EP0960221A1 - Verfahren zum beizen von eisen enthaltenden metallegierungen und titan und seinen legierungen - Google Patents

Verfahren zum beizen von eisen enthaltenden metallegierungen und titan und seinen legierungen

Info

Publication number
EP0960221A1
EP0960221A1 EP97949093A EP97949093A EP0960221A1 EP 0960221 A1 EP0960221 A1 EP 0960221A1 EP 97949093 A EP97949093 A EP 97949093A EP 97949093 A EP97949093 A EP 97949093A EP 0960221 A1 EP0960221 A1 EP 0960221A1
Authority
EP
European Patent Office
Prior art keywords
pickling
titanium
alloys
products made
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.)
Granted
Application number
EP97949093A
Other languages
English (en)
French (fr)
Other versions
EP0960221B1 (de
Inventor
Franco Mancia
Sandro Fortunati
Ezio Novaro
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.)
Acciai Speciali Terni SpA
Original Assignee
Centro Sviluppo Materiali SpA
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 Centro Sviluppo Materiali SpA filed Critical Centro Sviluppo Materiali SpA
Publication of EP0960221A1 publication Critical patent/EP0960221A1/de
Application granted granted Critical
Publication of EP0960221B1 publication Critical patent/EP0960221B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel
    • 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
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • 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
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/08—Refractory metals

Definitions

  • a method exists that foresees a reduction in the amount of nitrogen oxides N0 X that are developed by the bath.
  • Said method is generally based on the use of hydrogen peroxide, which not only makes it possible, if necessary, to reduce the total amount of nitric acid in the bath and required for the process, but also to oxidise the nitrogen oxides to the highest state of oxidation.
  • this method has the disadvantage that it only partially solves the problems mentioned above, as it only allows a reduction of the NO x content in the vapours, not its elimination, and it leaves the problem of nitrates in the exhausted baths unsolved.
  • more or less complex variations in the basic pickling process that is to say HF/HNO 3 mixtures
  • Another method is known, the purpose of which is to eliminate the presence of nitric acid altogether, using sulphuric acid, ferric sulphate and hydrogen peroxide alongside the hydrofluoric acid, the presence of which remains practically unchanged in the processes examined here .
  • the aim of the present invention is therefore to solve the above mentioned problems, providing a method for pickling products made of metal alloys containing iron, and products made of titanium and alloys thereof, in the absence of nitric acid as an oxidising agent, characterised by the fact that the product to be pickled is submerged in the anolyte (as the pickling solution) of an electrolytic cell in which the anolyte is made up of an aqueous solution of sulphuric acid, of hydrofluoric acid and optionally of phosphoric acid and hydrochloric acid, and with the catholyte made up of an aqueous solution of sulphuric acid, the oxidising agent in the pickling solution being the ferric ion, or the ions titanium (III) and titanium (IV) , formed in the anode by oxidation of the ferrous ion, or of the ion titanium (II) , resulting from dissolution of the surface layers of the product to be pickled.
  • the pickling bath forms the anolyte of the cell, and is maintained at a temperature preferably comprised between 45 and 85°C, and it is made up of an aqueous solution of sulphuric acid, of hydrofluoric acid and optionally of hydrochloric and phosphoric acid, with the following composition expressed as a percentage by weight:
  • the method according to the present invention does not resort to direct addition of reagents into the bath, but uses electro-chemical treatment of the solution which generates the desired oxidasing agent directly in the pickling bath.
  • reaction (7) and (4) would, in fact, decrease the efficiency of the cell, attenuating the undesired water hydrolysis reaction by developing oxygen.
  • the chosen potential E is thus in the range of between 771 and 1229 mV SHE.
  • potential values of this kind among other things, there is no formation of chrome with valence 6 (often toxic) , according to the simplified reaction:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Electrolytic Production Of Metals (AREA)
EP97949093A 1996-12-09 1997-12-05 Verfahren zum beizen von eisen enthaltenden metallegierungen und titan und seinen legierungen Expired - Lifetime EP0960221B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IT96RM000849A IT1288407B1 (it) 1996-12-09 1996-12-09 Metodo per il decapaggio di prodotti in lega metallica contenente ferro e di titanio e sue leghe
ITRM960849 1996-12-09
PCT/IT1997/000300 WO1998026111A1 (en) 1996-12-09 1997-12-05 Method for pickling products in a metal alloy containing iron and in titanium and alloys thereof

Publications (2)

Publication Number Publication Date
EP0960221A1 true EP0960221A1 (de) 1999-12-01
EP0960221B1 EP0960221B1 (de) 2002-03-13

Family

ID=11404582

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97949093A Expired - Lifetime EP0960221B1 (de) 1996-12-09 1997-12-05 Verfahren zum beizen von eisen enthaltenden metallegierungen und titan und seinen legierungen

Country Status (9)

Country Link
EP (1) EP0960221B1 (de)
AT (1) ATE214436T1 (de)
AU (1) AU7847898A (de)
DE (1) DE69711090T2 (de)
ES (1) ES2178023T3 (de)
IT (1) IT1288407B1 (de)
TW (1) TW451001B (de)
WO (1) WO1998026111A1 (de)
ZA (1) ZA9710983B (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1297076B1 (it) * 1997-11-24 1999-08-03 Acciai Speciali Terni Spa Metodo per il decapaggio di prodotti in acciaio
IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
DE19850524C2 (de) * 1998-11-03 2002-04-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Nitratfreies Recycling-Beizverfahren für Edelstähle
AT406486B (de) * 1998-12-22 2000-05-25 Andritz Patentverwaltung Verfahren zum beizen von edelstahl
IT1312556B1 (it) * 1999-05-03 2002-04-22 Henkel Kgaa Processo di decapaggio di acciaio inossidabile in assenza di acidonitrico ed in presenza di ioni cloruro
JP4332115B2 (ja) 2002-10-15 2009-09-16 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 鋼及びステンレス鋼の酸洗い又は光沢化／不動態化用溶液及び方法
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
EP1980650A1 (de) * 2007-04-05 2008-10-15 Kerma S.A. Nitrat- und Peroxydfreie Beizzusammensetzung und Verfahren zur Umsetzung einer solchen Zusammensetzung
CN103572303B (zh) * 2013-10-24 2015-11-25 中联重机股份有限公司 一种钢材化学前处理方法及所用酸洗液
CN111057935B (zh) * 2019-12-25 2021-04-02 浦项(张家港)不锈钢股份有限公司 一种耐热不锈钢的制备方法
CN113788520A (zh) * 2021-10-08 2021-12-14 北京首钢吉泰安新材料有限公司 一种铁铬铝酸洗的工艺及废水处理方法和废水处理装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50133125A (de) * 1974-04-10 1975-10-22
DE3937438C2 (de) * 1989-02-23 1998-01-29 Wilfried Simmer Verfahren zum Beizen von Stahl
FR2650303B1 (fr) * 1989-07-26 1993-12-10 Ugine Aciers Chatillon Gueugnon Procede de decapage en bain acide de produits metalliques contenant du titane ou au moins un element chimique de la famille du titane
JPH04362183A (ja) * 1991-06-07 1992-12-15 Nippon Paint Co Ltd アルミニウム表面洗浄浴の再生方法
IT1282979B1 (it) * 1996-05-09 1998-04-03 Novamax Itb S R L Procedimento per il decapaggio dell'acciaio nel quale la ossidazione dello ione ferroso formatosi viene effettuata per via elettrochimica

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9826111A1 *

Also Published As

Publication number Publication date
ITRM960849A1 (it) 1998-06-09
ITRM960849A0 (it) 1996-12-09
ATE214436T1 (de) 2002-03-15
AU7847898A (en) 1998-07-03
DE69711090D1 (de) 2002-04-18
DE69711090T2 (de) 2003-07-24
EP0960221B1 (de) 2002-03-13
IT1288407B1 (it) 1998-09-22
WO1998026111A1 (en) 1998-06-18
TW451001B (en) 2001-08-21
ES2178023T3 (es) 2002-12-16
ZA9710983B (en) 1998-06-15

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