EP3029164A1 - Method of treating a steel strip, especially for a pickling treatment of the steel strip and system for treating a steel strip - Google Patents

Method of treating a steel strip, especially for a pickling treatment of the steel strip and system for treating a steel strip Download PDF

Info

Publication number
EP3029164A1
EP3029164A1 EP14195952.8A EP14195952A EP3029164A1 EP 3029164 A1 EP3029164 A1 EP 3029164A1 EP 14195952 A EP14195952 A EP 14195952A EP 3029164 A1 EP3029164 A1 EP 3029164A1
Authority
EP
European Patent Office
Prior art keywords
steel strip
treatment
treatment liquid
section
spray
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.)
Granted
Application number
EP14195952.8A
Other languages
German (de)
French (fr)
Other versions
EP3029164B1 (en
Inventor
Thomas Marx
Wolfgang WALSDORF
Rafael Rituper
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.)
John Cockerill UVK GmbH
Original Assignee
CMI UVK 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
Priority to EP14195952.8A priority Critical patent/EP3029164B1/en
Application filed by CMI UVK GmbH filed Critical CMI UVK GmbH
Priority to PCT/EP2015/078314 priority patent/WO2016087494A1/en
Priority to CN201580065809.5A priority patent/CN107002255A/en
Priority to EP15804432.1A priority patent/EP3227467A1/en
Priority to CA2969274A priority patent/CA2969274A1/en
Priority to RU2017123253A priority patent/RU2691363C2/en
Priority to MX2017007108A priority patent/MX2017007108A/en
Priority to US15/532,138 priority patent/US20170268114A1/en
Priority to BR112017011360A priority patent/BR112017011360A2/en
Priority to KR1020177018060A priority patent/KR20170089919A/en
Priority to JP2017528778A priority patent/JP2017536481A/en
Publication of EP3029164A1 publication Critical patent/EP3029164A1/en
Application granted granted Critical
Publication of EP3029164B1 publication Critical patent/EP3029164B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00Apparatus for cleaning or pickling metallic material
    • C23G3/02Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/024Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by a combination of dipping and spraying
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00Apparatus for cleaning or pickling metallic material
    • C23G3/02Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously

Definitions

  • the present invention relates to a method for treating a steel strip especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank.
  • the present invention relates to a system for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank.
  • the steel strip to be treated according to the method of the present invention and in a system of the present invention is stainless steel.
  • oxide scale generally refers to the chemical compounds of iron and oxygen, as well as the chemical compounds of iron alloying elements, e.g. chromium and oxygen, formed on the surface of the steel by exposure to air while the metal is at an elevated temperature.
  • Chemical compounds thus formed include iron oxides, such as FeO, Fe2O3 and Fe3O4, oxides of alloying elements such as CrO3, NiO, SiO2 and complex oxide spinals like FeCr2O4, NiFe2O4, Fe2SiO4 and others.
  • stainless steel grades are heated up to a certain temperature (850-1150 °C depending on steel grade) and are kept at this temperature for some time to soften the metal in order to release the work hardening induced by hot and cold rolling.
  • a uniform grain structure is obtained depending on the annealing temperature, and oxide scale is formed on the surface.
  • a chromium-depleted zone is formed, which is different for austenitic, ferritic and duplex stainless steel grades.
  • Pickling is the process of chemically removing of oxide scale from the surface of a metal by the action of water solution of inorganic acids.
  • the stainless steel is widely pickled in diluted sulfuric or hydrochloric acid.
  • a mixture of nitric acid and hydrofluoric acid is widely applied.
  • the rate of pickling is affected by numerous variables, including the steel-based constituents and type and adherence of oxide to be removed. Pickling solution temperature, acid concentration, reaction product concentration, turbulence flow conditions, immersion time and presence or absence of inhibitors and accelerators influence the rate of acid attack.
  • hydrochloric acid has effectively displaced sulfuric acid as the acid of choice in industrial large-scale pickling lines for stainless steel. While the rate of pickling increases in direct proportion to the concentration of the acid, the influence of temperature is much more pronounced.
  • certain metals such as cooper, chromium and nickel, retard the rate of pickling when they occur in the steel base, since the scale bearing these alloying metals inhibits acid attack. Elements like aluminum and silicon form refractory-type oxides, which in turn lower the solubility rate of the oxide in the pickling acid.
  • the thickness of the oxide scale varies considerably with practice in rolling mills. E.g.
  • coiling temperature affects the adherence of the oxide and determines how easy or difficult it is to remove.
  • the lower coiling temperatures makes oxide removal easier, at higher coiling temperatures longer pickling times are required. E.g. at the coiling temperature of 750 °C, double pickling time is required compared to the coiling temperature of 570 °C.
  • the stainless steel Like with carbon steel, the stainless steel also oxidizes following hot rolling and coiling.
  • the oxide scale layer formed on the surface of the hot rolled stainless steel strip contains the alloying elements and is very tightly adhering on the surface, which makes the de-scaling or pickling of stainless steel very difficult as compared to the carbon steels.
  • To achieve efficient and thorough surface oxide removal from a stainless steel strip more severe processing techniques must be used which substantially increase processing time and operational costs.
  • chemical pickling of stainless steel strip must be preceded by mechanical de-scaling, e.g. by shot-blasting and/or scale breaking. Often nowadays additional methods of Pre-Pickling is applied to soften the oxide scale. E.g.
  • hot rolled stainless steel is conventionally pre-pickled in hot sulfuric acid and the cold rolled stainless steel is pre-pickled electrolytically in neutral electrolyte of Na 2 SO 4 solution prior the main pickling in mixed acid.
  • MD Mechanical de-scaling
  • PP Pre-Pickling
  • FP final pickling process
  • the pickling process most commonly used for stainless steel involves the use of a mixture of nitric and hydrofluoric acid, the mutual concentrations of which vary according to the type of stainless steel to be pickled (austenitic, ferritic, martensitic, duplex%), its surface characteristics and its past processing history.
  • various acid compositions Mat I and Mix II
  • various acid mixture temperatures are required.
  • the hydrofluoric acid is extremely corrosive and a harmful environmental pollutant.
  • the nitric acid is the source of highly polluting nitrogen oxide (NOx) vapors which are emitted into the atmosphere and which are highly aggressive towards metals and nonmetals with which they come into contact.
  • Today pickling lines are designed as shallow tank turbulence installations comprising of several consecutive pickling tanks.
  • the steel strip is pulled or pushed through the treatment tanks.
  • the complete pickling section is arranged as a cascade, i.e. the fresh or regenerated acid is added to the last treatment tank (i.e. the most downstream treatment tank according to the direction of movement of the steel strip) and is then processed in a countercurrent flow to the strip transport direction in order to maximize the use of the pickling acid.
  • wringer rolls are installed to remove the pickling acid from the strip to the greatest possible extend in order to enhance the cascade effect.
  • German patent disclosure DE 40 31 234 describes this technology.
  • the pickling acid is injected on both sides of the tank creating a high turbulence between the strip surface and the pickling acid.
  • the pickling acid is then overflowing from the treatment tank to a circulation tank from where it is again injected into the treatment tank by means of pumps.
  • the high turbulence reduces the thickness of the liquid boundary layer on the strip surface resulting in an improved media and energy exchange and consequently reducing the required pickling time.
  • pickling Another well known pickling method is the spray pickling, wherein the pickling acid is directly sprayed onto the strip surface using several spray nozzles installed both above and below the steel strip, cf. e.g. document DE 42 28 808 A1 .
  • the pickling acid is then collected in a circulation tank from where it is pumped to the spray nozzles and sprayed on to the strip surface again.
  • the spray nozzles are typically operated at a pressure above 1 bar. Due to the high impulse of the pickling acid sprayed onto the strip surface, the pickling efficiency and consequently the pickling time can be further improved.
  • this technology has never been used commercially in strip pickling lines.
  • hydrochloric acid as a pickling agent for stainless steel pickling allows the realization of pickling mechanisms of both the removal of oxide scale and the chromium-depleted zone.
  • the pickling of stainless steel in hydrochloric acid is a combined process of reduction and oxidation.
  • the chemical dissolution of steel in HCl is as follows: Fe + 2 HCl ⁇ FeCl 2 + H 2
  • the base metal, Fe is dissolved by the oxidizing agents, mainly FeCl 3 : 2 FeCl 3 + Fe ⁇ 3 FeCl 2
  • Oxidation reaction to produce the required oxidizing agent is as follows: 4 FeCl 2 + O 2 + 4 HCl ⁇ 4 FeCl 3 + 2 H 2 O
  • a minimum proper FeCl 3 concentration is required for the pickling process of stainless steel. This is today typically reached by adding H 2 O 2 to the pickling liquid.
  • chlorides of iron and chlorides of other metals are collectively referred to by the term MeCl.
  • FeCl 3 can be too high (to reach 60 g/l and above), making the whole pickling process difficult to control, with a high risk of over pickling the metal strip or causing inacceptable roughness of the strip surface.
  • Another drawback of the increased FeCl 3 concentration in the pickling acid is the effect on the regeneration process of the spent pickling acid. Spent pickling acid containing HCl is typically regenerated using the pyrohydrolysis process. In this process FeCl 2 and FeCl 3 are converted back to HCl and Fe 2 O 3 .
  • FeCl 3 however has a much lower evaporation temperature than FeCl 2 and evaporates in the pyrohydrolysis reactor causing very fine Fe 2 O 3 particles below 1 ⁇ m in size when converted to Fe 2 O 3 . These fine particles are difficult to remove from the process off-gases causing high dust emissions.
  • the object of the present invention is achieved by a method for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank with a spray section and an immersion section, and the treatment station comprising a common collection means for the treatment liquid, wherein the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions, wherein the steel strip has a top surface and a bottom surface, wherein the method comprises transporting the steel strip continuously through the treatment station in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip, such that
  • the present invention is related to a process for chemical or electrochemical treatment of the surface of stainless steel, preferably strip shaped, wherein the material is treated with a pickling solution, preferably containing HCl, in one or more treatment tanks to remove an oxide scale layer which was previously formed during the hot rolling process of the metal strip (steel strip).
  • This treatment is needed to reach a clean surface for either further processing it in a cold rolling process or for direct commercial use.
  • the process for chemical or electrochemical treatment of the surface of stainless steel is conducted using a pickling solution containing HCl as the only pickling agent, wherein the advantages of spray pickling are used to a maximum extend.
  • the process shall be controllable minimizing the risk of over-pickling so that the process can be realized in commercially used industrial scale pickling lines.
  • the spent acid of such a process is of a quality such that it can be treated in regeneration plants without additional investment considering in particular the FeCl 3 concentration in such spent acid.
  • the present invention is also directed to the possibility to revamp existing pickling lines, in particular the treatment tanks, and to use more efficient pickling technology with improved efficiency while re-using existing equipment in order to reduce installation costs, as for example acid circulation circuits etc. can be reused.
  • the present invention comprising a pickling process using an HCl containing pickling solution as the only pickling acid, wherein the material to be treated (i.e. the steel strip) is processed horizontally through one or more treatment tanks which are - in case of more than one treatment tank - operated as a pickling cascade.
  • each single treatment tank (of the treatment station) of the above described process comprises of one spray pickling zone and one dip pickling zone arranged as one unit using one common circulation circuit, i.e. one common circulation tank (common collection means) with several pump circuits as required. All pickling acid coming from the dip section and the spray section are collected and mixed in the common circulation tank (common collection means) and pumped back to the above mentioned two pickling sections (of the treatment tank of the treatment station).
  • a guide roll underneath the strip located between the spray and pickling section might be required to better position the steel strip inside the treatment tank.
  • a wringer roll unit - as it is typically installed between two pickling sections - is not required.
  • the first section of the treatment tank is a spray section while the second section of the dip pickling type, preferably with high efficiency such as shallow tank turbulence technology.
  • the steel strip is treated - in the treatment tank of the treatment station - by means of a treatment liquid such that the same treatment liquid is used both in the spray section and in the immersion section of the treatment tank.
  • a treatment liquid such that the same treatment liquid is used both in the spray section and in the immersion section of the treatment tank.
  • the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions, at least at the treatment station.
  • steel strip is mostly horizontally oriented in its transverse direction but is allowed to be sagging in its longitudinal direction.
  • the height variation through the treatment station of the steel strip in its longitudinal direction may reach, e.g., up to 0,5 m.
  • the height variations of the steel strip in its longitudinal direction are also comprised up to 0,5 m.
  • the height variation of the steel strip in its longitudinal direction is comprised between up to 0,5 m throughout the complete treatment system, that potentially (and typically) comprises a plurality of treatment stations one after the other in the transport direction of the steel strip.
  • the treatment liquid is sprayed - in a first step and by means of nozzles - onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip is in the spray section of the treatment station.
  • second step that is not necessarily subsequent to the first step but could also be preceding the first step
  • the steel strip is immersed in the treatment liquid while the steel strip is in the immersion section of the treatment station.
  • the treatment liquid of the treatment station is continuously pumped out of the common collection means (of that treatment station) and through both the spray section and the immersion section of the treatment tank, wherein spraying of the treatment liquid onto the top and bottom surfaces of the steel strip is provided using spray nozzles.
  • two pickling technologies are directly combined in one treatment tank (i.e. in one treatment station), i.e. using physically the same pickling acids (or the same treatment liquid) in both pickling sections (i.e. in both the spray section and the immersion section of the considered treatment station), as described.
  • the concentration of FeCl 3 can be kept below a critical level throughout the entire pickling process, guaranteeing a uniform pickling result without the risk of over-pickling.
  • the spent acid of such process can be easily regenerated in regeneration plants without additional investment to reach the legally required emission values, especially regarding dust emissions.
  • the efficiency of the treatment process is increased.
  • Tests have proven that a certain increase in the FeCl 3 concentration reduces the pickling time also for the dip pickling process. Consequently the process according to the present invention uses the advantage of the high efficient spray pickling process while the efficiency of the dip pickling process is improved as well, due to the common use of the pickling acid (i.e. the same treatment liquid is used both in the spray section and the immersion section of one and the same treatment station), and the consequently increased FeCl 3 level.
  • the pickling acid i.e. the same treatment liquid is used both in the spray section and the immersion section of one and the same treatment station
  • the design of the treatment line or pickling line is done in such a way that it is advantageously possible that the treatment stations or treatment tanks can easily replace existing treatment tanks in case of a required revamp (or refurbishment) while the circulation circuits can be reused.
  • This is mainly attributed to the fact that the spray pickling technology and the dip pickling technology (i.e. the spray section and the immersion section) are combined in one treatment tank (i.e. as part of one treatment tank).
  • the design of the present invention also allows the possibility to operate the treatment tanks without an additional (external) circulation tank - or common collection means - (i.e. external or separate to the treatment tank).
  • the treatment tank itself in particular the area underneath the spray section, and, if required, also underneath the dip section, is used as circulation tank (or common collection means), i.e. the circulation tank (or common collection means) is realized in a manner integrated with the treatment tank.
  • circulation tank or common collection means
  • the spray section comprises an effective spray length in parallel to the longitudinal direction of the steel strip such that - during the first step - the top and bottom surfaces of the steel strip receive the treatment liquid while being located within the effective spray length
  • the immersion section comprises an effective immersion length in parallel to the longitudinal direction of the steel strip such that - during the second step - the steel strip is immersed - with its top and bottom surfaces - in the treatment liquid while being located within the effective immersion length
  • the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  • the present invention it is thereby advantageously possible to flexibly adapt process parameters of a pickling line to fit best with the intended operative use after construction.
  • the time is defined during which the treatment liquid is effectively treating the steel strip in the immersion section.
  • the maximum time of spray pickling is defined in relation to the dip pickling time.
  • the effective spray length and hence the ratio of the effective spray length vs. the effective immersion length is varied by activating only a part of the spray nozzles.
  • the present invention it is thereby advantageously possible to vary the spray pickling time even during operational use of the pickling line, i.e. by de-activating a part of the spray nozzles.
  • By selectively activating and/or de-activating groups of spray nozzles is it advantageously possible according to the present invention, that also the manner or the intensity of the spray pickling step can be varied in operational use of the pickling line, e.g. by using only every second spray nozzle such that spray pickling is less intensive in the spray section.
  • the spray section is located - along the transport direction of the steel strip - upstream with respect to the immersion section. According to an alternative preferred embodiment of the present invention, the spray section is located - along the transport direction of the steel strip - downstream with respect to the immersion section.
  • the present invention it is thereby advantageously possible to provide the possibility of different pickling line architectures.
  • the first treatment station such that the spray section is located downstream with respect to the immersion section (i.e. the steel strip passes the immersion section first and afterwards the spray section)
  • the second treatment station such that the spray section is located upstream with respect to the immersion section (i.e. the steel strip passes the spray section (of the second treatment station) first and afterwards the dip section (of the second treatment station)):
  • these building blocks of two treatment stations can be either repeated or combined with other treatment stations or configurations of treatment stations.
  • the method comprises using - besides using the treatment liquid in the treatment station - a further treatment liquid in a further treatment station, the further treatment station comprising a further treatment tank with a further spray section and a further immersion section, and the further treatment station comprising a further common collection means for the further treatment liquid, wherein the method comprises transporting the steel strip continuously through the further treatment station in the transport direction such that
  • the two inventive treatment station are either located directly subsequent one after the other along the transport direction of the steel strip or the combination with one or a plurality of conventional treatment stations is provided such that the treatment station (or the first treatment station) is located upstream according to the transport direction of the steel strip with respect to a conventional treatment station (or with respect to a plurality of conventional treatment stations) and downstream with respect to this or these conventional treatment station(s) is located the further treatment station (or second treatment station) according to the present invention.
  • the treatment liquid and/or the further treatment liquid comprises
  • the present invention also relates to a system for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the system comprising the treatment station, wherein the treatment station comprises a treatment tank with a spray section, an immersion section, and the treatment station comprising a common collection means for the treatment liquid, wherein the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions, wherein the steel strip has a top surface and a bottom surface, wherein the system is configured to transport the steel strip continuously through the treatment station in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip, such that
  • the present invention it is thereby advantageously possible to provide a system (or a treatment station) that requires comparatively low installation costs as well as reduced maintenance costs. According to the present invention, it is advantageously possible to combine the advantages of spray pickling and dip pickling and to minimize the risk of over-pickling. It is furthermore advantageous that the spent acid of such a system is of a quality such that it can be treated in regeneration plants without additional investment considering in particular the FeCl 3 concentration in such spent acid.
  • the spray section comprises an effective spray length in parallel to the longitudinal direction of the steel strip such that the top and bottom surfaces of the steel strip receive the treatment liquid while being located within the effective spray length
  • the immersion section comprises an effective immersion length in parallel to the longitudinal direction of the steel strip such that the steel strip is immersed - with its top and bottom surfaces - in the treatment liquid while being located within the effective immersion length
  • the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  • the spray section is located - along the transport direction of the steel strip - upstream with respect to the immersion section.
  • the spray section is located - along the transport direction of the steel strip - downstream with respect to the immersion section.
  • the common collection means for the treatment liquid of both the spray section and the immersion section is a collection means separated from the treatment tank of the treatment station.
  • the treatment tank in a very cost effective manner such that especially the volume of the treatment tank is comparably small (and hence less treatment liquid is to be used).
  • the treatment liquid is pumped through the common collection means (or circulation tank) that is separated from the treatment tank.
  • the common collection means for the treatment liquid of both the spray section and the immersion section is a collection means integrated with the treatment tank of the treatment station, especially integrated such that the bottom part of the treatment tank forms the common collection means.
  • the system comprises - besides the treatment liquid in the treatment station - a further treatment liquid in a further treatment station, the further treatment station comprising a further treatment tank with a further spray section and a further immersion section, and the further treatment station comprising a further common collection means for the further treatment liquid, wherein the system is configured such that the steel strip is transported continuously through the further treatment station in the transport direction such that
  • the system comprises - besides the treatment liquid in the treatment station and the further treatment liquid in the further treatment station - a third treatment liquid in a third treatment station, the third treatment station comprising a third treatment tank with a third spray section and a third immersion section, and the third treatment station comprising a third common collection means for the third treatment liquid.
  • the system comprises - besides the treatment liquid in the treatment station, the further treatment liquid in the further treatment station, and the third treatment liquid in the third treatment station - a fourth treatment liquid in a fourth treatment station, the fourth treatment station comprising a fourth treatment tank with a fourth spray section and a fourth immersion section, and the fourth treatment station comprising a fourth common collection means for the fourth treatment liquid.
  • the combination of five treatment stations according to the present invention is possible and preferred according to the present invention.
  • the treatment liquid and/or the further treatment liquid and/or the third treatment liquid comprises
  • FIG 1 schematically illustrates a treatment system comprising three different treatment stations 3, 31, 32 as an example of a pickling line according to the present invention.
  • all three treatment stations 3, 31, 32 represent treatment stations according to the present invention, i.e. having a treatment tank with both a spray section and an immersion section such that a common collection means and the same treatment liquid is used for the treatment of the steel strip in both the respective spray section and the immersion section.
  • all three treatment stations 3, 31, 32 are realized either according to a first embodiment of the present invention, represented in Figure 2 for the exemplary case of the treatment station being represented by reference sign 3, or according to a second embodiment of the present invention, represented in Figure 3 for the exemplary case of the treatment station being represented by reference sign 3.
  • a part of the three treatment stations 3, 31, 32 is or are realized according to the first embodiment of the present invention ( Figure 2 ) and another part is or are realized according to the second embodiment of the present invention ( Figure 3 ).
  • the terms 'treatment station' and 'first treatment station' as well as 'further treatment station' and 'second treatment station' are used synonymously and only aim to differentiate the treatment stations from one another.
  • the naming convention typically (but not necessarily) relates to the location of a treatment station along the transport direction of the steel strip, the transport direction being represented by reference sign 2.
  • a treatment station (or first treatment station) 3 is located upstream of a further treatment station (or second treatment station) 31.
  • the further treatment station (or second treatment station) 31 is located upstream of a third treatment station 32.
  • the treatment station (or first treatment station) 3 comprises a treatment tank (or first treatment tank) 4, and a common collection means (or first common collection means) 5.
  • the further treatment station (or second treatment station) 31 comprises a further treatment tank (or second treatment tank) 41, and a further common collection means (or second common collection means) 51.
  • the third treatment station 32 comprises a third treatment tank 42, and a third common collection means 52.
  • all tree treatment stations 3, 31, 32 each have a spray section and an immersion section as part of their respective treatment tank 4, 41, 42, i.e.
  • the treatment station (or first treatment station) 3 has a spray section (or first spray section) and an immersion section (or first immersion section) using a treatment liquid (or first treatment liquid)
  • the further treatment station (or second treatment station) 31 has a further spray section (or second spray section) (not depicted in Figure 1 ) and a further immersion section (or second immersion section) (not depicted in Figure 1 ) using a further treatment liquid (or second treatment liquid)
  • the third treatment station 32 has a third spray section (not depicted in Figure 1 ) and a third immersion section (not depicted in Figure 1 ) using a third treatment liquid.
  • a first and a second embodiment of the present invention is schematically shown in Figures 2 and 3 .
  • Figure 2 schematically illustrates the first embodiment of the treatment station 3 having the treatment tank 4 and the common collection means 5 separated from the treatment tank 4, the treatment tank 4 having its spray section 13 and its immersion section 14 to treat the steel strip 1 with a common treatment liquid circulating between - and within - the common collection means 5 on the one hand, and the spray and immersion sections 13, 14 on the other hand.
  • Figure 3 schematically illustrates a second embodiment of a treatment station 3 having the treatment tank 4 and the common collection means 5 separated from the treatment tank 4, the treatment tank 4 having its spray section 13 and its immersion section 14 to treat the steel strip 1 with a common treatment liquid circulating between - and within - the common collection means 5 on the one hand, and the spray and immersion sections 13 on the other hand.
  • FIGs 1, 2 and 3 combined illustrate the inventive treatment process and system (or treatment station) for chemical or electrochemical treatment of the surface of the steel strip 1, the steel strip 1 being a stainless steel strip.
  • the steel strip 1 is first horizontally transported through the treatment stations 3, 31, 32 in which the steel strip 1 is treated with a treatment liquid in the form of a pickling acid, normally containing HCl.
  • At least one of the treatment stations 3, 31, 32 (or their respective treatment tanks 4, 41, 42) comprises a spray pickling section (as represented in Figures 2 and 3 as spray section 13 of the treatment station 3) and a dip pickling section (as represented in Figures 2 and 3 as immersion section 14 of the treatment station 3) according to the present invention.
  • Figure 1 shows an exemplary implementation with three treatment station 3, 31, 32 (each having a treatment tank) as a preferred embodiment, however the number of treatment stations (and treatment tanks) is at least one and is not limited to three.
  • All treatment stations 3, 31, 32 comprise a common collection means, respectively (i.e. the respective treatment tanks 4, 41, 42 are connected to respective common collection means (or circulation tanks) 5, 51, 52), wherein the common collection means 5, 51, 52 are either (i.e. potentially for each treatment station 3, 31, 32 differently) realized as separate tanks as shown in the first embodiment represented in Figure 2 or are realized as common collection means 5, 51, 52 integrated in the respective treatment tank 4, 41, 42 as shown in Figure 3 .
  • the common collection means (or circulation tanks) 5, 51, 52 are operated as a cascade, i.e. the fresh or regenerated acid (i.e. the treatment liquid) is added (cf. reference sign 54) to the last common collection means (or last circulation tank) 52 - i.e. being related to the most downstream treatment station 32 according to the transport direction 2 of the steel strip 1 - and is consequently transferred to the other common collection means (or circulation tanks) in counter direction to the strip transport direction 2.
  • the level of free acid is the highest in the third treatment liquid (circulating in the third treatment station 32), the level of free acid is medium in the further treatment liquid (second treatment liquid) (circulating in the further (second) treatment station 31), and lowest in the treatment liquid (first treatment liquid) (circulating in the (first) treatment station 3.
  • the spent acid is removed (reference sign 55) from the (first) common collection means (or (first) circulation tank) 5.
  • the steel strip 1 is further processed in section 6 which comprises a rinse section and a dryer, if required.
  • the treatment station 3 comprises the treatment tank 4 with a separate common collection means 5 (or separate circulation tank 5).
  • wringer rolls 12 are installed to remove pickling acid from the strip and to guide the steel strip 1 inside the treatment tank 4.
  • the wringer roll 12 in the entry section is only used when the treatment tank is the first tank in the pickling process like the treatment station 3 in Figure 1 .
  • the following treatment stations (or treatment tanks), like treatment stations 31, 32 in Figure 1 do not need such wringer roll 12.
  • Figure 2 i.e.
  • the first part (according to the transport direction of the steel strip 1) of the treatment tank 4 is a spray pickling section 13 or spray section 13, followed by a dip pickling section 14 or immersion section 14.
  • spray nozzles 15 are mounted above and below the surface of the steel strip 1.
  • the pickling acid (or treatment liquid) is pumped from the circulation tank 5 (or common collection means 5) by means of pumps 17, 18 to both the spray pickling section 13 and the dip pickling section 14.
  • a heat exchanger 19 is installed to heat the pickling acid (treatment liquid) to the required temperature.
  • a guide roll 20 can be installed between the spray pickling section 13 and the dip pickling section 14 in order to reduce the slack of the strip.
  • the treatment station 3 comprises the treatment tank 4 with an integrated common collection means 5.
  • the other components of the treatment station 3 are analogous to the description of Figure 2 .
  • the pickling line is configured for a maximum width of the steel strip 1 of 1890 mm, a maximum speed of the steel strip 1 of 85 m/min.
  • the distance of the spray nozzles 15 to the steel strip 1 (both from the spray nozzles to the top surface 1' of the steel strip 1, and to the bottom surface 1" of the steel strip 1) is 200 mm or approximately 200 mm.
  • the distance of the spray nozzles 15 to each other in the lateral direction of the steel strip 1 corresponds to 200 mm or approximately 200 mm.
  • the distance of the spray nozzles 15 to each other in the longitudinal direction of the steel strip 1 corresponds to 500 mm or approximately 500 mm.
  • the treatment liquid is preferably pumped out of the spray nozzles having a pressure of between and including 1 bar to and including 3 bar, and the amount of treatment liquid per spray nozzle is preferably 12 l/min or approximately 12 l/min.
  • the total number of spray nozzles per treatment station corresponds to 306 or approximately 306, and the amount of pumped treatment liquid per treatment station corresponds to 220 m 3 /h or approximately 220 m 3 /h.
  • Test trials were carried out in a pilot plant.
  • the pilot plant consisted of two treatment stations (each having a treatment tank) both arranged as described in the present invention with a first spray pickling section followed by a dip pickling section in each of the treatment tanks.
  • the treatment tanks were designed so that the length of both sections was approximately the same.
  • the pickling acid used was HCl with a concentration of approx. 200 g/l total acid in both tanks.
  • the material treated during the test runs were different austenitic steel grades such as AlSI 304 and 316.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The present invention relates to method for treating a steel strip by means of a treatment liquid in a treatment station, the treatment station comprising at least a spray section, an immersion section, and a common collection means for the treatment liquid,
wherein the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions, wherein the steel strip has a top surface and a bottom surface,
wherein the method comprises transporting the steel strip continuously through the treatment station in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip, such that
-- in a first step, the treatment liquid is sprayed onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip being in the spray section of the treatment station,
-- in a second step, the steel strip is immersed in the treatment liquid while the steel strip being in the immersion section of the treatment station,
wherein, while treating the steel strip, the treatment liquid is continuously pumped out of the common collection means and through both the spray section and the immersion section of the treatment station, wherein spraying of the treatment liquid onto the top and bottom surfaces of the steel strip is provided using spray nozzles.

Description

    BACKGROUND
  • The present invention relates to a method for treating a steel strip especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank.
  • Furthermore, the present invention relates to a system for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank.
  • The steel strip to be treated according to the method of the present invention and in a system of the present invention is stainless steel.
  • The presence of oxide scale on the surface of steel strip is formed during high temperature processing. The term oxide scale generally refers to the chemical compounds of iron and oxygen, as well as the chemical compounds of iron alloying elements, e.g. chromium and oxygen, formed on the surface of the steel by exposure to air while the metal is at an elevated temperature. Chemical compounds thus formed include iron oxides, such as FeO, Fe2O3 and Fe3O4, oxides of alloying elements such as CrO3, NiO, SiO2 and complex oxide spinals like FeCr2O4, NiFe2O4, Fe2SiO4 and others. During annealing, stainless steel grades are heated up to a certain temperature (850-1150 °C depending on steel grade) and are kept at this temperature for some time to soften the metal in order to release the work hardening induced by hot and cold rolling. A uniform grain structure is obtained depending on the annealing temperature, and oxide scale is formed on the surface. Underneath the surface of stainless steel, a chromium-depleted zone is formed, which is different for austenitic, ferritic and duplex stainless steel grades.
  • Processes are required in the stainless steel industry to remove that oxide scale and the chromium depleted layer to obtain technological products, but that has to be achieved with a minimum loss of base material. Pickling is the process of chemically removing of oxide scale from the surface of a metal by the action of water solution of inorganic acids. The stainless steel is widely pickled in diluted sulfuric or hydrochloric acid. For pickling of the stainless steel, a mixture of nitric acid and hydrofluoric acid is widely applied. The rate of pickling is affected by numerous variables, including the steel-based constituents and type and adherence of oxide to be removed. Pickling solution temperature, acid concentration, reaction product concentration, turbulence flow conditions, immersion time and presence or absence of inhibitors and accelerators influence the rate of acid attack. Because of production factors including pickling speed, quality and efficiency, as well as reduced attack of HCl on base metal, hydrochloric acid has effectively displaced sulfuric acid as the acid of choice in industrial large-scale pickling lines for stainless steel. While the rate of pickling increases in direct proportion to the concentration of the acid, the influence of temperature is much more pronounced. On the other hand, certain metals, such as cooper, chromium and nickel, retard the rate of pickling when they occur in the steel base, since the scale bearing these alloying metals inhibits acid attack. Elements like aluminum and silicon form refractory-type oxides, which in turn lower the solubility rate of the oxide in the pickling acid. The thickness of the oxide scale varies considerably with practice in rolling mills. E.g. loose coiling permits greater atmospheric penetration into the wraps, with corresponding heavier oxide formation on the edge areas. In addition, coiling temperature affects the adherence of the oxide and determines how easy or difficult it is to remove. The lower coiling temperatures makes oxide removal easier, at higher coiling temperatures longer pickling times are required. E.g. at the coiling temperature of 750 °C, double pickling time is required compared to the coiling temperature of 570 °C.
  • Like with carbon steel, the stainless steel also oxidizes following hot rolling and coiling. The oxide scale layer formed on the surface of the hot rolled stainless steel strip contains the alloying elements and is very tightly adhering on the surface, which makes the de-scaling or pickling of stainless steel very difficult as compared to the carbon steels. To achieve efficient and thorough surface oxide removal from a stainless steel strip, more severe processing techniques must be used which substantially increase processing time and operational costs. Frequently, to effect complete oxide scale removal, chemical pickling of stainless steel strip must be preceded by mechanical de-scaling, e.g. by shot-blasting and/or scale breaking. Often nowadays additional methods of Pre-Pickling is applied to soften the oxide scale. E.g. hot rolled stainless steel is conventionally pre-pickled in hot sulfuric acid and the cold rolled stainless steel is pre-pickled electrolytically in neutral electrolyte of Na2SO4 solution prior the main pickling in mixed acid. In today state-of-the-art practice, the Mechanical de-scaling (MD) and Pre-Pickling (PP) can remove the oxide scale layer only, the chromium-depleted zone and partly the base material can be only removed by the final pickling process (FP).
  • The pickling process most commonly used for stainless steel involves the use of a mixture of nitric and hydrofluoric acid, the mutual concentrations of which vary according to the type of stainless steel to be pickled (austenitic, ferritic, martensitic, duplex...), its surface characteristics and its past processing history. When processing of 300 and 400 series in the same line, various acid compositions (Mix I and Mix II) and various acid mixture temperatures are required. Since austenitic steel grades are pickled at 50-65 °C, the most of ferritic and martensitic stainless steel grades generate exothermal reaction during the pickling, which require cooling facilities in the pickling line in order to keep the acid mixture temperature in the range of 35-40 °C .Although the process enables excellent pickling results to be obtained, it has the very serious drawback that it creates considerable and substantial ecological problems due to the use of these particular acids. The hydrofluoric acid is extremely corrosive and a harmful environmental pollutant. The nitric acid is the source of highly polluting nitrogen oxide (NOx) vapors which are emitted into the atmosphere and which are highly aggressive towards metals and nonmetals with which they come into contact. In addition, high nitrate levels exist in the rinse water and in the spent pickling baths and create a major disposal problem. The elimination of NOx vapors in the air by catalytic DENOX plants and nitrates in the neutralized waste water creates considerable plant operational problems, very high investment costs for equipment, high maintenance demand and very high operational costs. As a result, there has been considerable interest in researching and developing stainless steel pickling processes and plants which do not use either nitric acid or hydrofluoric acid and which are ecologically safe and environmental-friendly.
  • Today pickling lines are designed as shallow tank turbulence installations comprising of several consecutive pickling tanks. The steel strip is pulled or pushed through the treatment tanks. The complete pickling section is arranged as a cascade, i.e. the fresh or regenerated acid is added to the last treatment tank (i.e. the most downstream treatment tank according to the direction of movement of the steel strip) and is then processed in a countercurrent flow to the strip transport direction in order to maximize the use of the pickling acid. At the entry and exit of the treatment tanks, wringer rolls are installed to remove the pickling acid from the strip to the greatest possible extend in order to enhance the cascade effect. German patent disclosure DE 40 31 234 describes this technology.
  • Inside the treatment tank, the pickling acid is injected on both sides of the tank creating a high turbulence between the strip surface and the pickling acid.
  • The pickling acid is then overflowing from the treatment tank to a circulation tank from where it is again injected into the treatment tank by means of pumps. The high turbulence reduces the thickness of the liquid boundary layer on the strip surface resulting in an improved media and energy exchange and consequently reducing the required pickling time.
  • Another well known pickling method is the spray pickling, wherein the pickling acid is directly sprayed onto the strip surface using several spray nozzles installed both above and below the steel strip, cf. e.g. document DE 42 28 808 A1 . The pickling acid is then collected in a circulation tank from where it is pumped to the spray nozzles and sprayed on to the strip surface again. The spray nozzles are typically operated at a pressure above 1 bar. Due to the high impulse of the pickling acid sprayed onto the strip surface, the pickling efficiency and consequently the pickling time can be further improved. However this technology has never been used commercially in strip pickling lines.
  • The use of hydrochloric acid as a pickling agent for stainless steel pickling allows the realization of pickling mechanisms of both the removal of oxide scale and the chromium-depleted zone. The pickling of stainless steel in hydrochloric acid is a combined process of reduction and oxidation.
    The chemical dissolution of steel in HCl is as follows:

             Fe + 2 HCl → FeCl2 + H2

    The base metal, Fe, is dissolved by the oxidizing agents, mainly FeCl3:

             2 FeCl3 + Fe → 3 FeCl2

    Oxidation reaction to produce the required oxidizing agent is as follows:

             4 FeCl2 + O2 + 4 HCl → 4 FeCl3 + 2 H2O

    A minimum proper FeCl3 concentration is required for the pickling process of stainless steel. This is today typically reached by adding H2O2 to the pickling liquid.
  • In the context of the present invention, chlorides of iron and chlorides of other metals (especially chromium) are collectively referred to by the term MeCl.
  • Laboratory tests, carried out for different steel grades, have proven for HCl containing pickling solution, that the pickling speed of spray-pickling is up to five times higher compared to the shallow tank turbulence technology. In addition, the spray nozzles used in the spray pickling technology create fine droplets with a high surface which are in direct contact with air. The air, in particular the oxygen contained in the air, dissolves in the pickling acid and oxidizes the FeCl2 together with the HCl forming FeCl3. Therefore using HCl in a spray pickling section to treat stainless steel has the advantage, that no H2O2 is needed to create FeCl3. However, in pure spray pickling tanks, the formation of FeCl3 can be too high (to reach 60 g/l and above), making the whole pickling process difficult to control, with a high risk of over pickling the metal strip or causing inacceptable roughness of the strip surface. Another drawback of the increased FeCl3 concentration in the pickling acid is the effect on the regeneration process of the spent pickling acid. Spent pickling acid containing HCl is typically regenerated using the pyrohydrolysis process. In this process FeCl2 and FeCl3 are converted back to HCl and Fe2O3. FeCl3 however has a much lower evaporation temperature than FeCl2 and evaporates in the pyrohydrolysis reactor causing very fine Fe2O3 particles below 1 µm in size when converted to Fe2O3. These fine particles are difficult to remove from the process off-gases causing high dust emissions.
  • SUMMARY
  • It is therefore an object of the present invention to provide method and a system for an improved steel strip treatment, especially pickling, such that fixed investment as well as maintenance costs are reduced, the treatment and pickling process is realized comparatively quickly, with high quality, and in an environmentally friendly manner.
  • The object of the present invention is achieved by a method for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the treatment station comprising a treatment tank with a spray section and an immersion section, and the treatment station comprising a common collection means for the treatment liquid,
    wherein the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions,
    wherein the steel strip has a top surface and a bottom surface,
    wherein the method comprises transporting the steel strip continuously through the treatment station in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip, such that
    • -- in a first step, the treatment liquid is sprayed onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip being in the spray section of the treatment station,
    • -- in a second step, the steel strip is immersed in the treatment liquid while the steel strip being in the immersion section of the treatment station,
    wherein, while treating the steel strip, the treatment liquid is continuously pumped out of the common collection means and through both the spray section and the immersion section of the treatment station, wherein spraying of the treatment liquid onto the top and bottom surfaces of the steel strip is provided using spray nozzles.
  • According to the present invention, it is thereby advantageously possible to provide a treatment station that requires comparatively low installation costs as well as reduced maintenance costs. The present invention is related to a process for chemical or electrochemical treatment of the surface of stainless steel, preferably strip shaped, wherein the material is treated with a pickling solution, preferably containing HCl, in one or more treatment tanks to remove an oxide scale layer which was previously formed during the hot rolling process of the metal strip (steel strip). This treatment is needed to reach a clean surface for either further processing it in a cold rolling process or for direct commercial use.
  • According to the present invention, it is preferred that the process for chemical or electrochemical treatment of the surface of stainless steel is conducted using a pickling solution containing HCl as the only pickling agent, wherein the advantages of spray pickling are used to a maximum extend. Furthermore the process shall be controllable minimizing the risk of over-pickling so that the process can be realized in commercially used industrial scale pickling lines.
  • This drastically shortening of the pickling time in case of spray and turbulence pickling can be explained by a very thin laminar boundary layer, which is much more thinner than in case of turbulence dip process. The drive force of heat, mass and momentum transfer across the boundary layer is faster, since the thickness of this layer is significantly reduced.
  • According to the present invention, the spent acid of such a process is of a quality such that it can be treated in regeneration plants without additional investment considering in particular the FeCl3 concentration in such spent acid.
  • The present invention is also directed to the possibility to revamp existing pickling lines, in particular the treatment tanks, and to use more efficient pickling technology with improved efficiency while re-using existing equipment in order to reduce installation costs, as for example acid circulation circuits etc. can be reused.
  • According to the present invention, it is advantageously possible that such requirements can be achieved by the present invention, comprising a pickling process using an HCl containing pickling solution as the only pickling acid, wherein the material to be treated (i.e. the steel strip) is processed horizontally through one or more treatment tanks which are - in case of more than one treatment tank - operated as a pickling cascade.
  • According to the present invention, each single treatment tank (of the treatment station) of the above described process comprises of one spray pickling zone and one dip pickling zone arranged as one unit using one common circulation circuit, i.e. one common circulation tank (common collection means) with several pump circuits as required. All pickling acid coming from the dip section and the spray section are collected and mixed in the common circulation tank (common collection means) and pumped back to the above mentioned two pickling sections (of the treatment tank of the treatment station). Inside the single pickling tank (treatment tank), a guide roll underneath the strip located between the spray and pickling section might be required to better position the steel strip inside the treatment tank. Typically, a wringer roll unit - as it is typically installed between two pickling sections - is not required. Preferably the first section of the treatment tank is a spray section while the second section of the dip pickling type, preferably with high efficiency such as shallow tank turbulence technology.
  • According to the present invention, the steel strip is treated - in the treatment tank of the treatment station - by means of a treatment liquid such that the same treatment liquid is used both in the spray section and in the immersion section of the treatment tank. Advantageously, it is thereby possible to realize the treatment station (having both the spray section and the immersion section) in a more cost effective manner as the same common collection means (as well as at least a part of the circulation system) can be used for both the spray section and the immersion section, hence reducing the costs for realizing the possibility to treat the steel strip by means of both the spray section and the immersion section.
  • According to the present invention, the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions, at least at the treatment station. This means that steel strip is mostly horizontally oriented in its transverse direction but is allowed to be sagging in its longitudinal direction. The height variation through the treatment station of the steel strip in its longitudinal direction may reach, e.g., up to 0,5 m. Preferably, also between the treatment station or between the plurality of treatment stations, the height variations of the steel strip in its longitudinal direction are also comprised up to 0,5 m. Generally, it is preferred according to the present invention that the height variation of the steel strip in its longitudinal direction is comprised between up to 0,5 m throughout the complete treatment system, that potentially (and typically) comprises a plurality of treatment stations one after the other in the transport direction of the steel strip.
  • According to the present invention, the treatment liquid is sprayed - in a first step and by means of nozzles - onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip is in the spray section of the treatment station. In second step (that is not necessarily subsequent to the first step but could also be preceding the first step), the steel strip is immersed in the treatment liquid while the steel strip is in the immersion section of the treatment station. For the treatment of the steel strip, the treatment liquid of the treatment station is continuously pumped out of the common collection means (of that treatment station) and through both the spray section and the immersion section of the treatment tank, wherein spraying of the treatment liquid onto the top and bottom surfaces of the steel strip is provided using spray nozzles.
  • According to the present invention, two pickling technologies are directly combined in one treatment tank (i.e. in one treatment station), i.e. using physically the same pickling acids (or the same treatment liquid) in both pickling sections (i.e. in both the spray section and the immersion section of the considered treatment station), as described. By doing so, the concentration of FeCl3 can be kept below a critical level throughout the entire pickling process, guaranteeing a uniform pickling result without the risk of over-pickling. Furthermore the spent acid of such process can be easily regenerated in regeneration plants without additional investment to reach the legally required emission values, especially regarding dust emissions.
  • According to the present invention, the efficiency of the treatment process (or pickling process) is increased. Tests have proven that a certain increase in the FeCl3 concentration reduces the pickling time also for the dip pickling process. Consequently the process according to the present invention uses the advantage of the high efficient spray pickling process while the efficiency of the dip pickling process is improved as well, due to the common use of the pickling acid (i.e. the same treatment liquid is used both in the spray section and the immersion section of one and the same treatment station), and the consequently increased FeCl3 level. Of course, in (the typical) case that more than one treatment stations are used in a pickling line or steel strip pickling installation, this does not mean that the same treatment liquid is used in all of such different treatment stations. To the contrary, in case of a plurality of treatment stations (i.e. having each a treatment tank comprising a spray section and an immersion section), a different treatment liquid is normally used for a different treatment station; however within the same treatment station/treatment tank, the same treatment liquid is used for both kinds of pickling processes (spray and dip pickling). Thereby, it is advantageously possible that the drawbacks of a comparatively high concentration in FeCl3 can be avoided that would typically arise in case of combining spray pickling and dib pickling using different treatment liquids in the same treatment station.
  • According to the present invention, the design of the treatment line or pickling line is done in such a way that it is advantageously possible that the treatment stations or treatment tanks can easily replace existing treatment tanks in case of a required revamp (or refurbishment) while the circulation circuits can be reused. This is mainly attributed to the fact that the spray pickling technology and the dip pickling technology (i.e. the spray section and the immersion section) are combined in one treatment tank (i.e. as part of one treatment tank).
  • The design of the present invention also allows the possibility to operate the treatment tanks without an additional (external) circulation tank - or common collection means - (i.e. external or separate to the treatment tank). In such an embodiment, the treatment tank itself, in particular the area underneath the spray section, and, if required, also underneath the dip section, is used as circulation tank (or common collection means), i.e. the circulation tank (or common collection means) is realized in a manner integrated with the treatment tank. This is advantageous for the replacement (refurbishment) of deep bath treatment tanks which have often been operated without circulation circuits. In this case only the pump circuit needs to be added while the circulation tank is incorporated (or integrated) in the treatment tank.
  • According to a preferred embodiment of the present invention, the spray section comprises an effective spray length in parallel to the longitudinal direction of the steel strip such that - during the first step - the top and bottom surfaces of the steel strip receive the treatment liquid while being located within the effective spray length, wherein the immersion section comprises an effective immersion length in parallel to the longitudinal direction of the steel strip such that - during the second step - the steel strip is immersed - with its top and bottom surfaces - in the treatment liquid while being located within the effective immersion length, wherein the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  • According to the present invention, it is thereby advantageously possible to flexibly adapt process parameters of a pickling line to fit best with the intended operative use after construction. By means of defining the length of the immersion section (at a given transport speed of the steel strip through the pickling line), the time is defined during which the treatment liquid is effectively treating the steel strip in the immersion section. By means of defining the length of the spray section (equally at a given transport speed of the steel strip trough the pickling line), the maximum time of spray pickling is defined in relation to the dip pickling time.
  • According to another preferred embodiment of the present invention, the effective spray length and hence the ratio of the effective spray length vs. the effective immersion length is varied by activating only a part of the spray nozzles.
  • According to the present invention, it is thereby advantageously possible to vary the spray pickling time even during operational use of the pickling line, i.e. by de-activating a part of the spray nozzles. By selectively activating and/or de-activating groups of spray nozzles, is it advantageously possible according to the present invention, that also the manner or the intensity of the spray pickling step can be varied in operational use of the pickling line, e.g. by using only every second spray nozzle such that spray pickling is less intensive in the spray section.
  • According to a preferred embodiment of the present invention, the spray section is located - along the transport direction of the steel strip - upstream with respect to the immersion section. According to an alternative preferred embodiment of the present invention, the spray section is located - along the transport direction of the steel strip - downstream with respect to the immersion section.
  • According to the present invention, it is thereby advantageously possible to provide the possibility of different pickling line architectures. E.g., it is advantageously possible (in case that at least two treatment stations are used) to provide both treatment stations such that the spray section is located upstream with respect to the immersion section (i.e. the steel strip passes the spray section first and afterwards the immersion section): This results in a pickling sequence of the kind of a spray and dip pickling (using a first treatment liquid) in the first (or upstream) treatment station, followed by a spray and dip pickling (using a second treatment liquid) in the second (or downstram) treatment station. Alternatively, it is also advantageously possible (in case that at least two treatment stations are used) to provide the first treatment station such that the spray section is located downstream with respect to the immersion section (i.e. the steel strip passes the immersion section first and afterwards the spray section), and to provide the second treatment station such that the spray section is located upstream with respect to the immersion section (i.e. the steel strip passes the spray section (of the second treatment station) first and afterwards the dip section (of the second treatment station)): This results in a pickling sequence of the kind of a dip and spray pickling (using a first treatment liquid) in the first (or upstream) treatment station, followed by a spray and dip pickling (using a second treatment liquid) in the second (or downstream) treatment station. Of course, these building blocks of two treatment stations can be either repeated or combined with other treatment stations or configurations of treatment stations.
  • According to a preferred embodiment of the present invention, the method comprises using - besides using the treatment liquid in the treatment station - a further treatment liquid in a further treatment station, the further treatment station comprising a further treatment tank with a further spray section and a further immersion section, and the further treatment station comprising a further common collection means for the further treatment liquid, wherein the method comprises transporting the steel strip continuously through the further treatment station in the transport direction such that
    • -- in a third step, the further treatment liquid is sprayed onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip being in the further spray section of the further treatment station,
    • -- in a fourth step, the steel strip is immersed in the further treatment liquid while the steel strip being in the further immersion section of the further treatment station,
    wherein, while treating the steel strip, the further treatment liquid is continuously pumped out of the further common collection means and through both the further spray section and the further immersion section of the further treatment station , wherein spraying of the further treatment liquid onto the top and bottom surfaces of the steel strip is provided using further spray nozzles, wherein the third and fourth steps are preceding the first and second steps or are subsequent to the first and second steps.
  • According to the present invention, it is thereby advantageously possible to combine at least two inventive treatment stations in a pickling line. Of course, it is also possible and preferred according to the present invention to combine such two inventive treatment stations with a conventional treatment station (i.e. having solely a spray section or solely an immersion section in a treatment tank) or with a plurality of conventional treatment stations. In such an architecture of the pickling line, the two inventive treatment station are either located directly subsequent one after the other along the transport direction of the steel strip or the combination with one or a plurality of conventional treatment stations is provided such that the treatment station (or the first treatment station) is located upstream according to the transport direction of the steel strip with respect to a conventional treatment station (or with respect to a plurality of conventional treatment stations) and downstream with respect to this or these conventional treatment station(s) is located the further treatment station (or second treatment station) according to the present invention.
  • According to another preferred embodiment of the present invention, the treatment liquid and/or the further treatment liquid comprises
    • -- hydrochloric acid in a concentration ranging from and including 150 g/l to and including 250 g/l and
    • -- FeCl3 in a concentration ranging from and including 10 g/l to and including 35 g/l, especially in a concentration ranging from and including 15 g/l to and including 30 g/l or especially in a concentration ranging from and including 19 g/l to and including 26 g/l and,
    • -- MeCl2 in a concentration ranging from and including 30 g/l to and including 300 g/l, especially in a concentration ranging from and including 30 g/l to and including 60 g/l or in a concentration ranging from and including 130 g/l to and including 180 g/l or in a concentration ranging from and including 230 g/l to and including 300 g/l.
  • According to the present invention, it is thereby advantageously possible to combine a high efficiency of the pickling process while retaining the possibility to comparatively easily regenerated the used pickling acids (treatment liquids).
  • The present invention also relates to a system for treating a steel strip, especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station, the system comprising the treatment station, wherein the treatment station comprises a treatment tank with a spray section, an immersion section, and the treatment station comprising a common collection means for the treatment liquid,
    wherein the steel strip comprises stainless steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions,
    wherein the steel strip has a top surface and a bottom surface,
    wherein the system is configured to transport the steel strip continuously through the treatment station in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip, such that
    • -- the treatment liquid is sprayed onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip being in the spray section of the treatment station,
    • -- the steel strip is immersed in the treatment liquid while the steel strip being in the immersion section of the treatment station,
    wherein the system is configured such that the treatment liquid is continuously pumped out of the common collection means and through both the spray section and the immersion section of the treatment station, wherein the system comprises spray nozzles such that the treatment liquid is sprayed onto the top and bottom surfaces of the steel strip using the spray nozzles.
  • According to the present invention, it is thereby advantageously possible to provide a system (or a treatment station) that requires comparatively low installation costs as well as reduced maintenance costs. According to the present invention, it is advantageously possible to combine the advantages of spray pickling and dip pickling and to minimize the risk of over-pickling. It is furthermore advantageous that the spent acid of such a system is of a quality such that it can be treated in regeneration plants without additional investment considering in particular the FeCl3 concentration in such spent acid.
  • According to a preferred embodiment of the present invention - especially regarding the inventive system -, the spray section comprises an effective spray length in parallel to the longitudinal direction of the steel strip such that the top and bottom surfaces of the steel strip receive the treatment liquid while being located within the effective spray length, wherein the immersion section comprises an effective immersion length in parallel to the longitudinal direction of the steel strip such that the steel strip is immersed - with its top and bottom surfaces - in the treatment liquid while being located within the effective immersion length, wherein the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  • According to the present invention, it is thereby advantageously possible to XXX
  • According to a preferred embodiment of the present invention - especially regarding the inventive system -, the spray section is located - along the transport direction of the steel strip - upstream with respect to the immersion section. According to an alternative preferred embodiment of the present invention - especially regarding the inventive system -, the spray section is located - along the transport direction of the steel strip - downstream with respect to the immersion section.
  • According to the present invention, it is thereby advantageously possible to flexibly adapt process parameters of a pickling line to fit best with the intended operative use after construction.
  • According to a preferred embodiment of the present invention - especially regarding the inventive system -, the common collection means for the treatment liquid of both the spray section and the immersion section is a collection means separated from the treatment tank of the treatment station.
  • According to the present invention, it is thereby advantageously possible to build the treatment tank in a very cost effective manner such that especially the volume of the treatment tank is comparably small (and hence less treatment liquid is to be used). The treatment liquid is pumped through the common collection means (or circulation tank) that is separated from the treatment tank.
  • According to a preferred embodiment of the present invention - especially regarding the inventive system -, the common collection means for the treatment liquid of both the spray section and the immersion section is a collection means integrated with the treatment tank of the treatment station, especially integrated such that the bottom part of the treatment tank forms the common collection means.
  • According to the present invention, it is thereby advantageously possible to realize the treatment station in a very cost effective manner as no separate common collection means (or circulation tank) is required.
  • According to a preferred embodiment of the present invention - especially regarding the inventive system -, the system comprises - besides the treatment liquid in the treatment station - a further treatment liquid in a further treatment station, the further treatment station comprising a further treatment tank with a further spray section and a further immersion section, and the further treatment station comprising a further common collection means for the further treatment liquid, wherein the system is configured such that the steel strip is transported continuously through the further treatment station in the transport direction such that
    • -- the further treatment liquid is sprayed onto the top surface of the steel strip and onto the bottom surface of the steel strip while the steel strip being in the further spray section of the further treatment station,
    • -- the steel strip is immersed in the further treatment liquid while the steel strip being in the further immersion section of the further treatment station,
    wherein the system is configured such that the further treatment liquid is continuously pumped out of the further common collection means and through both the further spray section and the further immersion section of the further treatment station, wherein the system comprises further spray nozzles such that the further treatment liquid is sprayed onto the top and bottom surfaces of the steel strip using the further spray nozzles.
  • According to the present invention, it is thereby advantageously possible to combine at least two inventive treatment stations in a pickling line. Of course, it is also possible and preferred according to the present invention to combine such two inventive treatment stations with a conventional treatment station (i.e. having solely a spray section or solely an immersion section in a treatment tank) or with a plurality of conventional treatment stations.
  • According to a preferred embodiment of the present invention, the system comprises - besides the treatment liquid in the treatment station and the further treatment liquid in the further treatment station - a third treatment liquid in a third treatment station, the third treatment station comprising a third treatment tank with a third spray section and a third immersion section, and the third treatment station comprising a third common collection means for the third treatment liquid.
  • According to the present invention, it is thereby advantageously possible to combine at least three inventive treatment stations in a pickling line. Of course, it is also possible and preferred according to the present invention to combine such three inventive treatment stations with a conventional treatment station (i.e. having solely a spray section or solely an immersion section in a treatment tank) or with a plurality of conventional treatment stations.
  • According to a further preferred embodiment of the present invention, the system comprises - besides the treatment liquid in the treatment station, the further treatment liquid in the further treatment station, and the third treatment liquid in the third treatment station - a fourth treatment liquid in a fourth treatment station, the fourth treatment station comprising a fourth treatment tank with a fourth spray section and a fourth immersion section, and the fourth treatment station comprising a fourth common collection means for the fourth treatment liquid. According to other embodiments, also the combination of five treatment stations according to the present invention is possible and preferred according to the present invention.
  • According to another preferred embodiment of the present invention, the treatment liquid and/or the further treatment liquid and/or the third treatment liquid comprises
    • -- hydrochloric acid in a concentration ranging from and including 150 g/l to and including 250 g/l and
    • -- FeCl3 in a concentration ranging from and including 10 g/l to and including 35 g/l, especially in a concentration ranging from and including 15 g/l to and including 30 g/l or especially in a concentration ranging from and including 19 g/l to and including 26 g/l and,
    • -- FeCl2 in a concentration ranging from and including 30 g/l to and including 300 g/l, especially in a concentration ranging from and including 30 g/l to and including 60 g/l or in a concentration ranging from and including 130 g/l to and including 180 g/l or in a concentration ranging from and including 230 g/l to and including 300 g/l.
  • According to the present invention, it is thereby advantageously possible to combine a high efficiency of the pickling process while retaining the possibility to comparatively easily regenerated the used pickling acids (treatment liquids).
  • These and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. The description is given for the sake of example only, without limiting the scope of the invention. The reference figures quoted below refer to the attached drawings.
  • BRIEF DESCRIPTION OF THE DRAWINGS
    • Figure 1 schematically illustrates a treatment system comprising three different treatment stations, each one being configured according to the present invention, i.e. having a treatment tank with both a spray section and an immersion section such that a common collection means and the same treatment liquid is used for the treatment of the steel strip in both the respective spray section and the immersion section.
    • Figure 2 schematically illustrates a first embodiment of a treatment station having a treatment tank and a common collection means separated from the treatment tank, the treatment tank having its spray section and its immersion section to treat the steel strip with a common treatment liquid circulating between - and within - the common collection means on the one hand, and the spray and immersion sections on the other hand.
    • Figure 3 schematically illustrates a second embodiment of a treatment station having a treatment tank and a common collection means separated from the treatment tank, the treatment tank having its spray section and its immersion section to treat the steel strip with a common treatment liquid circulating between - and within - the common collection means on the one hand, and the spray and immersion sections on the other hand.
    DETAILED DESCRIPTION
  • The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn on scale for illustrative purposes.
  • Where an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an", "the", this includes a plural of that noun unless something else is specifically stated.
  • Furthermore, the terms first, second, third and the like in the description and in the claims are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described of illustrated herein.
  • Figure 1 schematically illustrates a treatment system comprising three different treatment stations 3, 31, 32 as an example of a pickling line according to the present invention. In one possible and preferred implementation of the pickling line for the treatment of a steel strip 1, represented in Figure 1, all three treatment stations 3, 31, 32 represent treatment stations according to the present invention, i.e. having a treatment tank with both a spray section and an immersion section such that a common collection means and the same treatment liquid is used for the treatment of the steel strip in both the respective spray section and the immersion section. In this implementation or architecture of the pickling line, all three treatment stations 3, 31, 32 are realized either according to a first embodiment of the present invention, represented in Figure 2 for the exemplary case of the treatment station being represented by reference sign 3, or according to a second embodiment of the present invention, represented in Figure 3 for the exemplary case of the treatment station being represented by reference sign 3. Alternatively, a part of the three treatment stations 3, 31, 32 is or are realized according to the first embodiment of the present invention (Figure 2) and another part is or are realized according to the second embodiment of the present invention (Figure 3). In the context of the present invention, the terms 'treatment station' and 'first treatment station' as well as 'further treatment station' and 'second treatment station' are used synonymously and only aim to differentiate the treatment stations from one another. Typically, the naming convention typically (but not necessarily) relates to the location of a treatment station along the transport direction of the steel strip, the transport direction being represented by reference sign 2. In the implementation represented in Figure 1, a treatment station (or first treatment station) 3 is located upstream of a further treatment station (or second treatment station) 31. The further treatment station (or second treatment station) 31 is located upstream of a third treatment station 32. The treatment station (or first treatment station) 3 comprises a treatment tank (or first treatment tank) 4, and a common collection means (or first common collection means) 5. The further treatment station (or second treatment station) 31 comprises a further treatment tank (or second treatment tank) 41, and a further common collection means (or second common collection means) 51. The third treatment station 32 comprises a third treatment tank 42, and a third common collection means 52. In the exemplary implementation of the pickling line represented in Figure 1 (where all treatment stations are configured according to the present invention), all tree treatment stations 3, 31, 32 each have a spray section and an immersion section as part of their respective treatment tank 4, 41, 42, i.e. the treatment station (or first treatment station) 3 has a spray section (or first spray section) and an immersion section (or first immersion section) using a treatment liquid (or first treatment liquid), the further treatment station (or second treatment station) 31 has a further spray section (or second spray section) (not depicted in Figure 1) and a further immersion section (or second immersion section) (not depicted in Figure 1) using a further treatment liquid (or second treatment liquid), and the third treatment station 32 has a third spray section (not depicted in Figure 1) and a third immersion section (not depicted in Figure 1) using a third treatment liquid. For the exemplary case of the treatment station 3 (first treatment station 3), a first and a second embodiment of the present invention is schematically shown in Figures 2 and 3.
  • Figure 2 schematically illustrates the first embodiment of the treatment station 3 having the treatment tank 4 and the common collection means 5 separated from the treatment tank 4, the treatment tank 4 having its spray section 13 and its immersion section 14 to treat the steel strip 1 with a common treatment liquid circulating between - and within - the common collection means 5 on the one hand, and the spray and immersion sections 13, 14 on the other hand.
  • Figure 3 schematically illustrates a second embodiment of a treatment station 3 having the treatment tank 4 and the common collection means 5 separated from the treatment tank 4, the treatment tank 4 having its spray section 13 and its immersion section 14 to treat the steel strip 1 with a common treatment liquid circulating between - and within - the common collection means 5 on the one hand, and the spray and immersion sections 13 on the other hand.
  • Figures 1, 2 and 3 combined illustrate the inventive treatment process and system (or treatment station) for chemical or electrochemical treatment of the surface of the steel strip 1, the steel strip 1 being a stainless steel strip. The steel strip 1 is first horizontally transported through the treatment stations 3, 31, 32 in which the steel strip 1 is treated with a treatment liquid in the form of a pickling acid, normally containing HCl. At least one of the treatment stations 3, 31, 32 (or their respective treatment tanks 4, 41, 42) comprises a spray pickling section (as represented in Figures 2 and 3 as spray section 13 of the treatment station 3) and a dip pickling section (as represented in Figures 2 and 3 as immersion section 14 of the treatment station 3) according to the present invention. Figure 1 shows an exemplary implementation with three treatment station 3, 31, 32 (each having a treatment tank) as a preferred embodiment, however the number of treatment stations (and treatment tanks) is at least one and is not limited to three.
  • All treatment stations 3, 31, 32 comprise a common collection means, respectively (i.e. the respective treatment tanks 4, 41, 42 are connected to respective common collection means (or circulation tanks) 5, 51, 52), wherein the common collection means 5, 51, 52 are either (i.e. potentially for each treatment station 3, 31, 32 differently) realized as separate tanks as shown in the first embodiment represented in Figure 2 or are realized as common collection means 5, 51, 52 integrated in the respective treatment tank 4, 41, 42 as shown in Figure 3.
  • In the exemplary embodiment shown in Figure 1, the common collection means (or circulation tanks) 5, 51, 52 are operated as a cascade, i.e. the fresh or regenerated acid (i.e. the treatment liquid) is added (cf. reference sign 54) to the last common collection means (or last circulation tank) 52 - i.e. being related to the most downstream treatment station 32 according to the transport direction 2 of the steel strip 1 - and is consequently transferred to the other common collection means (or circulation tanks) in counter direction to the strip transport direction 2. Thereby, the level of free acid is the highest in the third treatment liquid (circulating in the third treatment station 32), the level of free acid is medium in the further treatment liquid (second treatment liquid) (circulating in the further (second) treatment station 31), and lowest in the treatment liquid (first treatment liquid) (circulating in the (first) treatment station 3. Finally the spent acid is removed (reference sign 55) from the (first) common collection means (or (first) circulation tank) 5. After the pickling treatment in the three treatment stations 3, 31, 32 (in the exemplary implementation shown in Figure 1), the steel strip 1 is further processed in section 6 which comprises a rinse section and a dryer, if required.
  • According to the first embodiment of the common collection means (or circulation tank) 5, shown in Figure 2, the treatment station 3 comprises the treatment tank 4 with a separate common collection means 5 (or separate circulation tank 5). At the entry and exit section, wringer rolls 12 are installed to remove pickling acid from the strip and to guide the steel strip 1 inside the treatment tank 4. The wringer roll 12 in the entry section is only used when the treatment tank is the first tank in the pickling process like the treatment station 3 in Figure 1. The following treatment stations (or treatment tanks), like treatment stations 31, 32 in Figure 1, do not need such wringer roll 12. In the exemplary representation of Figure 2 (i.e. not necessarily), the first part (according to the transport direction of the steel strip 1) of the treatment tank 4 is a spray pickling section 13 or spray section 13, followed by a dip pickling section 14 or immersion section 14. In the spray pickling section 13, spray nozzles 15 are mounted above and below the surface of the steel strip 1. The pickling acid (or treatment liquid) is pumped from the circulation tank 5 (or common collection means 5) by means of pumps 17, 18 to both the spray pickling section 13 and the dip pickling section 14. In one or more of the pump circuits, a heat exchanger 19 is installed to heat the pickling acid (treatment liquid) to the required temperature. If required, a guide roll 20 can be installed between the spray pickling section 13 and the dip pickling section 14 in order to reduce the slack of the strip.
  • According to the second embodiment of the common collection means (or circulation tank) 5, shown in Figure 3, the treatment station 3 comprises the treatment tank 4 with an integrated common collection means 5. The other components of the treatment station 3 are analogous to the description of Figure 2.
  • While specific embodiments of the invention have been shown and described in detail to illustrate the inventive principles, it will be understood that the invention may be embodied otherwise without departing from such principles.
  • For example, the pickling line is configured for a maximum width of the steel strip 1 of 1890 mm, a maximum speed of the steel strip 1 of 85 m/min. Furthermore exemplarily, the distance of the spray nozzles 15 to the steel strip 1 (both from the spray nozzles to the top surface 1' of the steel strip 1, and to the bottom surface 1" of the steel strip 1) is 200 mm or approximately 200 mm. Additionally, the distance of the spray nozzles 15 to each other in the lateral direction of the steel strip 1 corresponds to 200 mm or approximately 200 mm. Additionally, the distance of the spray nozzles 15 to each other in the longitudinal direction of the steel strip 1 corresponds to 500 mm or approximately 500 mm. The treatment liquid is preferably pumped out of the spray nozzles having a pressure of between and including 1 bar to and including 3 bar, and the amount of treatment liquid per spray nozzle is preferably 12 l/min or approximately 12 l/min. For example, the total number of spray nozzles per treatment station corresponds to 306 or approximately 306, and the amount of pumped treatment liquid per treatment station corresponds to 220 m3/h or approximately 220 m3/h.
  • Test trials were carried out in a pilot plant. The pilot plant consisted of two treatment stations (each having a treatment tank) both arranged as described in the present invention with a first spray pickling section followed by a dip pickling section in each of the treatment tanks. The treatment tanks were designed so that the length of both sections was approximately the same. The pickling acid used was HCl with a concentration of approx. 200 g/l total acid in both tanks. The material treated during the test runs were different austenitic steel grades such as AlSI 304 and 316. The test results have proven that the pickling time could be reduced by 40 - 45% compared to the conventional pickling process using dip pickling with shallow tank turbulence technology, while the FeCl3 concentration was constantly below 30 g/l which is considered to be uncritical as far as the acid regeneration process is concerned. All tested materials showed uniform pickling results without any signs of over-pickling.
  • In another test using the same pilot plant, the material was treated with a reduced temperature of the pickling acid (treatment liquid). The results showed that the temperature could be reduced from 90°C down to 70 °C while still reaching the same pickling time as for the conventional dip pickling process with shallow tank turbulence technology. This result is equivalent to a 20 % reduction of the energy which is needed to keep the process temperature in the pickling process.
  • As an example of the operation of the system and especially of the use of the treatment liquids as a cascade, an example is given of the concentration values for an example of using three treatment stations in a pickling line:
    • In the first treatment station 3, the concentration of HCl is in the range of between and comprising 201 g/l to and comprising 215 g/l, the concentration of MeCl2 is in the range of between and comprising 270 g/l to and comprising 286 g/l, the concentration of FeCl3 is in the range of between and comprising 23 g/l to and comprising 29 g/l. The temperature of the treatment liquid is in the range of between and comprising 87 °C to and comprising 89 °C.
    • In the second treatment station 31, the concentration of HCl is in the range of between and comprising 204 g/l to and comprising 214 g/l, the concentration of MeCl2 is in the range of between and comprising 141 g/l to and comprising 149 g/l, the concentration of FeCl3 is in the range of between and comprising 19 g/l to and comprising 23 g/l. The temperature of the treatment liquid is in the range of between and comprising 91 °C to and comprising 93 °C.
    • In the third treatment station, the concentration of HCl is in the range of between and comprising 190 g/l to and comprising 201 g/l, the concentration of MeCl2 is in the range of between and comprising 40 g/l to and comprising 50 g/l, the concentration of FeCl3 is in the range of between and comprising 20 g/l to and comprising 22 g/l. The temperature of the treatment liquid is in the range of between and comprising 88 °C to and comprising 91 °C.
  • Various tests were made with different qualities of the hot rolled stainless steel strips. Tests were done majority with austenitic AlSI 304 and 316 grades as well as with ferritic AlSI 409 and 430 grades, but also with other steel grades. The best results were achieved with steel that has been either shot-blasted or the scale-broken off prior to pickling in hydrochloric acid. In these trials some of the stainless steel grades were compared under the same pickling conditions. In all trials combined spray pickling and dip pickling in one treatment step using a common circulation system gave the shortest pickling time and excellent surface quality while the FeCl3 concentration could be kept at a level below 30g/l Significantly reduction of the pickling time were achieved for heavy to pickle steel grades as this is the case of coils coiled at higher coiling temperature e.g. > 700 °C.
  • REFERENCE SIGNS
  • 1
    steel strip
    2
    transport direction of the steel strip
    3
    treatment station
    4
    treatment tank (of the treatment station)
    5
    common collection means (of the treatment station)
    12
    wringer roll(s)
    13
    spray section (of the treatment station)
    14
    immersion section (of the treatment station)
    15
    spray nozzles (of the treatment station)
    17, 18
    pumps
    19
    heat exchanger
    20
    guide roll(s)
    31
    further treatment station
    41
    further treatment tank (of the further treatment station)
    51
    further common collection means (of the further treatment station)
    32
    third treatment station
    42
    third treatment tank (of the third treatment station)
    52
    third common collection means (of the third treatment station)
    54
    feeding of fresh treatment liquid
    55
    removing of used treatment liquid

Claims (14)

  1. Method for treating a steel strip (1), especially for a pickling treatment of the steel strip (1), by means of a treatment liquid in a treatment station (3), the treatment station (3) comprising a treatment tank (4) with a spray section (13) and an immersion section (14), and the treatment station (3) comprising a common collection means (16) for the treatment liquid,
    wherein the steel strip (1) comprises stainless steel and is a continuous steel strip (1) being oriented substantially horizontally, both in its longitudinal and transverse directions,
    wherein the steel strip (1) has a top surface (1') and a bottom surface (1 "),
    wherein the method comprises transporting the steel strip (1) continuously through the treatment station (3) in a transport direction (2), the transport direction being parallel to the longitudinal direction of the steel strip (1), such that
    -- in a first step, the treatment liquid is sprayed onto the top surface (1') of the steel strip (1) and onto the bottom surface (1 ") of the steel strip (1) while the steel strip (1) being in the spray section (13) of the treatment station (3),
    -- in a second step, the steel strip (1) is immersed in the treatment liquid while the steel strip (1) being in the immersion section (14) of the treatment station (3), wherein, while treating the steel strip (1), the treatment liquid is continuously pumped out of the common collection means (16) and through both the spray section (13) and the immersion section (14) of the treatment station (3), wherein spraying of the treatment liquid onto the top and bottom surfaces (1', 1 ") of the steel strip (1) is provided using spray nozzles (15).
  2. Method according to claim 1, wherein the spray section (13) comprises an effective spray length in parallel to the longitudinal direction of the steel strip (1) such that-during the first step - the top and bottom surfaces (1', 1 ") of the steel strip (1) receive the treatment liquid while being located within the effective spray length, wherein the immersion section (14) comprises an effective immersion length in parallel to the longitudinal direction of the steel strip (1) such that - during the second step - the steel strip (1) is immersed - with its top and bottom surfaces (1', 1") - in the treatment liquid while being located within the effective immersion length, wherein the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  3. Method according to one of the preceding claims, wherein the effective spray length and hence the ratio of the effective spray length vs. the effective immersion length is varied by activating only a part of the spray nozzles (15).
  4. Method according to one of the preceding claims, wherein - along the transport direction of the steel strip (1) - the spray section (14) is located upstream or downstream with respect to the immersion section (15).
  5. Method according to one of the preceding claims, wherein the method comprises using - besides using the treatment liquid in the treatment station (3) - a further treatment liquid in a further treatment station (31), the further treatment station (31) comprising a further treatment tank (41) with a further spray section and a further immersion section, and the further treatment station (31) comprising a further common collection means (51) for the further treatment liquid,
    wherein the method comprises transporting the steel strip (1) continuously through the further treatment station (31) in the transport direction such that
    -- in a third step, the further treatment liquid is sprayed onto the top surface (1') of the steel strip (1) and onto the bottom surface (1 ") of the steel strip (1) while the steel strip (1) being in the further spray section of the further treatment station (31),
    -- in a fourth step, the steel strip (1) is immersed in the further treatment liquid while the steel strip (1) being in the further immersion section of the further treatment station (31),
    wherein, while treating the steel strip (1), the further treatment liquid is continuously pumped out of the further common collection means (51) and through both the further spray section and the further immersion section of the further treatment station (31), wherein spraying of the further treatment liquid onto the top and bottom surfaces (1', 1 ") of the steel strip (1) is provided using further spray nozzles, wherein the third and fourth steps are preceding the first and second steps or are subsequent to the first and second steps.
  6. Method according to one of the preceding claims, wherein the treatment liquid and/or the further treatment liquid comprises
    -- hydrochloric acid in a concentration ranging from and including 150 g/l to and including 250 g/l and
    -- FeCl3 in a concentration ranging from and including 10 g/l to and including 35 g/l, especially in a concentration ranging from and including 15 g/l to and including 30 g/l or especially in a concentration ranging from and including 19 g/l to and including 26 g/l and,
    -- MeCl2 in a concentration ranging from and including 30 g/l to and including 300 g/l, especially in a concentration ranging from and including 30 g/l to and including 60 g/l or in a concentration ranging from and including 130 g/l to and including 180 g/l or in a concentration ranging from and including 230 g/l to and including 300 g/l.
  7. System for treating a steel strip (1), especially for a pickling treatment of the steel strip, by means of a treatment liquid in a treatment station (3), the system comprising the treatment station (3), wherein the treatment station (3) comprises a treatment tank (4) with a spray section (13), an immersion section (14), and the treatment station (3) comprising a common collection means (16) for the treatment liquid,
    wherein the steel strip (1) comprises stainless steel and is a continuous steel strip (1) being oriented substantially horizontally, both in its longitudinal and transverse directions,
    wherein the steel strip (1) has a top surface (1') and a bottom surface (1"), wherein the system is configured to transport the steel strip (1) continuously through the treatment station (3) in a transport direction, the transport direction being parallel to the longitudinal direction of the steel strip (1), such that
    -- the treatment liquid is sprayed onto the top surface (1') of the steel strip (1) and onto the bottom surface (1 ") of the steel strip (1) while the steel strip (1) being in the spray section (13) of the treatment station (3),
    -- the steel strip (1) is immersed in the treatment liquid while the steel strip (1) being in the immersion section (14) of the treatment station (3),
    wherein the system is configured such that the treatment liquid is continuously pumped out of the common collection means (16) and through both the spray section (13) and the immersion section (14) of the treatment station (3), wherein the system comprises spray nozzles (15) such that the treatment liquid is sprayed onto the top and bottom surfaces (1', 1") of the steel strip (1) using the spray nozzles (15).
  8. System according to claim 7, wherein the spray section (13) comprises an effective spray length in parallel to the longitudinal direction of the steel strip (1) such that the top and bottom surfaces (1', 1 ") of the steel strip (1) receive the treatment liquid while being located within the effective spray length, wherein the immersion section (14) comprises an effective immersion length in parallel to the longitudinal direction of the steel strip (1) such that the steel strip (1) is immersed - with its top and bottom surfaces (1', 1") - in the treatment liquid while being located within the effective immersion length, wherein the effective spray length and the effective immersion length are provided having a ratio of between and including 30:70 to 70:30, especially a ratio of 50:50.
  9. System according to one of claims 7 to 8, wherein - along the transport direction of the steel strip (1) - the spray section (14) is located upstream or downstream with respect to the immersion section (15).
  10. System according to one of claims 7 to 9, wherein the common collection means (5) for the treatment liquid of both the spray section (13) and the immersion section (14) is a collection means (5) separated from the treatment tank (4) of the treatment station (3).
  11. System according to one of claims 7 to 9, wherein the common collection means (5) for the treatment liquid of both the spray section (13) and the immersion section (14) is a collection means (5) integrated with the treatment tank (4) of the treatment station (3), especially integrated such that the bottom part of the treatment tank (4) forms the common collection means (5).
  12. System according to one of claims 7 to 11, wherein the system comprises - besides the treatment liquid in the treatment station (3) - a further treatment liquid in a further treatment station (31), the further treatment station (31) comprising a further treatment tank (41) with a further spray section and a further immersion section, and the further treatment station (31) comprising a further common collection means (51) for the further treatment liquid,
    wherein the system is configured such that the steel strip (1) is transported continuously through the further treatment station (31) in the transport direction such that
    -- the further treatment liquid is sprayed onto the top surface (1') of the steel strip (1) and onto the bottom surface (1 ") of the steel strip (1) while the steel strip (1) being in the further spray section of the further treatment station (31),
    -- the steel strip (1) is immersed in the further treatment liquid while the steel strip (1) being in the further immersion section of the further treatment station (31), wherein the system is configured such that the further treatment liquid is continuously pumped out of the further common collection means (51) and through both the further spray section and the further immersion section of the further treatment station (31), wherein the system comprises further spray nozzles such that the further treatment liquid is sprayed onto the top and bottom surfaces (1', 1 ") of the steel strip (1) using the further spray nozzles.
  13. System according to one of claims 7 to 12, wherein the system comprises - besides the treatment liquid in the treatment station (3) and the further treatment liquid in the further treatment station (31) - a third treatment liquid in a third treatment station (32), the third treatment station (32) comprising a third treatment tank (42) with a third spray section and a third immersion section, and the third treatment station (32) comprising a third common collection means (52) for the third treatment liquid.
  14. System according to one of claims 7 to 13, wherein the treatment liquid and/or the further treatment liquid and/or the third treatment liquid comprises
    -- hydrochloric acid in a concentration ranging from and including 150 g/l to and including 250 g/l and
    -- FeCl3 in a concentration ranging from and including 10 g/l to and including 35 g/l, especially in a concentration ranging from and including 15 g/l to and including 30 g/l or especially in a concentration ranging from and including 19 g/l to and including 26 g/l and,
    -- MeCl2 in a concentration ranging from and including 30 g/l to and including 300 g/l, especially in a concentration ranging from and including 30 g/l to and including 60 g/l or in a concentration ranging from and including 130 g/l to and including 180 g/l or in a concentration ranging from and including 230 g/l to and including 300 g/l.
EP14195952.8A 2014-12-02 2014-12-02 Method of treating a stainless steel strip, especially for a pickling treatment Active EP3029164B1 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
EP14195952.8A EP3029164B1 (en) 2014-12-02 2014-12-02 Method of treating a stainless steel strip, especially for a pickling treatment
BR112017011360A BR112017011360A2 (en) 2014-12-02 2015-12-02 method and system of treatment of a stainless steel strip, especially for a pickling treatment
EP15804432.1A EP3227467A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment
CA2969274A CA2969274A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment
RU2017123253A RU2691363C2 (en) 2014-12-02 2015-12-02 Method and system for processing stainless steel strip, primarily for etching
MX2017007108A MX2017007108A (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment.
PCT/EP2015/078314 WO2016087494A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment
CN201580065809.5A CN107002255A (en) 2014-12-02 2015-12-02 Handle stainless steel band, the particularly method and system for pickling processes
KR1020177018060A KR20170089919A (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment
JP2017528778A JP2017536481A (en) 2014-12-02 2015-12-02 Method and system for treating stainless steel strip, in particular for pickling treatment
US15/532,138 US20170268114A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP14195952.8A EP3029164B1 (en) 2014-12-02 2014-12-02 Method of treating a stainless steel strip, especially for a pickling treatment

Publications (2)

Publication Number Publication Date
EP3029164A1 true EP3029164A1 (en) 2016-06-08
EP3029164B1 EP3029164B1 (en) 2020-06-17

Family

ID=51999369

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14195952.8A Active EP3029164B1 (en) 2014-12-02 2014-12-02 Method of treating a stainless steel strip, especially for a pickling treatment
EP15804432.1A Withdrawn EP3227467A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP15804432.1A Withdrawn EP3227467A1 (en) 2014-12-02 2015-12-02 Method and system of treating a stainless steel strip, especially for a pickling treatment

Country Status (10)

Country Link
US (1) US20170268114A1 (en)
EP (2) EP3029164B1 (en)
JP (1) JP2017536481A (en)
KR (1) KR20170089919A (en)
CN (1) CN107002255A (en)
BR (1) BR112017011360A2 (en)
CA (1) CA2969274A1 (en)
MX (1) MX2017007108A (en)
RU (1) RU2691363C2 (en)
WO (1) WO2016087494A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111663145A (en) * 2020-06-08 2020-09-15 浦项(张家港)不锈钢股份有限公司 Jet pickling system, austenitic stainless steel cold rolling pickling process and stainless steel
US12123100B2 (en) 2018-07-19 2024-10-22 Sms Group Gmbh Pickling plant for surface treatment of strip steel

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109594086A (en) * 2018-12-29 2019-04-09 佛山市诚德新材料有限公司 A kind of pickler of stainless steel band
CN111719162A (en) * 2019-03-21 2020-09-29 宝山钢铁股份有限公司 Strip steel pickling system
IT201900006234A1 (en) * 2019-04-23 2020-10-23 Danieli Off Mecc PLANT AND PICKLING PROCESS
EP3967789A1 (en) 2020-09-11 2022-03-16 Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW Ultrafast pickling method and installation therefor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4031234A1 (en) 1990-10-04 1992-04-09 Gewerk Keramchemie Rolled material surface treatment appts. - has jets on both sides of workpiece below fluid wheel in vessel at an acute angle to the material surface
DE4228808A1 (en) 1992-08-29 1994-03-03 Gewerk Keramchemie Surface treatment of strip material - includes an additional spraying stage
JPH06128774A (en) * 1992-10-19 1994-05-10 Nippon Steel Corp Pickling device and pickling treatment method
US5759307A (en) * 1995-09-01 1998-06-02 Keramchemie Gmbh Method of producing a cold-rolled strip in one pass
US5840173A (en) * 1996-06-19 1998-11-24 Keramchemie Gmbh Process for treating the surface of material of high-grade steel
WO2002081776A1 (en) * 2001-04-09 2002-10-17 Ak Properties, Inc. Hydrogen peroxide pickling of silicon-containing electrical steel grades

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2529762A (en) * 1946-04-11 1950-11-14 Carnegie Illinois Steel Corp Method and apparatus for continuous cleaning of metal strip
US2529672A (en) * 1947-02-06 1950-11-14 William A Black Dispensing apparatus
SU113230A1 (en) * 1957-07-12 1957-11-30 И.М. Сидоренко Multi-chamber unit for blasting and passivating sheet steel
US3896828A (en) * 1973-10-23 1975-07-29 Interlake Inc Treatment of pickle liquor rinse water
PL124218B1 (en) * 1979-04-26 1983-01-31 Produkcji Montazu Obiek K Process for wasteless metallizing,especially zinc coating of steel surface
CA1141629A (en) * 1979-07-31 1983-02-22 Roger F. Potts Machine for cleaning plastic containers
JPS63192882A (en) * 1987-02-06 1988-08-10 Mitsubishi Heavy Ind Ltd Continuous pickling method
US4920995A (en) * 1988-08-18 1990-05-01 Continental Installers Corporation Process for continuous strip pickling
JPH03100189A (en) * 1989-09-14 1991-04-25 Kobe Steel Ltd Treatment of continuous pickling of steel sheet
US5593507A (en) * 1990-08-22 1997-01-14 Kabushiki Kaisha Toshiba Cleaning method and cleaning apparatus
JPH07188958A (en) * 1993-12-28 1995-07-25 Mitsubishi Heavy Ind Ltd Continuous type band steel pickling equipment
JP3551809B2 (en) * 1999-02-10 2004-08-11 住友金属工業株式会社 How to descaling stainless steel sheet
TWI270626B (en) * 2002-04-23 2007-01-11 Display Mfg Service Co Ltd Wet processing bath and fluid supplying system for liquid crystal display manufacturing equipment
RU2308544C2 (en) * 2006-01-10 2007-10-20 Открытое акционерное общество "Северсталь" Method of pickling hot-rolled bars
EP2143824B1 (en) * 2007-05-01 2015-04-15 Nippon Steel & Sumitomo Metal Corporation Steel sheet rinsing method, and steel sheet continuous rinsing apparatus
JP2009001876A (en) * 2007-06-22 2009-01-08 Daido Steel Co Ltd Pickling device for beltlike metal
JP5300122B2 (en) * 2007-12-27 2013-09-25 花王株式会社 Steel strip cleaning method
CN102965675B (en) * 2011-09-01 2015-05-13 沈阳远大铝业工程有限公司 Pickling passivation method of stainless steel
UA104710C2 (en) * 2012-08-02 2014-02-25 Харьковский Национальный Университет Радиоэлектроники device for the continuous etching of rolled carbon steel strip
US8871166B2 (en) * 2013-01-16 2014-10-28 Linde Aktiengesellschaft Method for removing contaminants from exhaust gases

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4031234A1 (en) 1990-10-04 1992-04-09 Gewerk Keramchemie Rolled material surface treatment appts. - has jets on both sides of workpiece below fluid wheel in vessel at an acute angle to the material surface
DE4228808A1 (en) 1992-08-29 1994-03-03 Gewerk Keramchemie Surface treatment of strip material - includes an additional spraying stage
JPH06128774A (en) * 1992-10-19 1994-05-10 Nippon Steel Corp Pickling device and pickling treatment method
US5759307A (en) * 1995-09-01 1998-06-02 Keramchemie Gmbh Method of producing a cold-rolled strip in one pass
US5840173A (en) * 1996-06-19 1998-11-24 Keramchemie Gmbh Process for treating the surface of material of high-grade steel
WO2002081776A1 (en) * 2001-04-09 2002-10-17 Ak Properties, Inc. Hydrogen peroxide pickling of silicon-containing electrical steel grades

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12123100B2 (en) 2018-07-19 2024-10-22 Sms Group Gmbh Pickling plant for surface treatment of strip steel
CN111663145A (en) * 2020-06-08 2020-09-15 浦项(张家港)不锈钢股份有限公司 Jet pickling system, austenitic stainless steel cold rolling pickling process and stainless steel

Also Published As

Publication number Publication date
RU2017123253A3 (en) 2019-04-15
EP3227467A1 (en) 2017-10-11
CN107002255A (en) 2017-08-01
US20170268114A1 (en) 2017-09-21
WO2016087494A1 (en) 2016-06-09
JP2017536481A (en) 2017-12-07
KR20170089919A (en) 2017-08-04
BR112017011360A2 (en) 2018-04-03
EP3029164B1 (en) 2020-06-17
RU2691363C2 (en) 2019-06-11
CA2969274A1 (en) 2016-06-09
RU2017123253A (en) 2019-01-09
MX2017007108A (en) 2017-08-18

Similar Documents

Publication Publication Date Title
EP3029164B1 (en) Method of treating a stainless steel strip, especially for a pickling treatment
KR100492841B1 (en) Hydrogen Peroxide Pickling in Stainless Steel
AU2006224727A1 (en) Method and device for descaling a metal strip
JP4431045B2 (en) Method and apparatus for descaling and / or cleaning metal continuum
KR101249167B1 (en) Pickling method for steel plates, and pickling apparatus
EP2978879A1 (en) Method for treating in continuous the surface of a laminate made of stainless steel in a solution based on sulfuric acid
EP3029163B1 (en) Method and system of treating a carbon steel strip, especially for pickling
JP4830513B2 (en) Method and apparatus for cleaning hot dip galvanized steel sheet
US5743968A (en) Hydrogen peroxide pickling of stainless steel
US5702534A (en) Hydrogen peroxide pickling of stainless steel
KR101611768B1 (en) The apparatus for descaling of hot rolled steel sheet and the method thereof
Hudson Pickling and descaling
JP2001191108A (en) Descaling method and device for the same
WO2021186375A1 (en) Process for pickling and/or passivating a stainless steel
ITMI20130494A1 (en) METHOD OF TREATING CONTINUOUSLY THE SURFACE OF A STAINLESS STEEL LAMINATE IN A CHLORIDRID ACID-BASED SOLUTION
Shoemaker New molten salt systems for cleaning stainless steels

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161208

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180209

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190725

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CMI UVK GMBH

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTC Intention to grant announced (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200109

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014066642

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1281369

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200917

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200918

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200917

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1281369

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201019

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201017

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014066642

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

26N No opposition filed

Effective date: 20210318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201202

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201202

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201202

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201017

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602014066642

Country of ref document: DE

Owner name: JOHN COCKERILL UVK GMBH, DE

Free format text: FORMER OWNER: CMI UVK GMBH, 56410 MONTABAUR, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231214

Year of fee payment: 10