US20170268113A1 - Method and system of treating a carbon steel strip, especially for a pickling treatment - Google Patents

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

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Publication number
US20170268113A1
US20170268113A1 US15/532,121 US201515532121A US2017268113A1 US 20170268113 A1 US20170268113 A1 US 20170268113A1 US 201515532121 A US201515532121 A US 201515532121A US 2017268113 A1 US2017268113 A1 US 2017268113A1
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Prior art keywords
steel strip
treatment
section
treatment liquid
spray
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US15/532,121
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English (en)
Inventor
Thomas Marx
Wolfgang WALSDORF
Rafael Rituper
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John Cockerill UVK GmbH
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CMI UVK GmbH
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING 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
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/024—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by a combination of dipping and spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously

Definitions

  • the present invention relates to a method and 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.
  • metal surfaces are treated by removing impurities such as typically rust or scale using treatment liquids, or pickle liquors, typically containing strong acids.
  • Scale itself is chemically quite similar to rust, being made up of iron and oxygen bonded together in various molecular arrangements. Like rust, scale typically develops at the surface of the steel product where the metal surface is exposed to air.
  • a pickling line having one or a plurality of acid baths, typically using a plurality of pickling tanks or pickling stations in a row, normally containing hydrochloric acid at a certain temperature in the range of typically between 50° C. and 95° C.
  • hydrochloric acid e.g. hydrochloric acid, sulfuric acid, etc.
  • pickling agents or treatment liquid for pickling of e.g. ferrous metals.
  • the steel strip is pulled (or pushed or both pulled and pushed) through the pickling line—especially the treatment tank (or pickling tank)—at a certain speed (e.g. up to a couple of meters per second), then rinsed—typically with water—, and dried, normally air-dried.
  • the layer of scale dissolves in the acid.
  • the concentration of the acid itself becomes depleted during the pickling operation, so that it is necessary to add fresh acid continuously.
  • large amounts of spent acids are not only hazardous to the environment but usually also expensive.
  • the pickling operation should be carried out such that the regeneration of the acids spent can be realized in a comparatively simple and comparatively environmentally compatible manner.
  • HCl acts less aggressive to the base metal than H 2 SO 4 and consequently reducing the risk of over-pickling.
  • 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.
  • the air dissolves in the pickling acid and oxidizes the FeCl 2 together with the HCl forming FeCl 3 .
  • HCl is a non oxidizing acid and therefore dissolving the base metal only slowly
  • FeCl 3 is an oxidizing agent, consequently increasing the dissolving speed of the base material.
  • the FeCl 3 concentration can reach 60 g/L and above.
  • FeCl 3 concentration in the pickling acid is the effect on the regeneration process of the spent pickling acid.
  • Spent pickling acid is typically regenerated using the pyrohydrolysis 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.
  • An aspect of the invention provides a method for treating a steel strip using a first treatment liquid in a treatment station having at least a treatment tank with a spray section and an immersion section, and a common collector for the first treatment liquid, the steel strip including carbon steel, and having a top surface, and a bottom surface, and being a continuous steel strip, oriented substantially horizontally, both in its longitudinal and transverse directions.
  • 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; spraying, using spray nozzles, the first treatment liquid onto the top and bottom surfaces of the steel strip while the steel strip is in the spray section; immersing the steel strip in the first treatment liquid while the steel strip is in the immersion section; and while treating the steel strip, continuously pumping the first treatment liquid out of the common collector and through both the spray section and the immersion section.
  • FIG. 1 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;
  • FIG. 2 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; and
  • FIG. 3 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.
  • An aspect of 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.
  • An aspect of 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 may be a carbon steel.
  • An aspect of the present invention provides a 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.
  • An aspect of the present invention provides 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 carbon steel and is a continuous steel strip being oriented substantially horizontally, both in its longitudinal and transverse directions,
  • the steel strip has a top surface and a bottom surface
  • 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.
  • the present invention is related to a process for chemical or electrochemical treatment of the surface of carbon 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 steel strip instead of the steel strip comprising carbon steel, it is also preferred that the steel strip consists of carbon steel.
  • the process for chemical or electrochemical treatment of the surface of carbon 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.
  • An aspect of 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 carbon 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 an aspect 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 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 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):
  • 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
  • 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, where
  • 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
  • An aspect of 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 carbon 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
  • 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 steel strip instead of the steel strip comprising carbon steel, it is also preferred that the steel strip consists of carbon steel.
  • 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 length of the treatment station is preferably 20 m or less, preferably between 16 m and 20 m.
  • the treatment station comprising both the spray section and the immersion section is preferably assembled using two main components of the treatment tank such that the treatment tank is—after assembling the two main components—integrally formed using the two main components.
  • each of the main components have a maximum length of 11.6 m, i.e. the two main components have a length of 11.6 m or less.
  • transport these main components of the treatment tank, used in a treatment station according to the inventive method such that no welding of the two main components is required.
  • the main components of the treatment tank are slid into one another. This enables a much faster setup of the treatment station which is especially advantageous in case of re-furbishing existing pickling lines, as the down-time due to the refurbishment can be considerably reduced.
  • 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
  • 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.
  • 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
  • the fourth treatment station comprising a fourth common collection means for the fourth treatment liquid.
  • 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—FeCl 3 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,—FeCl 2 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.
  • 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 FIG.
  • FIG. 2 for the exemplary case of the treatment station being represented by reference sign 3
  • FIG. 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 ( FIG. 2 ) and another part is or are realized according to the second embodiment of the present invention ( FIG. 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 FIG. 1 ) and a further immersion section (or second immersion section) (not depicted in FIG.
  • FIGS. 2 and 3 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 FIGS. 2 and 3 .
  • FIG. 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.
  • FIG. 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 carbon 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 FIGS. 2 and 3 as spray section 13 of the treatment station 3 ) and a dip pickling section (as represented in FIGS. 2 and 3 as immersion section 14 of the treatment station 3 ) according to the present invention.
  • FIG. 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 FIG. 2 or are realized as common collection means 5 , 51 , 52 integrated in the respective treatment tank 4 , 41 , 42 as shown in FIG. 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 FIG. 1 .
  • the following treatment stations (or treatment tanks), like treatment stations 31 , 32 in FIG. 1 do not need such wringer roll 12 .
  • FIG. 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 FIG. 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 255 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 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 IF steel grades (interstitial Free steel), which belong to the group of steel grades that are more difficult to pickle mainly due to their high recoiling temperature.
  • 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.
  • the concentration of HCl is in the range of between and comprising 205 g/L to and comprising 220 g/L
  • the concentration of FeCl2 is in the range of between and comprising 260 g/L to and comprising 278 g/L
  • the concentration of FeCl3 is in the range of between and comprising 22 g/L to and comprising 26 g/L.
  • the temperature of the treatment liquid is in the range of between and comprising 88° C. to and comprising 91° C.
  • the concentration of HCl is in the range of between and comprising 201 g/L to and comprising 211 g/L
  • the concentration of FeCl2 is in the range of between and comprising 140 g/L to and comprising 146 g/L
  • the concentration of FeCl3 is in the range of between and comprising 21 g/L to and comprising 26 g/L.
  • the temperature of the treatment liquid is in the range of between and comprising 88° C. to and comprising 91° C.
  • the concentration of HCl is in the range of between and comprising 193 g/L to and comprising 206 g/L
  • the concentration of FeCl 2 is in the range of between and comprising 43 g/L to and comprising 47 g/L
  • the concentration of FeCl 3 is in the range of between and comprising 19 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.
  • the recitation of “at least one of A, B, and C” should be interpreted as one or more of a group of elements consisting of A, B, and C, and should not be interpreted as requiring at least one of each of the listed elements A, B, and C, regardless of whether A, B, and C are related as categories or otherwise.
  • the recitation of “A, B, and/or C” or “at least one of A, B, or C” should be interpreted as including any singular entity from the listed elements, e.g., A, any subset from the listed elements, e.g., A and B, or the entire list of elements A, B, and C.

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US15/532,121 2014-12-02 2015-12-02 Method and system of treating a carbon steel strip, especially for a pickling treatment Abandoned US20170268113A1 (en)

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EP14195949.4A EP3029163B9 (en) 2014-12-02 2014-12-02 Method and system of treating a carbon steel strip, especially for pickling
PCT/EP2015/078311 WO2016087493A1 (en) 2014-12-02 2015-12-02 Method and system of treating a carbon steel strip, especially for a pickling treatment

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KR20220072983A (ko) 2020-11-26 2022-06-03 한동희 리튬이온 이차전지용 음극 복합체, 그의 제조방법, 그를 포함하는 리튬이온 이차전지
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CN107002254A (zh) 2017-08-01
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RU2017123254A3 (es) 2019-04-09
EP3227466A1 (en) 2017-10-11
RU2017123254A (ru) 2019-01-09
RU2691688C2 (ru) 2019-06-17
CA2969369A1 (en) 2016-06-09
WO2016087493A1 (en) 2016-06-09
EP3029163A1 (en) 2016-06-08
EP3029163B9 (en) 2019-11-27
MX2017007112A (es) 2017-08-18
KR20170088433A (ko) 2017-08-01
JP2018502985A (ja) 2018-02-01

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