EP0960221B1 - 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 Download PDF

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Publication number
EP0960221B1
EP0960221B1 EP97949093A EP97949093A EP0960221B1 EP 0960221 B1 EP0960221 B1 EP 0960221B1 EP 97949093 A EP97949093 A EP 97949093A EP 97949093 A EP97949093 A EP 97949093A EP 0960221 B1 EP0960221 B1 EP 0960221B1
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EP
European Patent Office
Prior art keywords
pickling
titanium
alloys
products made
solution
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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
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EP97949093A
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English (en)
French (fr)
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EP0960221A1 (de
Inventor
Franco Mancia
Sandro Fortunati
Ezio Novaro
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Acciai Speciali Terni SpA
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Acciai Speciali Terni SpA
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    • 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

  • the present invention relates to a method for pickling products made of stainless steel, which avoids the use of nitric acid as an oxidising agent.
  • the present invention can also be applied for pickling of titanium and alloys thereof.
  • pickling is the process used to remove the layer of oxidation that forms as a result of heat treating of steel.
  • nitric acid HNO 3
  • hydrofluoric acid HF
  • a method exists that foresees a reduction in the amount of nitrogen oxides NO 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.
  • 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 stainless steel, and products made of titanium and alloys thereof, in the absence of nitric acid as an oxidising agent, wherein the product to be pickled is submerged in the pickling solution which forms the anolyte 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, and the anodic reaction being potentiostatically controlled.
  • the catholyte of the cell is preferably made up of an aqueous solution of sulphuric acid and is send out of the cathodic compartment into the pickling solution, to reintegrate the H 2 SO 4 that is consumed during the pickling reaction.
  • 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:
  • products containing iron for which the method according to the present invention is applicable are selected from the group comprising:
  • products containing titanium for which the method according to the present invention is applicable are selected from the group comprising:
  • the method object of the present invention is based on the replacement of nitric acid and on the theory that this acid performs two basic operations:
  • the overall action of the nitric acid can thus be obtained using various reagents capable of guaranteeing these two specific actions, even separately.
  • the reagents selected to control the total acidity are therefore mineral acids and oxidising agents.
  • 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 oxidising agent directly in the pickling bath.
  • the method object of the present invention is based on the used of a pickling bath that does not contain nitric acid, but contains in its place a mineral acid (for example sulphuric acid) and as an oxidant contains only the ferric ion Fe 3+ (or, in the case of titanium, the ions Ti 3+ and Ti 4+ ).
  • the ferric ion is not added in the form of a reagent, but is obtained directly in the pickling solution by anodic oxidation in an electrolytic cell of the ions Fe 2+ that are generated during the pickling process itself (dissolution of the steel).
  • anodic oxidation of the Ti 2+ ions to Ti 3+ and Ti 4+ ions is carried out in the cell.
  • FIG. 1 A diagram of a preferred embodiment of the method according to the invention is illustrated in figure 1.
  • an electro-chemical cell of the membrane type is used, worked by controlling the anodic potential or using a galvanostatic control.
  • the cell anolyte (in which the reaction generating Fe 3+ ions takes place) is made of the same solution as the pickling bath, whereas the catholyte used is a solution of sulphuric acid that is destined to be sent to the pickling bath.
  • the mineral acids used as anolyte are mixtures of hydrofluoric, sulphuric, hydrochloric and phosphoric acid.
  • the method provides a self-balancing system, that is to say one that is capable of controlling the process kinetics and the final quality of the product.
  • the pickling kinetics are in fact directly controllable according to the speed of production of Fe 3+ ions in the cell.
  • Control of the concentration of Fe 3+ ions in the pickling bath also allows close control of the most critical process parameter (that is to say the redox potential value of the system), also giving obvious advantages for the final quality of the product.
  • the pickling bath can conveniently use the following reagents:
  • the method object of the invention foresees electro-chemical treatment of the solution, by which it is possible to obtain direct formation of the oxidising agent and control of the correct concentration levels directly within the bath.
  • the same pickling solution is used, and is continuously circulated (but discontinuous treatment can also be foreseen) from the bath by pumping;
  • This reaction produces the Fe 3+ that serves to maintain the concentration of the oxidising agent Fe 3+ in the pickling bath constant.
  • the pickling mechanism in the presence of Fe 3+ as an oxidant takes place using the following reactions: (1) Fe ⁇ Fe 2+ + 2e (primary oxidation semi-reaction to dissolve the metallic iron); (2) Fe 3+ + e ⁇ Fe 2+ (reduction semi-reaction).
  • reaction (4) is the inverse reaction to (2).
  • the ion Fe 3+ reduces to Fe 2+ during (2) in the bath and oxidises again in the cell from Fe 2+ in (4).
  • the oxidising capacity of the system is thus guaranteed by passage of the anodic current in the cell in reaction (4), in which the ion Fe 3+ is a go-between and, according to the present method, no other reagents are added as oxidants.
  • 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.
  • chrome with valence 6 often toxic
  • the cell is provided with a suitable membrane. It is possible to use membranes of different effectiveness, working temperature and duration.
  • the electro-chemical cell in reference when tested in the system has provided the following performance levels, which are given below in the form of an example:
  • the anodic cell potential in this case is selected within the range of between -368 mV SHE (oxidation of Ti 2+ to Ti 4+ ) and 1229 mV SHE (development of oxygen).
  • the method according to a second embodiment of the invention foresees, for pickling of titanium and alloys thereof, the use of the same baths and acid solutions containing Fe 3+ that are used for pickling of stainless steel. This method is very convenient, because the majority of titanium coil manufacturers process these coils on the same lines used for stainless steel.
  • the ion Fe 3+ (and the ion Fe 2+ from which it is formed) does not participate in the overall reaction balance, so there is no consumption of the quantity of iron ions contained in the bath, whereas the oxidising capacity, in terms of electron transfer, is ensured by the passage of current to the cell anode.
  • the example of a pickling process refers to a coil of hot laminated and peened AISI 304 steel.
  • the initial pickling solution is made up of:
  • the pickling process commences (tape sent into the pickling bath) at the line speed foreseen.
  • the line speed, the thickness and the width of the treated tape obviously define the production level per hour, expressed in t/h of pickled tape (e.g. at a speed of 18 metres/minute, tape thickness 3.2 mm and width 1500 mm the production of pickled tape will be approximately 40 t/h).
  • the tape is 3.2 mm thick (typical average thickness of hot-laminated products).
  • the pickling bath can be made up of the anodic part of the cell, without the need to create external circulation of the anolyte between the bath and the cell.
  • the catholyte it is not necessarily essential to resort to solutions using sulphuric acid, as different electrolytes can be chosen (e.g. HCl, mixtures of HCl/H 2 SO 4 or others), including the pickling solution itself which is eliminated as waste. Input of the catholyte into the bath may also not be necessary, in particular when electrolytes other than those used in the pickling bath are chosen. All the above variations are alternatives to the one described and illustrated as the preferred embodiment, and are understood to fall within the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (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)

Claims (11)

  1. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, oder von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, in Abwesenheit von Salpetersäure als Oxidationsmittel, wobei das zu beizende Erzeugnis in die Beizlösung eingetaucht wird, welche den Anoiyt einer elektrolytischen Zelle bildet, in welcher der Anolyt aus einer wässrigen Lösung von Schwefelsäure, von Fluorwasserstoffsäure und gegebenenfalls von Phosphorsäure und Chlorwasserstoffsäure gebildet ist, und wobei der Katholyt aus einer wässrigen Lösung von Schwefelsäure gebildet ist, wobei das Oxidationsmittel in der Beizlösung das Eisen(III)-Ion oder die lonen Titan(III) und Titan(IV) sind, die in der Anode durch Oxidation des Eisen(II)-Ions oder des Ions Titan(II) gebildet werden, welche von der Auflösung der Oberflächenschichten des zu beizenden Erzeugnisses herrühren, und wobei die Anodenreaktion potentiostatisch geregelt wird.
  2. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, nach Anspruch 1, in welchem das elektrochemische Arbeitspotential der Zellenanode zwischen 771 und 1229 mV SHE (Standardwasserstoffelektrode) beträgt.
  3. Verfahren zum Beizen von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach Anspruch 1, in welchem das elektrochemische Arbeitspotential der Zellenanode zwischen -368 und 1229 mV SHE (Standardwasserstoffelektrode) beträgt.
  4. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, und von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach einem der vorangehenden Ansprüche, in welchem die Beizvorgänge auf kontinuierliche oder diskontinuierliche Weise mittels einer kontinuierlichen oder diskontinuierlichen Umwälzung des Anolyts durchgeführt werden.
  5. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, und von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach dem vorangehenden Anspruch, in welchem das Beizbad, welches den Anolyt enthält, die Anodenkammer in der elektrochemischen Zelle bildet.
  6. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, und von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach einem der vorangehenden Ansprüche, in welchem der Katholyt der elektrolytischen Zelle aus einer Lösung von Schwefelsäure gebildet ist und beim Verlassen der Kathodenkammer in die Beizlösung als Anolyt geleitet wird.
  7. Verfahren nach dem vorangehenden Anspruch, in welchem die Katholytlösung aus einem beliebigen Elektrolyt gebildet ist, der entweder in den Anolyt geleitet oder nicht geleitet werden kann.
  8. Verfahren nach einem der vorangehenden Ansprüche, in welchem der Katholyt aus der Beizlösung gebildet ist und anschließend als Abfall aus dem Kathodenbereich ausgetragen wird.
  9. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, und von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach einem der vorangehenden Ansprüche, in welchem das Beizbad eine Temperatur zwischen 40 und 90°C hat und aus einer wässrigen Lösung gebildet ist, welche die folgenden Bestandteile enthält:
    freie HCl zwischen 0 und 50 g/l
    freie H3PO4 zwischen 0 und 200 g/l
    freie H2SO4 von 50 bis 250 g/l
    freie HF von 5 bis 50 g/l
    Fegesamt in Lösung ≥ 50 g/l
    und alternativ, für Erzeugnisse aus Titan und Legierungen davon, Tigesamt in Lösung ≥ 50 g/l.
  10. Verfahren zum Beizen von Erzeugnissen, die aus nichtrostendem Stahl gefertigt sind, nach einem der Ansprüche 1, 2 und 4-9, in welchem die Erzeugnisse, die aus nichtrostendem Stahl gefertigt sind, ausgewählt werden aus der Gruppe umfassend:
    nichtrostenden, laminierten oder jedenfalls warm- und/oder kaltverarbeiteten Stahl, insbesondere austenitischen Stahl, ferritischen Stahl, Duplex-Stahl und extrem nichtrostenden Stahl (super-stainless steel); und
    Superlegierungen auf Ni-Basis.
  11. Verfahren zum Beizen von Erzeugnissen, die aus Titan und Legierungen davon gefertigt sind, nach einem der Ansprüche 1, 3 und 4-10, in welchem die Erzeugnisse, die Titan und Legierungen davon enthalten, ausgewählt sind aus der Gruppe umfassend:
    CP-Titan (Titan mit handelsüblicher Reinheit) verschiedener Qualitätsstufen;
    Titanlegierungen.
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
ITRM960849 1996-12-09
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
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 EP0960221A1 (de) 1999-12-01
EP0960221B1 true EP0960221B1 (de) 2002-03-13

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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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
CN103572303A (zh) * 2013-10-24 2014-02-12 奇瑞重工股份有限公司 一种钢材化学前处理方法及所用酸洗液

Families Citing this family (9)

* 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
KR100777171B1 (ko) 2002-10-15 2007-11-16 헨켈 코만디트게젤샤프트 아우프 악티엔 강 및 스테인레스강을 위한 산세 또는 광택/부동태화 용액및 방법
EP1980650A1 (de) * 2007-04-05 2008-10-15 Kerma S.A. Nitrat- und Peroxydfreie Beizzusammensetzung und Verfahren zur Umsetzung einer solchen Zusammensetzung
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
CN103572303A (zh) * 2013-10-24 2014-02-12 奇瑞重工股份有限公司 一种钢材化学前处理方法及所用酸洗液

Also Published As

Publication number Publication date
DE69711090T2 (de) 2003-07-24
ZA9710983B (en) 1998-06-15
TW451001B (en) 2001-08-21
ITRM960849A0 (it) 1996-12-09
ITRM960849A1 (it) 1998-06-09
EP0960221A1 (de) 1999-12-01
ES2178023T3 (es) 2002-12-16
ATE214436T1 (de) 2002-03-15
AU7847898A (en) 1998-07-03
WO1998026111A1 (en) 1998-06-18
DE69711090D1 (de) 2002-04-18
IT1288407B1 (it) 1998-09-22

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