EP3215287B1 - Verfahren zur steuerung der korrosion in strangsgussvorrichtungen - Google Patents

Verfahren zur steuerung der korrosion in strangsgussvorrichtungen Download PDF

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Publication number
EP3215287B1
EP3215287B1 EP14793190.1A EP14793190A EP3215287B1 EP 3215287 B1 EP3215287 B1 EP 3215287B1 EP 14793190 A EP14793190 A EP 14793190A EP 3215287 B1 EP3215287 B1 EP 3215287B1
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EP
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Prior art keywords
water
aqueous solution
caster
buffer system
buffer
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EP14793190.1A
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English (en)
French (fr)
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EP3215287A1 (de
Inventor
Donald Johnson
Laia More ROCA
Craig Myers
Paloma Lopez Serrano
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Ecolab USA Inc
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Ecolab USA Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • B22D11/1245—Accessories for subsequent treating or working cast stock in situ for cooling using specific cooling agents
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation

Definitions

  • the present invention deals with continuous casters which are used in steel production, especially the control of the pH in those continuous casters.
  • pH One critical water quality parameter to control is pH: Low pH could result in high corrosion of carbon steel, while high pH could result in uncontrolled formation of mineral scale. The pH should therefore be maintained in all areas of the spray chamber at the right pH at which the corrosion and scale inhibitor program can be effective.
  • the spray chamber environment can be subdivided into three zones: 1. the fully submerged zone; 2. the spray wetted zone; and 3. the condensate wetted zone.
  • the corrosion challenges in these three zones are distinctly different.
  • the aqueous composition is substantially that of the bulk water, including all water components and inhibitors.
  • the water composition is defined by the volatility of the components of the water producing the vapors. Since inhibitors and inorganic ions are essentially nonvolatile, and acidic gasses such as CO 2 , HCl and HF are fairly volatile, the composition, and resulting corrosiveness are largely defined by the acidic gasses.
  • DE 33 17 126 A1 refers to a process to avoid acid caused corrosion in a caster for the production of steel, wherein to spray water a base solution and a dispersant is added.
  • WO 03/106074 A2 refers to a process for reducing the corrosiveness of cooling or process water, in which the pH is reduced by the addition of acids, at least one water-soluble salt with a buffering effect being added to the cooling or process water.
  • Hydrofluoric acid is a relatively and very volatile acid with a pKa of ⁇ 4 and an Henry's law constant of 3.2 at 40° C.
  • the most volatile form of fluoride is the protonated form with a Henry's law constant of 3.2 at 40° C.
  • the mold powder used during production produces said hydrofluoric acid when contacting water. If the cooling water is sufficient basic, then the alkalinity in the cooling water will neutralize the acidity, and the flouride produced will be predominantly in the ionized nonvolatile F - form, but, if the level is not sufficient for a complete neutralization, once the buffering capacity has been exhausted, the pH will rapidly drop down to 2-4, particularly in the high heat flux areas where mold powders are pyrolyzed into fluoride species. At these pH levels, fluoride will be converted into the undissociated HF species, which is quite volatile. This will facilitate acidification of vapors produced by contact with hot metals.
  • a buffer system for the production of steel by which water or aqueous solution can be sprayed by a caster comprising a plurality of water sprayers on the steel being molded in the caster, comprising:
  • buffer shall explicitly also include any basic or alkali substance that can be used to neutralize acids, i.e. also hydroxy salts which in another context might not usually be referred to as buffers.
  • the primary buffer system is adapted to buffer the water or aqueous solution so that after buffering the (then) aqueous solution has a total buffer concentration of ⁇ 10 ppm to ⁇ 1000 ppm.
  • buffer concentration in the sense of the present invention especially means and/or includes for a given substance both any acidic and basic forms, i.e. for citrate both citric acid and (in case that sodium is the counter-ion) the mono, bi, and trisodium citrate, in case they are present in the solution.
  • buffer concentration is also intended to be related to the representative buffers, e.g. in terms of the primary buffer system the buffers that belong to said primary buffer system.
  • total buffer concentration in the sense of the present invention especially means and/or includes the total buffer concentration of all appropriate and relating substances present in the solution.
  • the aqueous solution has a buffer concentration of ⁇ 25 ppm to ⁇ 750 ppm, more preferred ⁇ 50 ppm to ⁇ 600 ppm and most preferred ⁇ 100 ppm to ⁇ 500 ppm
  • the secondary buffer system is adapted to buffer the water or aqueous solution so that after buffering the (then) aqueous solution has a total buffer concentration of ⁇ 10 ppm to ⁇ 1000 ppm.
  • the aqueous solution has a buffer concentration of ⁇ 25 ppm to ⁇ 750 ppm, more preferred ⁇ 50 ppm to ⁇ 600 ppm and most preferred ⁇ 100 ppm to ⁇ 500 ppm
  • the secondary buffer system comprises at least one organic buffer.
  • organic buffer in the sense of the present invention especially means and/or includes any acid or salts thereof which does contain carbon in a different form than carbonate and/or bicarbonate, with a pKa in the claimed range. It should be noted that this may be the second protonation step for multiacids (such as e.g. citric acid with pKa's of 3.13, 4.76 and 6.39).
  • the secondary buffer system comprises at least one salt of a acid whereby the solubility of the salt in deionized water at 25°C is ⁇ 100g/l, preferably >200g/l. This has been found to be advantageous for many applications in the art.
  • said salt of a acid is a potassium and/or sodium salt.
  • the secondary buffer system comprises at least one acid whereby the solubility of the calcium or magnesium salt of the acid in deionized water at 25°C is ⁇ 0.7g/l, preferably ⁇ 1 g/l more preferred ⁇ 0 2g/l. This has been found to be advantageous for many applications in the art, because by doing so, the buffering capacity of the water can be increased without increasing the scaling potential of the cooling water.
  • the secondary buffer system comprises one or more salts from acids selected from the group of phosphorous acid, carboxylic acids, carboxylic/phosphoric acids, phosphinic acids, amino acids, polymers comprising acidic functionalities, or mixtures or conjugate base salts thereof.
  • Preferred polymers comprising acidic functionalities are poly(meth)acrylic acids, poly(meth)acrylic acid /(meth)acrylamide copolymers or mixtures thereof. These polymers are especially preferred due to their tendency to either suppress or not overly support microbial growth.
  • the secondary buffer system comprises one or more salts from acids selected from the group of phosphorous acid, citric acid, succinic acid, adipic acid, sebacic acid, malic acid or mixtures or conjugate base salts thereof.
  • the caster furthermore comprises at least one pH-meter by which the pH of said aqueous solution which has cooled the molded steel in the upper zone of the spray chamber can be measured and a flow control device by which the secondary buffer system can be controlled and adapted upon the measurement of the pH.
  • the amount of secondary buffer can then be increased or decreased depending on the need. This can be done e.g. by having a valve or a pump delivering high concentrated secondary buffer solution into the aqueous solution or by other devices or solution pertinent to those skilled in the art of the field of the invention.
  • the secondary buffer is increased when the measured pH is below a certain threshold.
  • This threshold preferably is a fixed pH and is preferably between ⁇ 6.0 to ⁇ 8.5.
  • the secondary buffer is increased when difference in pH between the average pH of the water or aqueous solution, either amongst all sprayers or for at least one preselected sprayer and the measured pH in the upper zone of the spray chamber is over a certain threshold.
  • the acid buffer can be added at any point in the system, and through intermixing of the recirculating water will provide benefits in the form of increased resistance to pH suppression.
  • Fig. 1 shows a very schematic illustration of a first embodiment of the present invention.
  • steel is made in a steel mill 1.
  • the hot liquid steel 15 enters the spray chamber at the outlet 10 and is then guided over a set of rolls 20 where it is formed and cooled down.
  • sprayers schematically represented as 40 to 43 which cool the steel with aqueous solution.
  • These sprayers are equipped with a delivery system for primary buffer and a delivery system for secondary buffer, both are not shown in Fig. 1 . This delivery can be achieved e.g. by valves or pumps.
  • a sampling device 50 is located under the upper segments. Said sampling device 50 collects water from the upper sprays and measures its pH. Alternatively, the pH can be directly measured without a sampling device. Once the pH deviates from a certain threshold, the secondary buffer is increased by the delivery system.
  • Fig. 1 is highly schematic and it is apparent to the skilled person in the art that other applications are easily possible. So it could be that there is more than one sampling device and different sprayers are controlled by different sampling devices (either that each sprayer has its own device or that a device controls several sprayers).
  • Fig. 2 is a diagram showing the changes in pH in a conventional steel caster spray chamber over time.
  • this caster only an inorganic buffer sodium bicarbonate buffer with pH control of the bulk water 8.7 was used.
  • the pH of the spray water of the upper zone which had passed the steel was continuously measured over several days.
  • the secondary buffer in the sprayers located in the upper zone of the spray chamber would be increased once the pH of the water collected with the sampling device deviates too much from the pH of the bulk water. Depending on the actual application this could either be set that once the pH goes under an absolute value (e.g. 8.0 or 7.5) then the dosage of secondary buffer is initiated or if the pH difference rises over 0.7 or 1.0.
  • an absolute value e.g. 8.0 or 7.5

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (7)

  1. Puffersystem für die Herstellung von Stahl, durch das Wasser oder eine wässrige Lösung von einer Stranggussanlage, die mehrere Wassersprühgeräte umfasst, auf den in der Stranggussanlage geformten Stahl gesprüht werden kann, Folgendes umfassend:
    a) ein primäres Puffersystem, das das Wasser oder die wässrige Lösung von wenigstens einem der Wassersprühgeräte puffert, das ein oder mehrere Salze umfasst, die aus der Gruppe von Carbonatsalzen, Bicarbonatsalzen, Hydroxysalzen ausgewählt sind; und
    b) ein sekundäres Puffersystem, das das Wasser oder die wässrige Lösung von wenigstens einem der Wassersprühgeräte puffert, wodurch sich das sekundäre Puffersystem von dem primären Puffersystem unterscheidet und der Puffer ein oder mehrere Salze aus Säuren umfasst, die aus der Gruppe der Phosphorsäuren Carbonsäuren, Carbon-/ Phosphorsäuren, Phosphinsäuren, Aminosäuren oder Gemischen oder konjugierten Basensalzen davon ausgewählt sind, wobei die Carbonsäuren aus Zitronensäure, Bernsteinsäure, Adipinsäure, Sebacinsäure, Äpfelsäure mit einem pKa von ≥ 4,5 bis ≤ 7,5 ausgewählt sind; und wodurch die Löslichkeit des Salzes der Säure des sekundären Puffersystems in entionisiertem Wasser bei 25°C ≥ 100 g/l ist;
    wodurch die Stranggussanlage ferner wenigstens ein pH-Meter umfasst, wodurch das pH-Meter der Stranggussanlage, durch das der pH-Wert der wässrigen Lösung, die den geformten Stahl abgekühlt hat, gemessen wird, und wobei die Durchflusssteuervorrichtung der Stranggussanlage bei der Messung des pH-Werts den sekundären Puffer steuert und anpasst.
  2. Puffersystem nach Anspruch 1, wodurch das sekundäre Puffersystem wenigstens einen organischen Puffer umfasst.
  3. Verfahren für die Herstellung von Stahl, wobei ein Puffersystem nach einem der Ansprüche 1 bis 2, zum Puffern des Wassers oder der wässrigen Lösung von wenigstens einem der Wassersprühgeräte verwendet wird, wodurch die Stranggussanlage ferner wenigstens ein pH-Meter umfasst, wodurch der pH-Wert der wässrigen Lösung, die den geformten Stahl abgekühlt hat, mit einem pH-Meter der Stranggussanlage gemessen wird, und wobei der sekundäre Puffer durch die Durchflusssteuervorrichtung der Stranggussanlage bei der Messung des pH-Werts gesteuert und angepasst wird.
  4. Verfahren nach Anspruch 3, wodurch der sekundäre Puffer gesteigert wird, wenn der gemessene pH-Wert unter einem bestimmten Schwellenwert liegt.
  5. Verfahren nach Anspruch 3 oder 4, wodurch der sekundäre Puffer gesteigert wird, wenn eine pH-Wert-Differenz zwischen dem durchschnittlichen pH-Wert des Wassers oder der wässrigen Lösung, entweder unter allen Sprühgeräten oder für wenigstens ein vorausgewähltes Sprühgerät, und dem gemessenen pH-Wert über einem bestimmten Schwellenwert liegt.
  6. Verfahren nach einem der Ansprüche 3 bis 5, wodurch das primäre Puffersystem nach dem Puffern der (dann) wässrigen Lösung eine Gesamtpufferkonzentration von ≥ 10 ppm bis ≤ 1000 ppm aufweist.
  7. Verfahren nach einem der Ansprüche 3 bis 6, wodurch das sekundäre Puffersystem nach dem Puffern der (dann) wässrigen Lösung eine Gesamtpufferkonzentration von ≥ 10 ppm bis ≤ 1000 ppm aufweist.
EP14793190.1A 2014-11-05 2014-11-05 Verfahren zur steuerung der korrosion in strangsgussvorrichtungen Active EP3215287B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14793190T PL3215287T3 (pl) 2014-11-05 2014-11-05 Sposób kontroli korozji w urządzeniach do odlewania ciągłego

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Application Number Priority Date Filing Date Title
PCT/EP2014/073826 WO2016070914A1 (en) 2014-11-05 2014-11-05 Method to control corrosion in continuous casters

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EP3215287A1 EP3215287A1 (de) 2017-09-13
EP3215287B1 true EP3215287B1 (de) 2020-04-08

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ES (1) ES2804623T3 (de)
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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3317126C2 (de) * 1983-05-06 1986-07-24 Mannesmann AG, 4000 Düsseldorf Verfahren zur Vermeidung von Säurekorrosion an Stranggießanlagen
DE10227040A1 (de) * 2002-06-17 2003-12-24 Henkel Kgaa Verfahren zur Verringerung der Korrosivität von Kühl- oder Prozeßwasser

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. D. POMOGAILO ET AL: "Monomeric and Polymeric Carboxylic Acids", MACROMOLECULAR METAL CARBOXYLATES AND THEIR NANOCOMPOSITES, 1 January 2010 (2010-01-01), Berlin, Heidelberg, XP055489755, ISBN: 978-3-642-10574-6, Retrieved from the Internet <URL:https://www.springer.com/cda/content/document/cda_downloaddocument/9783642105739-c1.pdf?SGWID=0-0-45-993442-p173959909> [retrieved on 20180703] *

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WO2016070914A1 (en) 2016-05-12
PL3215287T3 (pl) 2020-09-21
ES2804623T3 (es) 2021-02-08
EP3215287A1 (de) 2017-09-13

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