EP3215287B1 - Procédé de lutte contre la corrosion dans une coulée en continu - Google Patents

Procédé de lutte contre la corrosion dans une coulée en continu 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
European Patent Office
Prior art keywords
water
aqueous solution
caster
buffer system
buffer
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EP14793190.1A
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German (de)
English (en)
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EP3215287A1 (fr
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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Priority to PL14793190T priority Critical patent/PL3215287T3/pl
Publication of EP3215287A1 publication Critical patent/EP3215287A1/fr
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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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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (7)

  1. Système tampon pour la production d'acier, par lequel de l'eau ou une solution aqueuse peut être pulvérisée par une machine de coulée comprenant une pluralité de pulvérisateurs d'eau sur l'acier en cours de moulage dans la machine de coulée, comprenant :
    a) un système tampon primaire tamponnant l'eau ou la solution aqueuse d'au moins l'un desdits pulvérisateurs d'eau, lequel comprend un ou plusieurs sels choisis dans le groupe des sels de carbonate, des sels de bicarbonate, des sels d'hydroxyde ; et
    b) un système tampon secondaire tamponnant l'eau ou la solution aqueuse d'au moins l'un desdits pulvérisateurs d'eau, ledit système tampon secondaire étant différent du système tampon primaire et ledit tampon comprenant un ou plusieurs sels issus d'acides choisis dans le groupe constitué de l'acide phosphoreux, des acides carboxyliques, des acides carboxyliques/phosphoriques, des acides phosphiniques, des acides aminés, ou de mélanges ou sels de base conjuguée de ceux-ci, les acides carboxyliques étant choisis parmi l'acide citrique, l'acide succinique, l'acide adipique, l'acide sébacique, l'acide malique, ayant un pKa de ≥ 4,5 à ≤ 7,5 ; et la solubilité du sel de l'acide du système tampon secondaire dans l'eau désionisée à 25 °C étant ≥ 100 g/L ;
    la machine de coulée comprenant en outre au moins un pH-mètre, par lequel le pH de ladite solution aqueuse, laquelle a refroidi l'acier moulé, est mesuré, et le dispositif de régulation de débit de la machine de coulée régulant et adaptant le tampon secondaire lors du mesurage du pH.
  2. Système tampon selon la revendication 1 selon lequel le système tampon secondaire comprend au moins un tampon organique.
  3. Procédé de production d'acier, dans lequel un système tampon selon l'une quelconque des revendications 1 à 2 est utilisé pour tamponner l'eau ou la solution aqueuse d'au moins l'un desdits pulvérisateurs d'eau, la machine de coulée comprenant en outre au moins un pH-mètre, le pH de ladite solution aqueuse, qui a refroidi l'acier moulé, étant mesuré à l'aide d'un pH-mètre de la machine de coulée, et le tampon secondaire étant régulé et adapté par le dispositif de régulation de débit de la machine de coulée lors du mesurage du pH.
  4. Procédé selon la revendication 3, selon lequel le tampon secondaire est augmenté lorsque le pH mesuré est inférieur à un certain seuil.
  5. Procédé selon la revendication 3 ou 4, selon lequel le tampon secondaire est augmenté lorsque la différence de pH entre le pH moyen de l'eau ou de la solution aqueuse, soit parmi tous les pulvérisateurs, soit pour au moins un pulvérisateur présélectionné, et le pH mesuré, excède un certain seuil.
  6. Procédé selon l'une quelconque des revendications 3 à 5, selon lequel le système tampon primaire, après avoir tamponné (ce qui constituait alors) la solution aqueuse, présente une concentration totale de tampon de ≥ 10 ppm à ≤ 1000 ppm.
  7. Procédé selon l'une quelconque des revendications 3 à 6, selon lequel le système tampon secondaire, après avoir tamponné (ce qui constituait alors) la solution aqueuse, présente une concentration totale de tampon de ≥ 10 ppm à ≤ 1000 ppm.
EP14793190.1A 2014-11-05 2014-11-05 Procédé de lutte contre la corrosion dans une coulée en continu Active EP3215287B1 (fr)

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PL14793190T PL3215287T3 (pl) 2014-11-05 2014-11-05 Sposób kontroli korozji w urządzeniach do odlewania ciągłego

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PCT/EP2014/073826 WO2016070914A1 (fr) 2014-11-05 2014-11-05 Procédé de lutte contre la corrosion dans une coulée en continu

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EP3215287B1 true EP3215287B1 (fr) 2020-04-08

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

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