EP1513634B1 - Procede permettant de reduire la corrosivite d'une eau de refroidissement ou de traitement - Google Patents

Procede permettant de reduire la corrosivite d'une eau de refroidissement ou de traitement Download PDF

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Publication number
EP1513634B1
EP1513634B1 EP03735588A EP03735588A EP1513634B1 EP 1513634 B1 EP1513634 B1 EP 1513634B1 EP 03735588 A EP03735588 A EP 03735588A EP 03735588 A EP03735588 A EP 03735588A EP 1513634 B1 EP1513634 B1 EP 1513634B1
Authority
EP
European Patent Office
Prior art keywords
water
cooling
process water
soluble salt
buffering effect
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
EP03735588A
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German (de)
English (en)
Other versions
EP1513634A2 (fr
Inventor
Wolfgang Hater
Ulrich Kiedrowicz
Gerd Grelewitz
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1513634A2 publication Critical patent/EP1513634A2/fr
Application granted granted Critical
Publication of EP1513634B1 publication Critical patent/EP1513634B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8

Definitions

  • the invention includes a method for reducing corrosion in cooling and process waters, which can lead to an entry of acids in the system, for. B. in continuous casting plants of the steel industry.
  • the entry of silicon tetrafluoride and HF in the spray zones resulting from fluoride erosion of the casting powder leads to a drop in the pH in the spray water and to the corrosion of plant components.
  • the invention was based on the object to provide an effective method for reducing corrosion, without having the disadvantages of the known methods.
  • a method should be provided which is less critical in terms of pH increase while allowing rapid adaptation to changing operating conditions.
  • Non-prepublished DE 100 64 412 A1 describes a process for preventing the precipitation of calcium fluoride in a cooling or process water, in which at least one water-soluble salt containing at least one of the following ions is added to the process water: magnesium cations, cations of trivalent metals , Anions of oligo- or polyphosphate. Preferred cations of trivalent metals here are aluminum and iron.
  • a buffer substance is added to the water in order to avoid the drop in the pH value by the introduction of fluoride into the water.
  • water-soluble is meant here that dissolve at least 1 g of the salt at 20 ° C in 1 liter of water.
  • the water-soluble salt with a buffering effect is preferably used in the form of an aqueous solution, since it can be metered easily via metering pumps.
  • the cooling or process water In practice, facilities are frequently encountered in which the cooling or process water is circulated, comprising a reservoir, a conduit system and a working area, and the introduction of acid in the working area, the Amount of cooling or process water in the reservoir and in the piping system at least 5 times, preferably at least 10 times as large and in particular at least 20 times as large as the amount of cooling or process water in the work area.
  • the method is particularly suitable for such a device.
  • the method may also be practiced by passing the cooling or process water in a flow system comprising a conduit system and a work area.
  • the cooling or process water is therefore not circulated, but derived after a single use.
  • working area is meant that area of the facility in which the cooling or process water develops its technically intended effect. This may, for example, be the area in which the cooling or process water exchanges heat or substances with the ambient air or with other substrates. For example, it may be a cooling device in which the cooling or process water receives from this heat by direct or indirect contact with a medium to be cooled. An example of this is the evaporation zone of a cooling tower. However, this may also be an area in which the cooling or process water is brought into contact with warm substrate surfaces in order to cool them. This is the case, for example, in continuous casting plants of the steel industry, where the cooling or process water is sprayed onto the metal surfaces to be cooled.
  • the cooling or process water In the work area, the cooling or process water usually comes not only in contact with the intended substrate, but also with the ambient air. Therefore, the cooling or process water in this area receives foreign matter either directly from the substrate surface or from the ambient air. These can be gaseous, solid or liquid in nature. This substance uptake changes the chemical composition of the cooling or process water. In the example presented by way of introduction, acidic substances cause a drop in the pH in the cooling or process water. As a result, its corrosivity with respect to the materials of the device and possibly also with respect to the substrate is undesirably increased.
  • the decrease in the pH is counteracted by metering into the cooling or process water a water-soluble salt with a buffering action.
  • this does not take place in the reservoir itself, but in or just before the work area. Therefore, it is preferable that the water-soluble salt with buffers Added effect in the line system at a point that is seen in the flow direction of the cooling or process water before the work area. Accordingly, it is not necessary to change the chemical composition of the entire cooling or process water, the majority of which is in the reservoir, by adding the salt with a buffering effect. Rather, it changes only the composition of that part of the cooling or process water, which then enters the work area in a mass transfer with the environment.
  • the water-soluble salt is buffered with buffering action, based on empirical values, in proportion to the amount of water flowing through the working area. For example, can be added per m 3 of cooling or process water flowing through the work area, an empirically determined amount of salt with buffering effect. Accordingly, one embodiment of the method according to the invention consists in metering in the water-soluble salt with buffering action as a function of the amount of cooling or process water which flows through the working area within a predetermined time interval.
  • the proportionality factor depends, for example, on the volume of the water stream to be treated and can be calculated therefrom or preferably determined experimentally.
  • the guide may be selected, for example, from the pH, the fluoride ion concentration and the acid capacity of the cooling or process water.
  • the water-soluble salt with a buffering effect is metered in when the pH falls below a predetermined threshold value.
  • This threshold value which is to be determined depending on the material properties of the device and / or the substrate, can be, for example, in the range from 4 to 7, in particular from 5 to 6.
  • buffering salt is added either until the threshold value is exceeded again, or an amount of buffering salt is added which depends on the difference between the threshold value and the actually measured pH value.
  • the fluoride ion concentration As mentioned in the introduction, this is the case, for example, with continuous casting plants of the steel industry.
  • the acid entry is then proportional to the increase in fluoride ion concentration.
  • a predetermined threshold which may be, for example, in the range from 40 to 300 mg / l, in particular in the range from 60 to 200 mg / l.
  • the embodiment is particularly suitable for determining the deviation of the fluoride ion concentration from the predetermined threshold value and metering in the salt with buffering action as a function of the level of this deviation.
  • the acid capacity of the cooling or process water is selected as the guide variable. This is defined by the amount (in millimoles) of strong monobasic acid that must be added to one liter of water to its pH to lower to 4.3. It is expressed in millimoles of acid added per liter of water.
  • the water-soluble salt is buffered with buffering effect if the acid capacity falls below a predetermined threshold. This may for example be in the range of 0.1 to 1 millimoles / liter, in particular from 0.3 to 0.7 millimoles / liter. Again, you can either add as long salt with buffering effect until the acid capacity exceeds the threshold again. Or, determine the deviation of the actual acid capacity from the threshold value and add an amount of salt with buffering effect that is proportional to the deviation. The proportionality factor is preferably determined empirically again.
  • the water-soluble salt having a buffering effect may be selected from bicarbonates, carbonates, borates, orthophosphates and polyphosphates.
  • the water-soluble salt having a buffering effect may be selected from bicarbonates, carbonates, borates, orthophosphates and polyphosphates.
  • particularly preferred salts as buffering effect are alkali or ammonium salts, especially the sodium salts, with bicarbonate, carbonate, borate, ortho or polyphosphate ions.
  • the inventive method is particularly suitable for reducing the corrosivity of cooling or process water of continuous casting of the steel industry.
  • a preferred embodiment of the invention consists in additionally preventing the precipitation of calcium fluoride in the cooling or process water by additionally adding to the cooling or process water at least one further water-soluble salt containing at least one of the following ions: magnesium cations, cations trivalent metals, anions of oligo- or polyphosphate.
  • a water-soluble salt with magnesium cations is added to.
  • the pH value is measured continuously in the spray water of a continuous casting plant by means of a pH electrode, and when the temperature falls below a predetermined threshold value, the metering pump for the water-soluble, buffering salts is started. If the threshold value is exceeded, the dosage is stopped again.
  • the threshold here is usually in the pH range between 4 and 7, preferably in the pH range of 5 to 6.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)

Claims (11)

  1. Procédé pour diminuer la corrosivité d'eau de refroidissement ou de procédé, dans laquelle le pH est diminué en raison d'une introduction d'acides, dans lequel on ajoute en dosant à l'eau de refroidissement ou de procédé au moins un sel soluble dans l'eau à effet tampon, caractérisé en ce que l'eau de refroidissement ou de procédé est soit
    a) guidée dans un circuit, qui comprend un réservoir, un système de conduites et une zone de travail et l'introduction de l'acide est réalisée dans la zone de travail, la quantité d'eau de refroidissement ou de procédé dans le réservoir et dans le système de conduites étant au moins 5 fois plus grande que la quantité d'eau de refroidissement ou de procédé dans la zone de travail,
    soit
    b) est guidée dans un système continu, qui comprend un système de conduites et une zone de travail
    et soit
    c) on ajoute en dosant le sel soluble dans l'eau à effet tampon en fonction de la quantité d'eau de refroidissement ou de procédé qui s'écoule endéans un intervalle de temps prédéfini dans la zone de travail
    soit
    d) on mesure en continu ou en discontinu la valeur d'au moins une grandeur de référence dans l'eau de refroidissement ou de procédé et on ajoute en dosant le sel soluble dans l'eau à effet tampon en fonction de la valeur de la grandeur de référence.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on ajoute en dosant le sel soluble dans l'eau à effet tampon dans le système de conduites en un endroit qui est situé, dans le sens du flux, dans ou en amont de la zone de travail.
  3. Procédé selon l'une quelconque des revendications 1 et 2 ou les deux, caractérisé en ce qu'on travaille selon la variante d) et qu'on mesure la valeur de la grandeur de référence soit dans la zone de travail elle-même, dans un échantillon d'eau de refroidissement ou de procédé prélevé dans la zone de travail soit dans une partie du système de conduites qui se trouve, dans le sens du flux, en aval de la zone de travail.
  4. Procédé selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'on travaille selon la variante d) et on choisit la grandeur de référence parmi le pH, la concentration en ions fluorure et la capacité d'acide de l'eau de refroidissement ou de procédé.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on travaille selon la variante d) et on choisit comme grandeur de référence le pH et on ajoute en dosant le sel soluble dans l'eau à effet tampon lorsque le pH passe sous une valeur seuil prédéfinie dans la plage de 4 à 7, en particulier de 5 à 6.
  6. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on travaille selon la variante d) et, dans le cas où l'acide introduit dans l'eau de refroidissement ou de procédé est du HF ou un composé fluoré, qui forme du HF dans l'eau, on choisit comme grandeur de référence la concentration en ions fluorure et on ajoute en dosant le sel soluble dans l'eau à effet tampon lorsque la concentration en ions fluorure dépasse une valeur seuil prédéfinie dans la plage de 40 à 300 mg/l, en particulier de 60 à 200 mg/l.
  7. Procédé selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on travaille selon la variante d) et on choisit comme grandeur de référence la capacité d'acide de l'eau de refroidissement ou de procédé et on ajoute en dosant le sel soluble dans l'eau à effet tampon lorsque la capacité d'acide passe sous une valeur seuil prédéfinie dans la plage de 0,1 à 1 mmole/l, en particulier de 0,3 à 0,7 mmole/l.
  8. Procédé selon l'une ou plusieurs des revendications 1 à 7, caractérisé en ce que le sel soluble dans l'eau à effet tampon est choisi parmi les hydrogénocarbonates, les carbonates, les borates, les orthophosphates et les polyphosphates.
  9. Procédé selon l'une ou plusieurs des revendications 1 à 8, caractérisé en ce que le sel soluble dans l'eau à effet tampon est choisi parmi les sels de métal alcalin, alcalino-terreux et d'ammonium.
  10. Procédé selon l'une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'il s'agit, pour l'eau de refroidissement ou de procédé, d'eau de refroidissement ou de procédé d'installations de coulée continue de l'industrie de l'acier.
  11. Procédé selon l'une ou plusieurs des revendications 1 à 10, caractérisé en ce qu'on empêche en outre la précipitation du fluorure de calcium de l'eau de refroidissement ou de procédé en ce qu'on ajoute à l'eau de refroidissement ou de procédé en outre au moins un autre sel soluble dans l'eau qui contient au moins un des ions suivants : cations de magnésium, cations des métaux trivalents, anions d'oligophosphates ou de polyphosphates.
EP03735588A 2002-06-17 2003-06-10 Procede permettant de reduire la corrosivite d'une eau de refroidissement ou de traitement Expired - Lifetime EP1513634B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10227040A DE10227040A1 (de) 2002-06-17 2002-06-17 Verfahren zur Verringerung der Korrosivität von Kühl- oder Prozeßwasser
DE10227040 2002-06-17
PCT/EP2003/006041 WO2003106074A2 (fr) 2002-06-17 2003-06-10 Procede permettant de reduire la corrosivite d'une eau de refroidissement ou de traitement

Publications (2)

Publication Number Publication Date
EP1513634A2 EP1513634A2 (fr) 2005-03-16
EP1513634B1 true EP1513634B1 (fr) 2006-05-03

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EP03735588A Expired - Lifetime EP1513634B1 (fr) 2002-06-17 2003-06-10 Procede permettant de reduire la corrosivite d'une eau de refroidissement ou de traitement

Country Status (6)

Country Link
EP (1) EP1513634B1 (fr)
AT (1) ATE324954T1 (fr)
AU (1) AU2003236726A1 (fr)
DE (2) DE10227040A1 (fr)
ES (1) ES2263003T3 (fr)
WO (1) WO2003106074A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL3215287T3 (pl) * 2014-11-05 2020-09-21 Ecolab Usa Inc. Sposób kontroli korozji w urządzeniach do odlewania ciągłego
EP3528916A1 (fr) 2016-10-18 2019-08-28 Ecolab USA Inc. Dispositif pour séparer l'eau et les solides d'eau de pulvérisation dans une installation de coulée continue, et procédé pour surveiller et contrôler un fond de corrosion

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA805265B (en) * 1979-08-29 1982-10-27 Lysaght Australia Ltd Temper rolling fluids
JPS61190084A (ja) * 1985-02-16 1986-08-23 Yanmar Diesel Engine Co Ltd 冷却水系の防食法
JPH0843586A (ja) * 1994-04-08 1996-02-16 General Electric Co <Ge> 金属部品の表面における亀裂の発生又は成長を低減させるための方法
US6024892A (en) * 1997-10-06 2000-02-15 Fmc Corporation Anticorrosion and pH stable alkali metal halide solutions for air dehumidification
DE10064412A1 (de) * 2000-12-21 2002-06-27 Henkel Kgaa Verhinderung der Abscheidung von Calciumfluorid

Also Published As

Publication number Publication date
WO2003106074A3 (fr) 2004-09-10
DE50303211D1 (de) 2006-06-08
DE10227040A1 (de) 2003-12-24
AU2003236726A1 (en) 2003-12-31
ATE324954T1 (de) 2006-06-15
EP1513634A2 (fr) 2005-03-16
WO2003106074A2 (fr) 2003-12-24
ES2263003T3 (es) 2006-12-01

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