WO1993004779A1 - Procede pour le rinçage de surfaces metalliques degraissees et nettoyees - Google Patents

Procede pour le rinçage de surfaces metalliques degraissees et nettoyees Download PDF

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Publication number
WO1993004779A1
WO1993004779A1 PCT/EP1992/001902 EP9201902W WO9304779A1 WO 1993004779 A1 WO1993004779 A1 WO 1993004779A1 EP 9201902 W EP9201902 W EP 9201902W WO 9304779 A1 WO9304779 A1 WO 9304779A1
Authority
WO
WIPO (PCT)
Prior art keywords
treated
activated carbon
water
rinsing
rinsing water
Prior art date
Application number
PCT/EP1992/001902
Other languages
German (de)
English (en)
Inventor
Wolfgang Hater
Lutz Hüsemann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993004779A1 publication Critical patent/WO1993004779A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts

Definitions

  • the invention relates to a method for rinsing metal surfaces previously degreased and cleaned with aqueous cleaning media.
  • the used rinse water is recycled after the separation of ions and the separation of other ingredients using activated carbon.
  • Aqueous degreasing and cleaning media for metallic surfaces are widely used in industrial manufacturing and finishing processes.
  • the cleaned metal surfaces have to be rinsed in order to remove adhering residues of the used cleaning medium, which would impair the subsequent processing steps.
  • the rinsing water contains the usual cleaning components (cress J. et.al .: "Cleaning technical surfaces", Contact & series
  • volume 264 p. 5 ff., Expert-Ve lag, 1988
  • washed-off soiling of the cleaning solution namely synthetic and vegetable oils and fats, waxes, chips,
  • Concentration range usually between 0.01 and 10 g / 1.
  • Rinse water ingredients to each other can be any.
  • the used rinsing water is therefore not sufficiently pure for further use, so that large amounts of waste water are generated.
  • wastewater-free operation is desirable for economic and ecological reasons. With known methods, however, this is only achieved in an inadequate manner and with too much effort.
  • the method mentioned in the first paragraph is known from DE 25 27 853 B2.
  • metals are degreased, rinsed, phosphated and then rinsed again.
  • the used rinsing water is drawn off from the rinsing stages.
  • the anions contained in it are precipitated with calcium hydroxide, the sludge formed is separated off and the desludged solution is passed over a surfactant adsorber.
  • a regenerable exchanger system is preferably used.
  • a filter made of activated carbon can also be used. Since the rinse water to be treated is that of the last rinse stage, care must be taken that the phosphating is carried out with a solution which is essentially free of components which give water-soluble salts when the solution is neutralized with calcium hydroxide.
  • Another disadvantage of this process is the high sludge volume as well the complex process engineering due to the necessary sludge separation.
  • the workpiece is burned off with demineralized water, which is stored in an isolated circuit, e.g. can be regenerated by reverse osmosis or ion exchange.
  • the object of the invention is to provide a simple and universally applicable method of the type mentioned.
  • the invention lies in the selection of the special combination of the two process steps in the specific order from the large number of possible preparation processes and their combinations.
  • the sequence of the two process steps is particularly important and essential to the invention.
  • oils and surfactants are separated.
  • cations and / or anions are removed.
  • the investment costs are very low, so that the process is also suitable for small plants. It can also be adapted to changing water quality requirements by appropriate design.
  • Another advantage is the ability to regenerate the adsorption media (with regard to activated carbon: Perrich JR: Activated Carbon Adsorption for Waste Water Treatment, p.
  • the rinsing water be subjected to a coarse filtration before the treatment with activated carbon in order to separate undissolved contaminants. This removes chips, metal debris, pigments, dust , etc.
  • the one treated with activated carbon is preferably filtered
  • the activated carbon is preferably used in granular form.
  • a mixed bed exchanger containing a cation and anion exchanger is preferred for ion exchange.
  • a simple cation or anion exchanger can also be used.
  • the used rinsing water be passed through columns containing activated carbon or ion exchangers, in particular from the bottom up.
  • the loading of the ion exchanger in the upstream is e.g. in Galvanotechnik 73.8 (1982), page 843.
  • a further advantage of the process according to the invention results from the possibility that the treated rinsing water is additionally or completely reprocessed into ultrapure water and the partial streams obtained are used in different ways Places in the rinsing process.
  • the treated rinsing water is preferably passed through a fine filter (microfilter) before being treated to ultrapure water.
  • the preparation can take place, for example, by membrane filtration. Retentate and per eat are then returned to the rinsing process at various points.
  • the method according to the invention can be used particularly advantageously in combination with the water-saving flushing techniques known per se and mentioned above.
  • the used rinsing water is conveyed from a collecting tank 1 by a pump 2 through a microfilter 3 into one of the two active carbon adsorbers 4.
  • the column 4 is flowed through from bottom to top.
  • a further microfilter 5 is connected downstream, so that the subsequent mixed bed ion exchanger 6 is not contaminated by entrained carbon particles.
  • the exchanger is also flowed through from bottom to top.
  • a third microfilter 7 follows.
  • the quality of the regenerated rinsing water obtained is monitored at reference number 8 by continuous conductivity measurement.
  • the cleaned rinsing water is finally temporarily stored in a second reservoir 9.
  • 2 columns are installed, which can be operated optionally. This is particularly important for production plants. Any number of columns 4, 6 can be connected in parallel for larger plants or throughputs.
  • the activated carbon adsorber 4 and then the mixed bed ion exchanger 6 must be flowed through.
  • test results for the method according to the invention are presented.
  • the tests were carried out on aqueous solutions, each with an alkaline or neutral cleaner.
  • the alkaline product VR 5353-6 contains silicate, borate, carbonate and phosphate and nonionic surfactants as builder components.
  • the neutral cleaner VR 5271-1 is composed of salts of inorganic and organic acids as well as non-ionic surfactants.
  • Aqueous solutions of the products in a concentration of 0.1 g / 1 were added to 0.04 g / 1 of a cutting oil (Shell KS 212) or a mineral oil (Pioneer TYPE 4556) and emulsified using a rotor-stator stirrer.
  • the content of inorganic salts in the solutions was determined by conductivity, the content of organic components by COD (chemical oxygen demand).
  • the batch solution was pumped through a column filled with 120 ml of activated carbon and a column containing 60 ml of ion exchanger.
  • the operating temperature in all tests was 3 ° C, the volume flow 5 l / h.
  • Table 1 shows the conductivity and COD values of the batch solutions and the regenerates after a flow of 5 l.
  • Examples 1 and 2 (without ion exchanger) show that a satisfactory regeneration of the rinsing solution alone is not possible with an activated carbon treatment. In the process according to the invention, however, both organic and inorganic ingredients are largely removed from the rinse water.
  • Table 2 shows the results of a load test in which 50 l of the solution were regenerated in the test apparatus without changing the adsorption media. The tests were carried out under otherwise the same conditions as tests 3 and 4 (Table 1).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

La présente invention se rapporte à un procédé pour le lavage de surfaces métalliques dégraissées et nettoyées auparavant avec des agents de nettoyage aqueux. A cet effet, l'eau de rinçage usée est réutilisée après une séparation des ions et un dépôt d'autres substances contenues au moyen de charbon actif. Dans un procédé particulièrement simple et universellement applicable, il est proposé selon l'invention que l'on traite l'eau de rinçage usée tout d'abord avec du charbon actif et seulement ensuite avec un échangeur d'ions.
PCT/EP1992/001902 1991-08-29 1992-08-20 Procede pour le rinçage de surfaces metalliques degraissees et nettoyees WO1993004779A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914128648 DE4128648A1 (de) 1991-08-29 1991-08-29 Verfahren zum spuelen von entfetteten und gereinigten metalloberflaechen
DEP4128648.0 1991-08-29

Publications (1)

Publication Number Publication Date
WO1993004779A1 true WO1993004779A1 (fr) 1993-03-18

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Application Number Title Priority Date Filing Date
PCT/EP1992/001902 WO1993004779A1 (fr) 1991-08-29 1992-08-20 Procede pour le rinçage de surfaces metalliques degraissees et nettoyees

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DE (1) DE4128648A1 (fr)
WO (1) WO1993004779A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016215233A1 (de) * 2016-08-16 2018-02-22 Bayerische Motoren Werke Aktiengesellschaft Verfahren und Vorrichtung zum Entfetten eines Bauteils
JP6642782B1 (ja) * 2018-08-17 2020-02-12 Jfeスチール株式会社 絶縁被膜形成用処理液の製造方法および絶縁被膜付き鋼板の製造方法ならびに絶縁被膜形成用処理液の製造装置

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4822383A (fr) * 1971-07-29 1973-03-27 Nihon Filter Co Ltd
DE2262789A1 (de) * 1971-12-21 1973-07-05 Sanshin Mfg Co Ltd Verfahren zum regeln der zusammensetzung eines chromatierungsbades
JPS5038637A (fr) * 1973-08-09 1975-04-10
US4182676A (en) * 1974-06-27 1980-01-08 Almag Chemical Corp. Method and system for purifying liquid
DE2847435A1 (de) * 1978-11-02 1980-05-22 Dambach Guetling Gmbh Verfahren und vorrichtung zum entfernen von metallen und metallkomplexen aus abwaessern
GB2056314A (en) * 1979-08-13 1981-03-18 Vaponics Purification of water involving ultrafiltration
JPS5715885A (en) * 1980-06-30 1982-01-27 Nippon Rensui Kk Method for recovery of high-purity waste water of washing
US4863612A (en) * 1987-08-10 1989-09-05 Kinetico, Inc. Apparatus and method for recovering materials from process baths
US4952320A (en) * 1986-11-05 1990-08-28 Fremont Industries, Inc. Chromium recovery process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4822383A (fr) * 1971-07-29 1973-03-27 Nihon Filter Co Ltd
DE2262789A1 (de) * 1971-12-21 1973-07-05 Sanshin Mfg Co Ltd Verfahren zum regeln der zusammensetzung eines chromatierungsbades
JPS5038637A (fr) * 1973-08-09 1975-04-10
US4182676A (en) * 1974-06-27 1980-01-08 Almag Chemical Corp. Method and system for purifying liquid
DE2847435A1 (de) * 1978-11-02 1980-05-22 Dambach Guetling Gmbh Verfahren und vorrichtung zum entfernen von metallen und metallkomplexen aus abwaessern
GB2056314A (en) * 1979-08-13 1981-03-18 Vaponics Purification of water involving ultrafiltration
JPS5715885A (en) * 1980-06-30 1982-01-27 Nippon Rensui Kk Method for recovery of high-purity waste water of washing
US4952320A (en) * 1986-11-05 1990-08-28 Fremont Industries, Inc. Chromium recovery process
US4863612A (en) * 1987-08-10 1989-09-05 Kinetico, Inc. Apparatus and method for recovering materials from process baths
US4863612B1 (en) * 1987-08-10 1994-11-01 Kineticon Inc Apparatus and method for recovering materials from process baths

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7410, Derwent Publications Ltd., London, GB; AN 74-18090V & JP,A,48 022 383 (NIHON FILTER) 22. März 1973 *
DATABASE WPI Week 7633, Derwent Publications Ltd., London, GB; AN 76-62100X & JP,A,50 038 637 (DAI NIPPON TORYO) 10. April 1975 *
DATABASE WPIL Week 8209, Derwent Publications Ltd., London, GB; AN 82-16991E & JP,A,57 015 885 (MITSUBISHI ELECTRIC) 27. Januar 1982 *

Also Published As

Publication number Publication date
DE4128648A1 (de) 1993-03-04

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