EP0707668B1 - Verfahren zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband - Google Patents

Verfahren zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband Download PDF

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Publication number
EP0707668B1
EP0707668B1 EP94924237A EP94924237A EP0707668B1 EP 0707668 B1 EP0707668 B1 EP 0707668B1 EP 94924237 A EP94924237 A EP 94924237A EP 94924237 A EP94924237 A EP 94924237A EP 0707668 B1 EP0707668 B1 EP 0707668B1
Authority
EP
European Patent Office
Prior art keywords
rinsing
carbon dioxide
pickled
blown
hydrolysis
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
EP94924237A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0707668A1 (de
Inventor
Wilhelm Karner
Karl Jirenec
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.)
Andritz Patentverwaltungs GmbH
Original Assignee
Andritz Patentverwaltungs GmbH
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 Andritz Patentverwaltungs GmbH filed Critical Andritz Patentverwaltungs GmbH
Publication of EP0707668A1 publication Critical patent/EP0707668A1/de
Application granted granted Critical
Publication of EP0707668B1 publication Critical patent/EP0707668B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/02—Cleaning by the force of jets or sprays
    • B08B3/022—Cleaning travelling work
    • 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
    • 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
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/027—Associated apparatus, e.g. for pretreating or after-treating
    • C23G3/029—Associated apparatus, e.g. for pretreating or after-treating for removing the pickling fluid from the objects

Definitions

  • the invention relates to a method for the aftertreatment of pickled carbon steel hot strip by applying water in continuous rinsing systems.
  • the pickling acid carried out with the belt from the last pickling stage is fed into the rinsing system and treated with rinsing water from section to section in counterflow to the direction in which the belt runs. This results in a defined concentration gradation of hydrochloric acid and iron ions in the individual rinsing sections.
  • the following substances are essentially present in the rinsing water: Fe (II), Cl and H + ions.
  • the acidity of the rinsing water is determined by the H + ion concentration. This acidity is more conveniently given as a pH value, which is defined as a negative decimal logarithm of the H + ion concentration.
  • the divalent iron hydroxide Fe (OH) 2 is easily oxidized to the trivalent iron hydroxide Fe (OH) 3 by atmospheric oxygen: 2Fe (OH) 2 + H 2 O + 1/2 O 2 --- 2Fe (OH) 3
  • the object of the present invention is to avoid the formation of hydrolysis products on the surface of the products and thereby the quality of the bypassing the disadvantages of the abovementioned methods in the aftertreatment of pickled steel products, in particular pickled carbon steel hot strip, in continuous rinsing systems Improve surface.
  • this object is achieved in that carbon oxide (CO 2 ) is blown into at least one rinsing section of the rinsing system. It was also found here that by blowing carbon dioxide into the rinsing sections when the line was at a standstill, the formation of hydrolysis stains on the surface of pickled steel products could be completely prevented. By blowing in carbon dioxide, carbonate (CO 3 2- ) and hydrogen carbonate (HCO 3 - ) ions are formed in the rinsing water, which lead to a shift in the equilibrium of the hydrolysis reaction towards the starting products. In addition, the blowing in of carbon dioxide naturally also results in a reduction in the oxygen content, as a result of which the oxidation of Fe (II) ions is inhibited.
  • CO 2 carbon oxide
  • the object is further achieved in that a mixture of inert gas, e.g. Nitrogen or noble gas, and carbon dioxide is injected.
  • inert gas e.g. Nitrogen or noble gas
  • carbon dioxide is injected.
  • the efficiency of the process according to the invention is further increased by the combination of the oxygen-displacing action of the blown-in gases and the chemical action of carbon dioxide.
  • the inert gas and / or carbon dioxide is advantageously blown into the last rinsing section of the rinsing system, preferably into the last two rinsing sections.
  • the likelihood of the separation of hydrolysis products is most likely due to the pH value of the rinsing water, which has already risen due to the progressive dilution, and therefore the blowing in of inert gas and / or carbon dioxide at these points to avoid hydrolysis stains and to a resulting improvement in the quality of the surface of the product is particularly favorable.
  • the object is further achieved in that the inert gas and / or carbon dioxide is fed continuously.
  • the inert gas and / or carbon dioxide is fed in batchwise.
  • the gas used is not used until e.g. due to a breakdown caused by a malfunction, preventing the separation of hydrolysis products.
  • the amount of gas used can be reduced.
  • the choice of one of the two methods for supplying the gas used can also be determined by the nature and the infrastructure of the system.
  • the gas used is blown in above the flushing liquid.
  • the gas used is blown into the flushing liquid. This measure results in an even greater distribution and mixing of the gas in the flushing sections compared to blowing in from above. In addition, an improved displacement of the oxygen dissolved in the rinsing liquid or chemical suppression of the hydrolysis reactions is achieved evenly in the entire liquid volume of the rinsing liquid.
  • FIG. 1 schematically shows a system with gas injection into the last two containers of the flushing section and
  • FIG. 2 shows an example and schematically a system with gas circulation.
  • the four successive rinsing stages are denoted by the reference numerals 1, 2, 3 and 4 in the two figures in the order in which the pickled strip 5 passes.
  • pairs of squeeze rollers 6 are arranged.
  • the rinsing water is circulated in each of the four rinsing tanks 1, 2, 3 and 4 by means of a circulating pump 7, whereby it is applied to the steel strip 5 via spray pipes 8.
  • an exhaust gas fan 9 is located at the penultimate one Flushing stage 3 is provided, which sucks the air above the flushing liquid through a line 12.
  • the inert gas, the carbon dioxide or the mixture of these two gases is fed to the containers 3 and 4 via lines 10 and blown into the rinsing containers 3 and 4 via the introduction openings 19, 20.
  • a connecting line 11 is preferably provided between the two containers 3 and 4.
  • the insertion openings 19 are located above the liquid level of the flushing liquid in the respective flushing container 1, 2, 3 or 4 and are preferably dimensioned, like the exhaust gas fan 9 and the lines 10, such that the container is in the shortest possible time, preferably within a maximum of 20 seconds , can be completely filled with the injected gas.
  • Complete filling means filling with the gas to a residual content of approximately 1% by volume of oxygen.
  • Insertion openings 20 for the blown gas located below the liquid level of the flushing liquid in the respective container 1, 2, 3 or 4 are particularly advantageous for the introduction of carbon dioxide, which can partly dissolve in the flushing liquid and thus also chemically prevent the hydrolysis reaction.
  • the rinse water is preferably fed to the last rinse tank 4 via a line 13, then in the form of a countercurrent cascade rinse system via connecting lines 14 from the last rinse stage 4 to the first stage 1 and drawn off from there via a line 15.
  • Fig. 2 the same parts of the system are designated by the same reference numerals as in Fig. 1.
  • the exhaust gas fan 9 is now provided in the first purging stage 1 and inert gas, carbon dioxide or a mixture thereof is supplied to each purging tank 1, 2, 3 and 4 via the lines 10 and the introduction openings 19, 20.
  • each washing container 1, 2, 3 and 4 a circulation fan 16 and a circulation line 17 are provided for the atmosphere therein.
  • the individual rinsing containers 1, 2, 3 and 4 are in turn connected via lines 11.
  • the external circulation lines for the rinse water of the last three rinse tanks 2, 3 and 4 are connected to one another via lines 18.
  • Freshly pickled carbon steel hot strips of quality St 37-2 were treated with HCI-containing rinsing water in a normal atmosphere (air) by spraying, the total HCI concentration being 0.2 g / l and 0.02 g / l scam.
  • the temperature of the rinsing liquid was between 60 and 80 ° C.
  • the first hydrolysis stains appeared on the belt surface (formation of visible hydrolysis products). This effect increased with increasing duration of treatment, i.e. the formation of the hydrolysis products increases sharply.
  • the tape surface changes color from light brown to dark brown.
  • hydrolysis spots on the surface could also be prevented when a mixture of carbon dioxide and noble gas was blown in, the test conditions and parameters being chosen as in the previously described tests.

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)
EP94924237A 1993-07-08 1994-07-05 Verfahren zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband Expired - Lifetime EP0707668B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT1345/93 1993-07-08
AT0134593A AT403931B (de) 1993-07-08 1993-07-08 Verfahren und vorrichtung zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband
PCT/EP1994/002205 WO1995002080A1 (de) 1993-07-08 1994-07-05 Verfahren und vorrichtung zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband

Publications (2)

Publication Number Publication Date
EP0707668A1 EP0707668A1 (de) 1996-04-24
EP0707668B1 true EP0707668B1 (de) 1996-12-27

Family

ID=3511893

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94924237A Expired - Lifetime EP0707668B1 (de) 1993-07-08 1994-07-05 Verfahren zur nachbehandlung von gebeizten stahlprodukten, insbesondere von gebeiztem c-stahl-warmband

Country Status (11)

Country Link
US (1) US5837061A (zh)
EP (1) EP0707668B1 (zh)
KR (1) KR960703445A (zh)
CN (1) CN1057801C (zh)
AT (1) AT403931B (zh)
AU (1) AU7457794A (zh)
BR (1) BR9407004A (zh)
DE (1) DE59401423D1 (zh)
ES (1) ES2097660T3 (zh)
FI (1) FI103586B (zh)
WO (1) WO1995002080A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19902320C2 (de) * 1998-05-06 2001-02-08 Voest Alpine Ind Anlagen Verfahren und Vorrichtung zur Nachbehandlung von gebeiztem Stahlband
BE1015624A3 (fr) * 2002-08-07 2005-06-07 Andritz Ag Maschf Procede et un dispositif pour le decapage d'un ruban metallique.
WO2020207644A1 (de) 2019-04-09 2020-10-15 Sms Group Gmbh Kaskadenspülanlage zum behandeln eines bandförmigen flachprodukts

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5803984A (en) * 1996-02-09 1998-09-08 Danieli Wean, A Division Of Danieli Corporation Method and apparatus for rinsing steel product
CN103409764A (zh) * 2013-05-31 2013-11-27 江苏华阳管业股份有限公司 一种酸洗池
CN103409765A (zh) * 2013-05-31 2013-11-27 江苏华阳管业股份有限公司 一种酸洗系统
MX2017003104A (es) * 2014-09-10 2017-08-15 Nakagawa Special Steel Inc Metodo y aparato para limpieza de alambron.
CN110825062B (zh) * 2019-11-29 2021-04-09 北京首钢冷轧薄板有限公司 一种带钢清洗段信号的应急处理系统及方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3938214A (en) * 1974-01-14 1976-02-17 Inland Steel Company Cascade rinsing system and method
US4361444A (en) * 1979-09-26 1982-11-30 Teledyne Industries, Inc. Spray strip pickling of upright material
DE3048083C2 (de) * 1980-12-19 1983-09-29 Ludwig 8900 Augsburg Fahrmbacher-Lutz Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Titan oder Titanlegierungen
JPS59183987A (ja) * 1983-04-04 1984-10-19 Kawasaki Heavy Ind Ltd スポツト溶接における圧痕周辺部の変色防止方法
JPS60128274A (ja) * 1983-12-15 1985-07-09 Kawasaki Steel Corp 鋼帯酸洗での模様状スケ−ルの発生防止方法及びその装置
JPS60159124A (ja) * 1984-01-30 1985-08-20 Nippon Kokan Kk <Nkk> 連続焼鈍設備における酸化膜除去装置
JPH01111896A (ja) * 1987-10-27 1989-04-28 Nippon Steel Corp ステンレス鋼板の表面処理法
JPH01246384A (ja) * 1988-03-25 1989-10-02 Sumitomo Metal Ind Ltd 鋼板の変色防止方法
JPH0320486A (ja) * 1989-06-16 1991-01-29 Kobe Steel Ltd 金属材料のリンス方法
JPH0598466A (ja) * 1991-10-08 1993-04-20 Ebara Yuujiraito Kk ニツケル−クロムめつき方法およびこれに用いる装置
US5491036A (en) * 1992-03-27 1996-02-13 The Louis Berkman Company Coated strip

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19902320C2 (de) * 1998-05-06 2001-02-08 Voest Alpine Ind Anlagen Verfahren und Vorrichtung zur Nachbehandlung von gebeiztem Stahlband
BE1015624A3 (fr) * 2002-08-07 2005-06-07 Andritz Ag Maschf Procede et un dispositif pour le decapage d'un ruban metallique.
WO2020207644A1 (de) 2019-04-09 2020-10-15 Sms Group Gmbh Kaskadenspülanlage zum behandeln eines bandförmigen flachprodukts

Also Published As

Publication number Publication date
AT403931B (de) 1998-06-25
AU7457794A (en) 1995-02-06
EP0707668A1 (de) 1996-04-24
CN1057801C (zh) 2000-10-25
WO1995002080A1 (de) 1995-01-19
ES2097660T3 (es) 1997-04-01
DE59401423D1 (de) 1997-02-06
FI960071A (fi) 1996-01-08
FI103586B1 (fi) 1999-07-30
FI103586B (fi) 1999-07-30
CN1128548A (zh) 1996-08-07
ATA134593A (de) 1997-11-15
FI960071A0 (fi) 1996-01-08
BR9407004A (pt) 1996-08-06
KR960703445A (ko) 1996-08-17
US5837061A (en) 1998-11-17

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