WO2004063424A2 - Procede pour traiter de l'eau de rinçage phosphatee au moyen de membranes bi- ou multicouches - Google Patents

Procede pour traiter de l'eau de rinçage phosphatee au moyen de membranes bi- ou multicouches Download PDF

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Publication number
WO2004063424A2
WO2004063424A2 PCT/EP2003/013392 EP0313392W WO2004063424A2 WO 2004063424 A2 WO2004063424 A2 WO 2004063424A2 EP 0313392 W EP0313392 W EP 0313392W WO 2004063424 A2 WO2004063424 A2 WO 2004063424A2
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Prior art keywords
nanofiltration
phosphating
retentate
permeate
ions
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PCT/EP2003/013392
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German (de)
English (en)
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WO2004063424A3 (fr
Inventor
Patrick Droniou
Jens KRÖMER
Klaus Lepa
Jan-Willem Brouwer
Iradj Peirow
Peter Kuhm
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU2003283433A priority Critical patent/AU2003283433A1/en
Publication of WO2004063424A2 publication Critical patent/WO2004063424A2/fr
Publication of WO2004063424A3 publication Critical patent/WO2004063424A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B01D61/0271—Nanofiltration comprising multiple nanofiltration steps
    • 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
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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 process for the treatment of the overflow of the phosphating baths and / or the rinsing water after the phosphating, hereinafter referred to as "phosphating rinsing water".
  • phosphating rinsing water improves the wastewater treatment and enables the recycling of bath contents into the phosphating bath and / or water into the overall process.
  • the phosphating of metals pursues the goal k to produce 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. have about 0.5 to about 2 g / l.
  • 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. 0.05 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 electro-painting of car bodies, widely used.
  • 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, 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 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 and transfer it into the rinsing water.
  • 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.
  • DE-A-198 13 058 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 P ⁇ 4 3 " , 0.2 to 3 g / l zinc ions, optionally further metal ions and accelerators, the phosphating bath overflow and / or the rinsing water being subjected to nanofiltration, however, when the process is operated in practice, the filtration membrane becomes blocked within a few hours can be attributed to the fact that the phosphate sludge contained in the rinsing water after the phosphating and in the phosphating bath overflow cannot be completely removed from the solution by
  • DE-A-197 54 109 describes a treatment process for rinsing water after phosphating, which involves working with a phosphating solution which contains an organic molecule with a molecular weight of at least 80 as an accelerator. The mixture is worked up by ultrafiltration, the concentrate being discarded. The filtrate is preferably subjected to nanofiltration in a second step. The concentrate of the nanofiltration is returned to the phosphating solution, the filtrate is used again as rinsing water.
  • EP-A-1 106 711 uses a two-stage reverse osmosis.
  • the rinsing water is first acidified after phosphating and then subjected to the first reverse osmosis.
  • the concentrate from this is fed to the phosphating solution.
  • the filtrate from the first reverse osmosis is neutralized by adding alkali and subjected to a second reverse osmosis.
  • the concentrate from this is discarded, the filtrate is reused as rinsing water.
  • the aim of the present invention is to further improve membrane processes for working up phosphating rinse water, for example in order to reduce the consumption of chemicals, to increase membrane service life or to make the process sequence more cost-effective.
  • the object of the present invention is a method for phosphating metal surfaces, the metal surfaces being sprayed and / or dipped a) cleaned with at least one cleaning solution, b) rinsed after cleaning with at least a first rinse water, c) phosphated with a phosphating solution , which contains 3 to 50 g / l phosphate ions, calculated as P ⁇ 4 3 " , 0.2 to 3 g / l zinc ions, optionally further divalent metal ions and optionally accelerator, and d) after the phosphating, rinsed with at least one second rinse water and wherein e) continuously or discontinuously takes part of the second rinsing water, f) acidified and g) subject to a first nanofiltration, whereby a first retentate, in which zinc ions and possibly the other
  • Rinsing is usually operated in an overflow in a phosphating process. Therefore, the easiest way to remove part of the second rinse water in sub-step e) is to catch the overflow and treat it in accordance with the further process steps.
  • the acids used are preferably those which are valuable substances in industrially customary phosphating baths. These are in particular phosphoric acid, hydrofluoric acid and acids, the acid residues of which are complex fluorides of boron, silicon, titanium or zircon. If the phosphating bath should or may contain nitrate ions as an accelerator or co-accelerator, nitric acid is also suitable.
  • an acidic aqueous solution is preferably used as the acid in sub-step f), which was obtained during the regeneration of such a cation exchanger. This leads to an additional reuse of chemicals and thus to cost savings.
  • the first permeate can be at least partially transferred into the cleaning solution and / or into the first rinsing water and / or subjected to a further ion separation.
  • a further nanofiltration or a cation exchanger can, for example, be provided for this further ion separation.
  • Another alternative in sub-step h) is to adjust the permeate of the first nanofiltration to a pH in the range between 6 and 8 and to use it as rinsing water after cleaning the metal surfaces to be phosphated, ie between cleaning and phosphating.
  • sodium hydroxide solution is preferably used to adjust the pH.
  • the permeate of the first nanofiltration is adjusted to a pH in the range between 9 and 13 and used to supplement the cleaning solution for cleaning the metal surfaces to be phosphated.
  • sodium hydroxide is preferably used to adjust the pH, if not Potassium hydroxide solution is preferred for reasons of the solubility of salts formed.
  • the surfactants are preferably selected from nonionic surfactants, for example ethoxylates and / or propoxylates of alkyl alcohols or alkylamines having 8 to 22 carbon atoms in the alkyl chain. Ethoxylates and / or propoxylates of such alkyl alcohols or alkyl amines which are obtainable from vegetable or animal fats or oils are preferably used here.
  • builder substances can also be added to the permeate of the first nanofiltration in addition to the surfactants.
  • These are preferably selected from the group of water-soluble borates, silicates, carbonates, triphosphates or pyrophosphates.
  • the cations of these salts are preferably sodium and / or potassium ions.
  • the retentate of the first nanofiltration contains enriched layer-forming cations such as zinc, nickel and / or manganese ions.
  • This retentate is subjected to at least one further nanofiltration in sub-step i) and the layer-forming cations are thereby further enriched in its retentate (“further retentate”).
  • the further retentate is preferably worked up in such a way that it at least is proportionally returned to the phosphating bath if it is not subjected to one or more further nanofiltration stages and is thereby further concentrated in further retentates.
  • the "further" retentate obtained last is at least partially returned to the phosphating bath.
  • this is done in such a way that the retentate is used as the basis for the preparation of a supplementary solution for the phosphating bath and thus with active ingredients (for example with ion-forming metals, with acids selected from nitric acid, phosphoric acid, hydrofluoric acid or acids whose acid residues are complex fluorides of B, Si, Ti or Zr, or internal accelerators such as hydroxylamine) are added to form a supplemental solution for a phosphating bath.
  • active ingredients for example with ion-forming metals, with acids selected from nitric acid, phosphoric acid, hydrofluoric acid or acids whose acid residues are complex fluorides of B, Si, Ti or Zr, or internal accelerators such as hydroxylamine
  • active ingredients for example with ion-forming metals, with acids selected from nitric acid, phosphoric acid, hydrofluoric acid or acids whose acid residues are complex fluorides of B, Si, Ti or Zr, or internal accelerators such as hydroxyl
  • one embodiment of the process according to the invention consists in adjusting the pH of this further retentate to a value in the range between 2.55 to 3.2, preferably between 2.6 to 3.0, and the retentate then leads back into the phosphating solution.
  • An alkali such as caustic soda could be used to raise the pH.
  • substances which contain active substances for the phosphating bath are preferably used to raise the pH.
  • the hydroxylamine or oxides or carbonates of zinc, nickel and / or manganese which acts as a phosphating accelerator can be used to raise the pH, the content of layer-forming cations being added to the phosphating solution.
  • Phosphoric acid is preferably used to acidify the rinsing water or the phosphating bath overflow before membrane filtration, since this acid is a main component of the phosphating solution.
  • This two-stage or multi-stage procedure has the advantage over that in the unpublished German patent application DE-A-101 27 918 that lower enrichment factors can be used in each of the two or more nanofiltration stages. This reduces the pressures required and extends the membrane service life. A smaller amount of acid is sufficient for the acidification in sub-step f), so that less alkali is used for later neutralization. This makes the overall process more economical.
  • divalent cations are preferably retained, while monovalent ions largely pass through the membrane. In contrast, all ions are largely retained in reverse osmosis.
  • the further permeate obtained in sub-step i) can be further processed or discarded as desired.
  • the economy of the process according to the invention can be further increased by adding the further permeate at least partially to the part of the second rinse water removed in sub-step e) before subjecting it to the first nanofiltration in sub-step g).
  • the cycle for layer-forming divalent cations still present in a low concentration in the further permeate is completely closed.
  • Monovalent ions return to the first nanofiltration stage and in their first filtrate.
  • the first retentate obtained in sub-step g) can be mixed with additional acid analogous to sub-step f) (and the explanations given above for this) with acid before sub-step i) subjecting it to further nanofiltration. In general, however, this should not be necessary and is less desirable in terms of the economical use of chemicals.
  • the first nanofiltration g) is preferably carried out in such a way that the zinc ions contained in the feed of the nanofiltration and possibly the further divalent cations in the first retentate are concentrated by a first enrichment factor in the range from 3 to 20, preferably from 6 to 15. This is possible by choosing an appropriate pressure and adjusting the permeate flow. This first enrichment factor is less than that which is required for an economical one-step procedure according to the already cited DE-A-101 27 918. The membrane load is correspondingly lower.
  • the further nanofiltration i) is preferably carried out in such a way that the zinc ions contained in the feed of the further nanofiltration and possibly the further divalent cations in the further retentate can be concentrated by a further enrichment factor in the range from 3 to 15. This applies to every further nanofiltration stage.
  • a total enrichment factor in the last further retentate compared to the rinse water is obtained, which corresponds to the product of the individual enrichment factors of the two or more nanofiltration stages.
  • a particularly economical compromise between achieved enrichment, technical effort and membrane service life is obtained by coordinating the concentration enrichment factors in the first nanofiltration g) and in each further nanofiltration i) in such a way that the zinc ions contained in the feed of the first nanofiltration and optionally the further divalent cations in the last further retentate are concentrated by a total enrichment factor in the range from 20 to 80.
  • step h) the pH of the first permeate is preferably raised by adding alkali before it is at least partially transferred into the cleaning solution and / or the first rinsing water.
  • the zinc contents of the phosphating solution 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 phosphate baths can vary within wide limits, provided that 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 common in phosphating baths.
  • Phosphating solutions which contain further mono- or divalent metal ions, which experience has shown to have a favorable effect on the paint adhesion and the corrosion protection of the phosphate layers thus produced, are preferably used.
  • the phosphating solution according to the invention preferably additionally contains one or more of the following cations:
  • the phosphating solution contains 0.1 to 4 g / l of manganese ions and 0.002 to 0.2 g / l of copper ions as additional cations and not more than 0.05 g / l, in particular not more than 0.001 g / l, of nickel ions.
  • phosphating baths can be used which, in addition to zinc ions, contain 0.1 to 4, preferably up to 3 g / l manganese ions and additionally 0.05 to 2.5 g / l nickel ions.
  • 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 which are said to be suitable for different substrates, it has become customary to use free and / or complex-bound fluoride in amounts of up to 2.5 g / l of total fluoride, of which up to 750 mg / l of free fluoride, each calculated as F " ,
  • the aluminum content of the bath should not exceed 3 mg / l.
  • higher Al contents are tolerated as a result of the complex formation, provided the concentration of the uncomplexed AI does not exceed 3 mg / l.
  • 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.
  • the phosphating solution can contain one or more of the following accelerators: 0.3 to 4 g / l chlorine ions 0.01 to 0.2 g / l nitrite ions 0.1 to 10 g / l hydroxylamine
  • chlorine ions are formed from chloride ions, nitrate ions and ammonium ions from nitrate ions, ammonium ions from nitrate ions, ammonium ions from hydroxylamine and water from hydrogen peroxide.
  • the anions or ammonium ions formed can pass through the nanofiltration membrane, so that they are at least partially discharged from the phosphating bath overflow or from the rinsing water after the phosphating in the process according to the invention.
  • 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.
  • no polyvalent ions should preferably be formed as by-products, since these would be enriched in the phosphate bath when the concentrate of the nanofiltration was returned. 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 formed which can penetrate a nanofiltration membrane.
  • the nanofiltration membrane used should be acid-stable.
  • inorganic membranes such as. B. ceramic membranes.
  • Organic polymer membranes can also be used the.
  • a polyamide membrane is particularly suitable.
  • the membrane can be used, for example, as a winding module, tube module or plate module.
  • Rinsing water 2 was prepared from rinsing water 1 by adding 100 g / m 3 of 85% phosphoric acid in order to lower the pH to 3.
  • Flushing water (2) was circulated over a membrane NF TS 80 (company TRISEP) with the following parameters: membrane pressure: 12 bar working temperature: 35 ° C The rinsing water is separated through the membrane into a permeate (1) and a concentrate (retentate, taken from the circuit) (1).
  • composition Ni 184 mg / l
  • the concentrate (1) is used to apply the second membrane, see below.
  • composition Ni 2.5 mg / l
  • permeate (1) It can be sent to the central wastewater treatment, where the heavy metals are reduced to below the permitted limit values (eg in Germany: 0.5 mg / l for Ni). Alternatively, after neutralization, it can be used as rinsing water after cleaning in a phosphating system. Or it can continue locally up to the permitted limit values be purified, for example by ion exchange or further membrane filtration (nanofiltration or reverse osmosis)
  • the concentrate (1) is passed over a membrane NF TS 80 (TRISEP) under the following conditions (in the circuit as for stage 1): membrane pressure: 12 bar working temperature: 33 ° C
  • the concentrate (1) removed from the circuit in the first stage is separated through the membrane into a permeate (2) and a concentrate (retentate, removed from the circuit) (2).
  • composition Ni 700 mg / l
  • the concentrate (2) can be used without pH adjustment to supplement a phosphating solution. It is not necessary to add sodium hydroxide solution.
  • permeate (2) It can be sent to the central wastewater treatment facility, where the heavy metals are reduced to below the permitted limit values (e.g. in Germany: 0.5 mg / l for Ni). Alternatively, it can be returned to the rinse water (2) before the first membrane filtration. Or it can be further cleaned locally up to the permitted limit values, for example by ion exchange or further membrane filtration (nanofiltration or reverse osmosis).
  • Rinse water 2 was prepared from rinse water 1 by adding 5000 g / m 3 of 85% phosphoric acid in order to lower the pH to 1.9.
  • Flushing water (2) was passed over a membrane DESAL DK (company. Osmonic) with the following parameters: membrane pressure: 6 bar working temperature: 35 ° C
  • the rinsing water is separated through the membrane into a permeate (1) and a concentrate (retentate, taken from the circuit) (1).
  • composition Ni 800 mg / l
  • concentrate (1) After pH adjustment to 3.0, it can be used to supplement a phosphating solution. To bring the concentrate to the pH of the phosphating solution, 1070 g / m 3 NaOH (100%) are required.
  • permeate (1) It can be sent to the central wastewater treatment, where the heavy metals are reduced to below the permitted limit values (e.g. in Germany: 0.5 mg / l for Ni). Alternatively, after neutralization, it can be used as rinsing water after cleaning in a phosphating system. Or it can be further cleaned locally up to the permitted limit values, for example by ion exchange or further membrane filtration (nanofiltration or reverse osmosis)
  • a rinse water after phosphating contained:
  • volume ratio: permeate / retentate: 10/1 to 40/1 concentration factor:
  • Retentate a is used according to the invention for the second stage.
  • Nanofiltration retentate a (level 2, only in example 2)
  • Concentration factor H3P ⁇ 4 dosage 85%, kg / m 3 rinsing water
  • gate single stage
  • Embodiment 2 H3P04 dosing before the 1st nanofiltration stage: 1.25 kg of 85% phosphoric acid per m 3 of rinsing water
  • a total concentration factor of 40 is achieved by the two-stage nanofiltration according to the invention, corresponding to comparative example 2. However, only 1.25 kg of 85% phosphoric acid per m 3 of rinsing water are required for the acidification before the first nanofiltration (which, according to comparative example 3, by one for one-stage concentration Factor 40 would lead to blocking of the membrane).
  • a retentate with an acid content is obtained, which can be transferred directly to a phosphating solution without partial neutralization.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé pour phosphater des surfaces métalliques, les surfaces métalliques étant rincées avec de l'eau de rinçage après phosphatation, et l'eau de rinçage subissant un nanofiltrage en deux étapes ou plus. Selon l'invention, le concentré issu d'une étape de nanofiltrage est utilisé respectivement en tant que solution de départ pour l'étape de nanofiltrage suivante. Le concentré issu de la dernière étape de nanofiltrage est utilisé pour compléter la solution de phosphatation.
PCT/EP2003/013392 2003-01-13 2003-11-28 Procede pour traiter de l'eau de rinçage phosphatee au moyen de membranes bi- ou multicouches WO2004063424A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003283433A AU2003283433A1 (en) 2003-01-13 2003-11-28 Two-stage or multi-stage method for treating phosphated rinsing water using a membrane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10300879.9 2003-01-13
DE10300879A DE10300879A1 (de) 2003-01-13 2003-01-13 Zwei- oder mehrstufiges Membran-Aufbereitungsverfahren von Phosphatierspülwasser

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WO2004063424A2 true WO2004063424A2 (fr) 2004-07-29
WO2004063424A3 WO2004063424A3 (fr) 2004-12-02

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WO2008095555A1 (fr) * 2007-02-05 2008-08-14 Henkel Ag & Co. Kgaa Procédé de production d'eau dessalée à partir d'eau de rinçage contenant du zircon

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DE102009002144A1 (de) * 2009-04-02 2010-10-07 Henkel Ag & Co. Kgaa Umkehrosmoseverfahren zur Aufbereitung von Spülwaser enthaltend polyvalente Metall-Kationen

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DE19854431A1 (de) * 1998-11-25 2000-05-31 Henkel Kgaa Phosphatierverfahren mit Spülwasser-Einsparung
DE19918713A1 (de) * 1999-04-26 2000-11-02 Henkel Kgaa Abwasseraufbereitung bei der Phosphatierung
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WO2008095555A1 (fr) * 2007-02-05 2008-08-14 Henkel Ag & Co. Kgaa Procédé de production d'eau dessalée à partir d'eau de rinçage contenant du zircon
US9079787B2 (en) 2007-02-05 2015-07-14 Henkel Ag & Co. Kgaa Process for obtaining desalted water from zirconium-containing wash water

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DE10300879A1 (de) 2004-07-22
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