EP0603763B1 - Utilisation d'inhibiteurs facilement éliminables dans des acides de décapage - Google Patents

Utilisation d'inhibiteurs facilement éliminables dans des acides de décapage Download PDF

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Publication number
EP0603763B1
EP0603763B1 EP93120411A EP93120411A EP0603763B1 EP 0603763 B1 EP0603763 B1 EP 0603763B1 EP 93120411 A EP93120411 A EP 93120411A EP 93120411 A EP93120411 A EP 93120411A EP 0603763 B1 EP0603763 B1 EP 0603763B1
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EP
European Patent Office
Prior art keywords
inhibitor
inhibitors
pickling
pickling acids
acids
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.)
Expired - Lifetime
Application number
EP93120411A
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German (de)
English (en)
Other versions
EP0603763A1 (fr
Inventor
Günther Dr. Wasow
Lothar Klicker
Hay Fieten
Klaus Dr. Tebbe
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.)
Norsk Hydro Chemtech GmbH
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Norsk Hydro Chemtech GmbH
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Publication date
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Publication of EP0603763A1 publication Critical patent/EP0603763A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
    • 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
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the invention relates to the use of special inhibitors in pickling acids which can be eliminated by conventional methods in the processing of the used pickling acids.
  • the invention further relates to pickling acids which contain these inhibitors and to a process for cleaning the used pickling acids.
  • the stain itself not only has the task of creating a bright metallic surface, but also has to ensure complete wetting in the zinc bath, the subsequent treatment not being impaired.
  • the properties of the stains are largely determined by the addition of inhibitors and activators. Inhibitors delay the attack on the iron, but should hardly hinder the dissolution of the oxides.
  • Activators are generally nonionic surface-active substances (e.g. alkylphenol-ethylene oxide adducts), which are intended to guarantee a uniform attack of the acid even at those locations on the metal surface which still contain residual fat.
  • alkylphenol-ethylene oxide adducts e.g. alkylphenol-ethylene oxide adducts
  • Remaining organic contaminants can disrupt individual steps in the treatment process. B. diffusion dialysis, electrodialysis, electrolysis, precipitation reactions, liquid-liquid extraction and spray roasting. Furthermore, the presence of organic contaminants will have a very negative impact on the quality of the end products produced.
  • the additives used in the pickling process should not constitute or form toxic substances, since this would restrict the recyclability of the end products and would result in hazardous waste.
  • alkylamine polyethylene oxide compounds as inhibitors in metal stains.
  • certain alkylamine polyethylene oxide compounds are used in a mixture with thiourea compounds for this purpose.
  • US-A-2583098 shows the need to remove the corrosion inhibitor before working up the pickling solution, for example by means of activated carbon absorption. A connection between inhibitor type and removal options is not seen.
  • the invention therefore relates to the use of a mixture of alkylamine polyethylene oxide compounds of the general formula in which R is an alkyl radical having 16 to 18 carbon atoms, consisting of 95-97 parts by weight of alkylamine polyethylene oxide with a total of b + c of 6.8 to 7.2 and 3 - 5 parts by weight of alkylamine polyethylene oxide with a total of b + c of 2.8 to 3.5, as an inhibitor in acidic metal stains.
  • the surface tension of the inhibitor system measured in a solution of 50 mg inhibitor and 100 g FeCl2 in 1 liter of 5% hydrochloric acid, is in the range from 33 to 45 mN / m, preferably from 38 to 42 mN / m; the Nernst distribution coefficient of the inhibitor in the aforementioned hydrochloric iron (II) chloride solution compared to an oil phase consisting of 50 g octadecanoic acid (stearic acid) and 950 g n-heptane should be at least O / W - 1:25.
  • the invention furthermore relates to acidic metal pickles containing a mixture of alkylamine polyethylene oxide compounds according to claim 1 as inhibitors and a process for cleaning these metal pickles according to consumption, which is characterized in that the inhibitor / activator mixture contained is removed before further workup.
  • Further splitting methods include, for example, emulsion splitting (coalescence devices, micro- or ultrafiltration) and foaming (flotation).
  • the highly surface-active compound with the low degree of ethoxylation has a hydrophobic effect on the surface of the filter material, so that the entire inhibitor / activator system and if necessary, remove oily and surface-active substances from the degreasing bath.
  • adsorbents e.g. activated carbon
  • 25 m3 hydrochloric acid with a hydrogen chloride content of 15% and 2.4 kg of oxyethylated C16 / C18-alkylamine with a degree of oxyethylation of 7 and 0.1 kg of oxyethylated C16 / 18-alkylamine with a degree of oxyethylation of 3 are used as inhibitors for a freshly prepared acidic metal pickle -Activator system used.

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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (6)

  1. Utilisation d'un mélange de composés alkylaminepolyéthylèneoxydes, de formule générale
    Figure imgb0004
     dans laquelle R représente un radical alkyle ayant de 16 à 18 atomes de carbone, constitué par
    de 95 à 97 parties en poids d'alkylaminepolyéthylèneoxyde ayant une somme b+c de 6,8 à 7,2 et
    de 3 à 5 parties en poids d'alkylaminepolyéthylèneoxyde ayant une somme b+c de 2,8 à 3,5,
    comme inhibiteur dans les bains de décapage acides pour les métaux.
  2. Utilisation des composés alkylaminepolyéthylèneoxydes selon la revendication 1 dans des concentrations de 20 à 500 mg/l, en particulier de 50 à 150 mg/l, dans l'acide de décapage.
  3. Bains de décapage acides pour des métaux comportant des inhibiteurs selon les revendications 1 et 2.
  4. Procédé pour la purification de bains de décapage acides usés pour les métaux, comportant des inhibiteurs selon la revendication 3, caractérisé en ce que l'on élimine le système inhibiteur-activateur contenu avant le traitement ultérieur.
  5. Procédé selon la revendication 4, caractérisé en ce que l'élimination de l'inhibiteur s'effectue par adsorption sur des moyens d'adsorption conventionnels.
  6. Procédé selon la revendication 5, caractérisé en ce que l'élimination de l'inhibiteur s'effectue par adsorption sur du charbon actif.
EP93120411A 1992-12-24 1993-12-17 Utilisation d'inhibiteurs facilement éliminables dans des acides de décapage Expired - Lifetime EP0603763B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4244245 1992-12-24
DE4244245A DE4244245A1 (de) 1992-12-24 1992-12-24 Verwendung von leicht entfernbaren Inhibitoren in Beizsäuren

Publications (2)

Publication Number Publication Date
EP0603763A1 EP0603763A1 (fr) 1994-06-29
EP0603763B1 true EP0603763B1 (fr) 1995-09-06

Family

ID=6476650

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93120411A Expired - Lifetime EP0603763B1 (fr) 1992-12-24 1993-12-17 Utilisation d'inhibiteurs facilement éliminables dans des acides de décapage

Country Status (5)

Country Link
EP (1) EP0603763B1 (fr)
AT (1) ATE127538T1 (fr)
DE (2) DE4244245A1 (fr)
DK (1) DK0603763T3 (fr)
ES (1) ES2077465T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102023123910A1 (de) * 2023-09-05 2025-03-06 Spiraltec Gmbh Metallabtrennung aus sauren wässrigen Lösungen
DE102023123911A1 (de) * 2023-09-05 2025-03-06 Spiraltec Gmbh Abwasserfreie Behandlung von sauren wässrigen metallsalzhaltigen Lösungen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19618899A1 (de) * 1996-05-10 1997-11-13 Metallgesellschaft Ag Verfahren zum Entfernen von mit Seifen behafteten Konversionsschichten von metallischen Werkstücken

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE481309A (fr) * 1947-03-25
US3113113A (en) * 1958-11-07 1963-12-03 Armour & Co Corrosion inhibitor compositions
US3056746A (en) * 1959-02-24 1962-10-02 Jr Frederick C Brightly Acid pickling composition with inhibitor
FR1283323A (fr) * 1960-12-23 1962-02-02 Cie D Applic Chimiques A L Ind Produit inhibiteur de l'attaque des métaux par les acides forts
GB1010753A (en) * 1963-08-22 1965-11-24 Ici Ltd Corrosion restraining compositions
JPS4989635A (fr) * 1972-12-27 1974-08-27
US4381249A (en) * 1979-05-14 1983-04-26 Bouffard Joseph O Rust removing and metal surface protecting composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102023123910A1 (de) * 2023-09-05 2025-03-06 Spiraltec Gmbh Metallabtrennung aus sauren wässrigen Lösungen
DE102023123911A1 (de) * 2023-09-05 2025-03-06 Spiraltec Gmbh Abwasserfreie Behandlung von sauren wässrigen metallsalzhaltigen Lösungen
WO2025051484A1 (fr) 2023-09-05 2025-03-13 Spiraltec Gmbh Élimination de métal de solutions aqueuses acides

Also Published As

Publication number Publication date
DE59300568D1 (de) 1995-10-12
ES2077465T3 (es) 1995-11-16
ATE127538T1 (de) 1995-09-15
EP0603763A1 (fr) 1994-06-29
DE4244245A1 (de) 1994-06-30
DK0603763T3 (da) 1995-12-04

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