
JPS6357799A (ja) * 1986-08-25 1988-03-12 Kurita Water Ind Ltd メツキ液の処理方法
DE4226080A1 (de) * 1992-08-06 1994-02-10 Henkel Kgaa Aufbereitung wäßriger Spüllösungen aus Zinkphosphatierungsprozessen
DE4435774C1 (de) * 1994-10-06 1996-03-14 Rimmel Gmbh Verfahren zum Abtrennen von Zink aus Zink und Chrom enthaltenden Lösungen oder Schlämmen wie Abwässern, Prozeßbädern oder Galvanikschlämmen
DE19754109A1 (de) * 1997-12-05 1999-06-10 Henkel Kgaa Abwasseraufbereitung bei der Phosphatierung
DE19854431A1 (de) * 1998-11-25 2000-05-31 Henkel Kgaa Phosphatierverfahren mit Spülwasser-Einsparung
DE19813058A1 (de) * 1998-03-25 1999-09-30 Henkel Kgaa Abwasseraufbereitung bei der Phosphatierung
DE19918713C5 (de) * 1999-04-26 2005-09-15 Henkel Kgaa Abwasseraufbereitung bei der Phosphatierung
DE19958775A1 (de) * 1999-05-28 2000-11-30 Henkel Kgaa Nachpassivierung einer phosphatierten Metalloberfläche
CA2400695A1 (fr) * 1999-05-28 2000-12-07 Henkel Kommanditgesellschaft Auf Aktien Post-passivation d'une surface metallique phosphatee

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0240405A2 *

Also Published As

Publication number Publication date
DE10056629C1 (de) 2002-04-04
WO2002040405A2 (fr) 2002-05-23
BR0115363A (pt) 2003-08-26
CN1498193A (zh) 2004-05-19
WO2002040405A3 (fr) 2002-07-25
CA2429156A1 (fr) 2002-05-23
US20040037765A1 (en) 2004-02-26
AU2002219077A1 (en) 2002-05-27
JP2004514055A (ja) 2004-05-13

Similar Documents

Publication Publication Date Title
DE10056629C1 (de) Verfahren zur Aufbereitung von nickelhaltigem Abwasser bei der Phosphatierung
EP1198618B1 (fr) Post-passivation d'une surface metallique phosphatee
DE19918713C5 (de) Abwasseraufbereitung bei der Phosphatierung
EP1567689A1 (fr) Procede de phosphatation de surfaces metalliques presentant un meilleur taux de recuperation de phosphate
DE19854431A1 (de) Phosphatierverfahren mit Spülwasser-Einsparung
EP1392887B1 (fr) Procede permettant d'empecher l'encrassement de la membrane lors du traitement des eaux usees resultant de la phosphatation
EP1036036B1 (fr) Traitement d'eaux usees lors de la phosphatation
DE10142933A1 (de) Verhinderung von Membranverblockung bei der Abwasseraufbereitung bei der Phosphatierung
DE10254952A1 (de) Mehrstufiges Verfahren zur Aufarbeitung von Phosphatierabwasser unter Einsatz eines schwach sauren Ionenaustauschers
WO1999048819A1 (fr) Traitement des eaux usees lors de la phosphatation
EP3218531B1 (fr) Procédé d'élimination sélective d'ions zinc de solutions de bain alcalines dans le traitement de surface de composants métalliques en série
DE19958775A1 (de) Nachpassivierung einer phosphatierten Metalloberfläche
WO2002079541A2 (fr) Post-passivation d'une surface metallique phosphatee par processus en bande
WO2004024636A1 (fr) Procede a plusieurs etapes destine au traitement d'eaux usees de phosphatage a l'aide d'un echangeur ionique peu acide
DE19813058A1 (de) Abwasseraufbereitung bei der Phosphatierung
WO2003078684A1 (fr) Procede de phosphatation de surfaces metalliques assurant un recyclage ameliore des matieres revalorisables
EP1685274B1 (fr) Procede de phosphatation limitant la quantite d'eaux usees, par traitement de solution de degraissage et/ou d'eau de lavage
WO2004063424A2 (fr) Procede pour traiter de l'eau de rinçage phosphatee au moyen de membranes bi- ou multicouches
WO2004101866A2 (fr) Procede et dispositifs pour prolonger la duree d'utilisation d'une solution de procede utilisee dans un processus de revetement metallique par reduction chimique
DE10236293A1 (de) Verfahren zur Phosphatierung von Metalloberflächen mit verbesserter Wertstoff-Rückgewinnung
DE10257074B4 (de) Verfahren zum Aufbereiten von Phosphatierbadüberlauf oder Spülwasser nach einer Phosphatierung
DE102022133482A1 (de) Verfahren sowie Wasseraufbereitungsanlage zum Aufbereiten von Spülwasser aus einer Spülung von Metalloberflächen nach deren Phosphatierung
DE10341232A1 (de) Verfahren zur Phosphatierung von Metalloberflächen mit verbesserter Wertstoff-Rückgewinnung
DE10308426B4 (de) Verfahren zur Aufbereitung von Phosphatierbadüberlauf und/oder von Spülwasser nach der Phosphatierung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030506

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: RO SI

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20060712