EP0101126A2 - Procédé pour traiter des pâtes de décapage usées - Google Patents

Procédé pour traiter des pâtes de décapage usées Download PDF

Info

Publication number
EP0101126A2
EP0101126A2 EP83201149A EP83201149A EP0101126A2 EP 0101126 A2 EP0101126 A2 EP 0101126A2 EP 83201149 A EP83201149 A EP 83201149A EP 83201149 A EP83201149 A EP 83201149A EP 0101126 A2 EP0101126 A2 EP 0101126A2
Authority
EP
European Patent Office
Prior art keywords
paste
calcium carbonate
pickling
fluoride
particle size
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.)
Granted
Application number
EP83201149A
Other languages
German (de)
English (en)
Other versions
EP0101126A3 (en
EP0101126B1 (fr
Inventor
Josef Rones
Siegfried Möller
Kurt Moesner
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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 Metallgesellschaft AG filed Critical Metallgesellschaft AG
Priority to AT83201149T priority Critical patent/ATE19661T1/de
Publication of EP0101126A2 publication Critical patent/EP0101126A2/fr
Publication of EP0101126A3 publication Critical patent/EP0101126A3/de
Application granted granted Critical
Publication of EP0101126B1 publication Critical patent/EP0101126B1/fr
Expired 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes

Definitions

  • the invention relates to a method for transferring located on metal surfaces processed, fluoridated B eizpasten in environmentally friendly products.
  • metal surfaces e.g. made of steel and / or aluminum and their alloy
  • unsightly and corrosion-promoting oxide layers such as those e.g. in the heat treatment of metals (welding) or caused by the effects of the environment.
  • acid solutions e.g. based on hydrochloric acid, sulfuric acid, phosphoric acid or hydrofluoric acid.
  • Acid-containing pastes can also be applied to the areas to be cleaned, especially for large parts or local oxide formation. This dissolves part of the oxides and the base metal attached to them, so that the oxides lose their adhesion to the metal surface. After an appropriate time, they are rinsed off with water or removed by brushing.
  • Such a pickling or rust removal paste based on phosphoric acid contains e.g. As a thickener, saponifiable oil or a fatty acid that can be converted into a soap (DE-AS 10 82 475).
  • Another known cleaning and etching agent consists of hydrofluoric acid, a magnesium compound, at least one acid from the group consisting of nitric acid, phosphoric acid and sulfuric acid in the form of free acid or in the form of their salts and a certain sulfonic acid (DE-AS 19 50 560).
  • pickling and rust removal pastes have been proposed which, in addition to fluoride ions, contain a mixture of compounds of calcium and of trivalent iron and / or aluminum and have an acidity corresponding to at least 10% by weight of free acid (calculated as 100% HF) (DE -OS 31 05 508).
  • Such pickling pastes are primarily intended for the treatment of alloyed steels.
  • the object of the invention is to provide a method for transferring processed pickling pastes located on metal surfaces, which avoids the disadvantages of the known methods and yet can be carried out simply and without cost.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that an aqueous, calcium carbonate with a particle size of max. 5 ⁇ m and paste containing alkali bicarbonate with a pH of max. 9.5 applies.
  • the amount of calcium ions offered must be so high that the fluoride ions of the processed pickling paste can be converted into insoluble calcium fluoride by the calcium.
  • the simultaneous presence of alkali hydrogen carbonate has a neutralizing effect, the pH in aqueous solution - even when overdosed - not exceeding 8.4 (measured as a 1% sodium bicarbonate solution).
  • alkaline compounds e.g. of sodium carbonate
  • the pH can be increased to max. 9.5 can be increased.
  • the particle size of calcium carbonate plays a role insofar as particles larger than 5 / um react only imperfectly.
  • the inner layer of calcium carbonate becomes another Withdrawn reaction with fluoride ions or acid.
  • the completeness of the implementation, but also the speed of the reaction is increased.
  • the spreadability of the paste improves.
  • a preferred embodiment of the invention therefore provides to apply a paste whose calcium carbonate component is, preferably below 1 / um, having a particle size below 2 /.
  • Another particularly advantageous embodiment of the invention consists in applying a paste to the processed pickling paste, the calcium carbonate in an amount of 20 to 50% by weight, preferably 30 to 40% by weight, and alkali hydrogen carbonate in an amount of 20 to 50 wt .-%, preferably 30 to 40 wt .-%, (calculated as NaHC0 3 ) contains.
  • the surfactant in an amount of 0.1 to 10 g / kg paste, preferably 0.3 to 3 g / kg paste.
  • Particularly suitable surfactants are nonionic or anionic surfactants, in particular ethoxylated alkylphenols.
  • the paste is usually applied by brush application. Especially when the viscosity is low however, spray application is also possible.
  • the amount to be applied should be at least as large as the amount of pickling paste applied. A surplus is absolutely no problem because of the environmental compatibility.
  • the conversion of the processed pickling paste into environmentally friendly products is associated with a development of carbon dioxide gas, the completion of which simultaneously indicates the end of the reaction. It is therefore not necessary to observe the course of the reaction, for example by measuring the pH.
  • the duration of the reaction is generally from 1 to 5 minutes.
  • the reaction products on the metal surface are most conveniently removed with water. Depending on the nature of the treated metal surface, this can be done by brushing or spraying. Insofar as this is possible, the washing liquid can be freed from insoluble constituents by filtering or decanting and the aqueous phase can be drained into the sewage system.
  • the chemicals required for formulating the paste are inexpensive, that the paste has a long shelf life and that handling it requires no special precautionary measures.
  • a further significant advantage is that the metering presents no difficulties, in particular even a considerable overdosing does not require any special measures.
  • the reaction products obtained can also be deposited without special measures or their aqueous phase can be discharged into a sewage system which may be present.
  • a pickling paste was applied in a quantity of 100 g / m weld seam to various pipe sections made of chromium-nickel steel with a weld seam.
  • the pickling paste consisted of
  • the exposure time was set to 15 minutes.
  • a paste of likewise 40% by weight solids content (pH 8.5) was made from precipitated calcium carbonate with a particle size of approx. 1 ⁇ m and in. applied a quantity of 100 g / m weld seam to the processed pickling paste.
  • reaction products were rinsed off and a washing liquid with a pH of 5.4 and a fluoride content of 70 mg / l was obtained. It too could not be drained without a pH correction.
  • a paste was produced which duration. It was again applied in a quantity of 100 g / m of weld seam to the pickling paste being worked off and rinsed off after 5 minutes of exposure.
  • the washing liquid obtained had a pH of 7.2 and a fluoride content of 20 mg / l. Without further treatment, i.e. be drained into the sewage system only after decantation of the water-insoluble components.
  • Example 3 was repeated with the variant that the application quantity was doubled to 200 g / m weld seam.

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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Processing Of Solid Wastes (AREA)
EP83201149A 1982-08-18 1983-08-03 Procédé pour traiter des pâtes de décapage usées Expired EP0101126B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83201149T ATE19661T1 (de) 1982-08-18 1983-08-03 Verfahren zur behandlung abgearbeiteter beizpasten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3230603 1982-08-18
DE19823230603 DE3230603A1 (de) 1982-08-18 1982-08-18 Verfahren zur behandlung abgearbeiteter beizpasten

Publications (3)

Publication Number Publication Date
EP0101126A2 true EP0101126A2 (fr) 1984-02-22
EP0101126A3 EP0101126A3 (en) 1984-03-21
EP0101126B1 EP0101126B1 (fr) 1986-05-07

Family

ID=6171062

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83201149A Expired EP0101126B1 (fr) 1982-08-18 1983-08-03 Procédé pour traiter des pâtes de décapage usées

Country Status (5)

Country Link
US (1) US4478647A (fr)
EP (1) EP0101126B1 (fr)
JP (2) JPS5956585A (fr)
AT (1) ATE19661T1 (fr)
DE (2) DE3230603A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4847818A (en) * 1988-10-31 1989-07-11 Timex Corporation Wristwatch radiotelephone
JP2576323B2 (ja) * 1991-10-03 1997-01-29 カシオ計算機株式会社 演奏記録再生装置
US5467324A (en) * 1994-11-23 1995-11-14 Timex Corporation Wristwatch radiotelephone with deployable voice port
FI120742B (fi) * 2006-05-10 2010-02-15 Outokumpu Oy Menetelmä terästuotannon yhteydessä
GB201312158D0 (en) * 2013-07-05 2013-08-21 Xeros Ltd Method of treating a metal substrate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB843100A (en) * 1956-01-14 1960-08-04 Geigy Co Ltd Improvements in the cleaning of metal surfaces
CH359950A (de) * 1956-04-12 1962-01-31 Parker Ste Continentale Entrostungspaste, Verfahren zu deren Herstellung und Verwendung derselben
GB1067293A (en) * 1964-09-28 1967-05-03 Ici Ltd Treatment of waste liquor from pickling of ferrous metals
US4032466A (en) * 1976-04-16 1977-06-28 Basf Wyandotte Corporation Acid cleaner and process for disposal thereof
FR2382406A1 (fr) * 1977-03-02 1978-09-29 Voest Ag Procede de neutralisation de liquides contenant des acides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE351444B (fr) * 1970-11-03 1972-11-27 Nordstjernan Rederi Ab
US3959132A (en) * 1974-10-25 1976-05-25 Galson Technical Services, Inc. Methods for removing fluoborates from aqueous media
US4045339A (en) * 1975-08-05 1977-08-30 Dart Industries Inc. Waste treatment of fluoroborate solutions
DE3105508A1 (de) * 1981-02-14 1982-09-02 Metallgesellschaft Ag, 6000 Frankfurt Beiz- und entrostungspaste fuer metalle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB843100A (en) * 1956-01-14 1960-08-04 Geigy Co Ltd Improvements in the cleaning of metal surfaces
CH359950A (de) * 1956-04-12 1962-01-31 Parker Ste Continentale Entrostungspaste, Verfahren zu deren Herstellung und Verwendung derselben
GB1067293A (en) * 1964-09-28 1967-05-03 Ici Ltd Treatment of waste liquor from pickling of ferrous metals
US4032466A (en) * 1976-04-16 1977-06-28 Basf Wyandotte Corporation Acid cleaner and process for disposal thereof
FR2382406A1 (fr) * 1977-03-02 1978-09-29 Voest Ag Procede de neutralisation de liquides contenant des acides

Also Published As

Publication number Publication date
EP0101126A3 (en) 1984-03-21
US4478647A (en) 1984-10-23
JPS5956585A (ja) 1984-04-02
ATE19661T1 (de) 1986-05-15
EP0101126B1 (fr) 1986-05-07
DE3230603A1 (de) 1984-02-23
DE3363397D1 (en) 1986-06-12
JPS5956586A (ja) 1984-04-02

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