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WO2021105215A1 - Procédé de récupération de métal - Google Patents

Procédé de récupération de métal Download PDF

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Publication number
WO2021105215A1
WO2021105215A1 PCT/EP2020/083375 EP2020083375W WO2021105215A1 WO 2021105215 A1 WO2021105215 A1 WO 2021105215A1 EP 2020083375 W EP2020083375 W EP 2020083375W WO 2021105215 A1 WO2021105215 A1 WO 2021105215A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
nickel
acid
unit
dewatering
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.)
Ceased
Application number
PCT/EP2020/083375
Other languages
English (en)
Inventor
David Stenman
Helen WINBERG WANG
Johan ROHDE-NIELSEN
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.)
Scanacon AB
Original Assignee
Scanacon AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Scanacon AB filed Critical Scanacon AB
Publication of WO2021105215A1 publication Critical patent/WO2021105215A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present application relates to a method for recovery of metals in aqueous solutions of acids.
  • Pickling liquids are frequently used in the manufacture of e.g. stainless steel where the pickling liquids are used for removing metal oxides and chrome-depleted layers from the steel.
  • a mix of nitric, hydrochloric and hydrofluoric acid solutions are used or a combination of sulfuric and hydrofluoric acid.
  • other inorganic or organic additives are used in the mix.
  • a fraction of the acids are consumed and some amounts of metals are dissolved into the pickling acid.
  • the solution after pickling will thus contain an acidic solution with various metals such as iron, chrome and nickel and others depending on the alloy being treated. When the amount of dissolved metal in the solution becomes too high the pickling liquid will lose its pickling properties.
  • Document US3800024 discloses a process for separating acids from metal salts in aqueous solutions of acids and dissolved metals, such as pickling baths and/or acid galvanic baths, where the object is to separate acids from metal salts, to separate the metal ions included in the metal salt solution in order to recover nickel and to recycle the acid solution to the pickling baths.
  • the process uses a number of steps including separating spent pickling baths into acid and metal salt fractions, neutralizing the metal salt solution by pH-regulation whereby Fe and Cr are precipitated, dewatering in order to solidify Fe and Cr hydroxides, neutralizing the solution from the dewatering step by adding precipitation agents and dewatering the suspension from the precipitation step in order to obtain a solid product containing nickel hydroxide.
  • Ca(OH)2 One of the main precipitation agents suggested by US3800024 for use in the process is calcium hydroxide Ca(OH)2.
  • a drawback with the use of Ca(OH)2 is that it provides solids such as calcium nitrate Ca(N03)2 and/or calcium sulphate CaS04 that will dilute the metal ions. This means that the recovered neutralisation sludge containing the metals cannot be returned to the metal production plant directly because it contains slag forming materials that is really unwanted in the metal production process.
  • WO 2010051992 discloses a method for the recovery of iron, chrome and nickel from an acid solution.
  • the solution is given a pH level of 3.5 to 4.5 by adding sodium hydroxide. In this pH range, the nickel is in the solution while chromium and iron are almost totally precipitated.
  • the solution is neutralized up to a pH level of 8-9 for a complete nickel precipitation.
  • the precipitated nickel hydroxide, Ni(OH)2 is then dewatered.
  • the Ni(OH)2 is then fed to a dissolution equipment with a pH of about 3.5 - 4.5 wherein the nickel hydroxide goes in solution as sulphate.
  • the nickel sulphate is then fed to a cathode area of an electrodialysis cell where the nickel is formed in metal form on the cathode.
  • the aim of the present invention is to provide a method for recovery of metals from exhausted acid solutions with the features of the independent patent claims.
  • Preferable embodiments of the invention form the subject of the dependent patent claims.
  • the invention comprises a method for recovery of metals from exhausted acid solutions, which acid solutions contain metal oxides comprising iron, chrome and nickel.
  • the method may comprise the steps of adjusting the solution, by adding precipitation agents, to a pH level where at least iron is precipitated and then dewatering of the precipitated solids.
  • the iron in the acid solution is then recovered.
  • the acid solution may be adjusted to a pH level where chrome is precipitated followed by dewatering of the precipitated solids.
  • the chrome in the acid solution is then also recovered.
  • the pH of the solution may be adjusted so that both iron and chrome are recovered at the same time.
  • a further step of the method is treatment of liquid solution from the dewatering step in order to recover nickel.
  • several metals are recovered from the acid solution and may be brought back to a metal production plant.
  • the precipitation agents comprise agents that do not contaminate the metals that are to be recovered. This is important in particular if the recovered metals are to be returned to smelting furnaces without additional treatment, since many precipitation agents that may be used for the recovery produce unwanted biproducts such as slag, for instance.
  • the precipitation agents may comprise sodium hydroxide.
  • the pH level for precipitating iron may be adjusted to 3 - 4.5 and the pH level for precipitating chrome is adjusted to 4.5 - 5.5.
  • the treatment of the liquid solution from the dewatering step may comprise using ion exchange for recovery of nickel as nickel hydroxide in a solution.
  • the ion exchange step may further comprise an acid elution process of the saturated ion exchange for recovery of nickel and in that regard, the acid used for the elution process may be sulphuric acid H2SO4. It is of course to be understood that other acids may be used in order to obtain the desired result.
  • the method according to the invention may comprise the further step of treatment of the recovered nickel by electrowinning. With this step nickel metal is recovered, which may be used directly in the metal production process.
  • the method may further comprise the step of adjusting the pH value of the solution to about 4 before the treatment by electrowinning. Moreover, it may also comprise the step of adjusting the temperature of the solution to about 45 - 65 ° C.
  • the method may further comprise the step of acid retardation before the step of pH adjustment of the solution.
  • a further step may be to remove fluorides in the solution.
  • the removal of fluorides is important if the resulting metal oxides and hydroxides are to be returned to the metal production plant. The fluorides are sometimes unwanted in the smelt due to metallurgical reasons and may be seen as an impurity.
  • the step of removal of fluorides may be performed after the step of acid retardation or the step of removal of fluorides is performed before the step of electrowinning.
  • a further alternative may comprise the step of treatment of the precipitated chrome by electrowinning.
  • both the nickel and the chrome may be recovered in electrowinning processes.
  • FIG. 1 is a schematic overview of a process step comprised in a system for recovering metals from pickling liquid solutions.
  • the system comprises a process line with an inlet 10 from a production plant for e.g. stainless-steel production. Through the inlet pickling acid residue may be fed.
  • the inlet is connected to an acid recovery and acid/metal separation or retardation unit 12.
  • the unit 12 has a first outlet branch 14 connected to the production plant.
  • a second outlet branch 16 is connected to a first separation unit 18 that in the embodiment may be arranged as a precipitation unit.
  • the precipitation unit 18 is arranged with an inlet 20 for supply of pH affecting matter as will be described.
  • the precipitation unit is provided with a controller 22 capable of controlling the environment inside the precipitation unit 18 as will be described.
  • the controller 22 is connected to the precipitation unit by at least one inlet and at least one outlet 24.
  • a sensor may be submerged in the unit and connected to the controller. With that solution, the sample will not be circulated between the precipitation unit and the controller.
  • the precipitation unit 18 is further arranged with an outlet 26 that is connected to a dewatering unit 28.
  • the dewatering unit 28 shall remove the majority of solids in the liquid, so that no particles remain that may have an adverse effect on the next coming step of the process.
  • the solution shall contain no particles larger than 0.1-1 micron. This may be achieved by the use of a particle removal technique such as a dead-end or cross flow filter being cylindrical, drum-, automatic self-cleaning-, sand-, batch-, press- or variants of these filtration types. It is of course possible to use other types of particle removal systems such as gravitational settling, lamellar or constricted flow type reactors as well as by centrifugal means or membrane separation.
  • the dewatering unit 28 is arranged with a first outlet 30 through which filtered solids may be removed and collected in suitable containers.
  • the dewatering unit 28 is further arranged with a second outlet 32 that is connected to a second separation unit 34 that in the embodiment may be an ion exchange unit.
  • the ion exchange unit is arranged with an inlet 36 for supply of a suitable acid solution as will be described.
  • the ion exchange unit is further arranged with a first outlet 38 for solutions free of metal produced from the ion exchange process as will be described.
  • a second inlet 39 may be used for resin regeneration chemicals. Further, this process may also be controller with a unit similar to 22 and it may also be connected to a spectrometer cell to monitor the concentrations in the unit.
  • the ion exchange unit 34 is arranged with a second outlet 40 connected to a pre conditioning unit 42 that may be a suitable receptacle such as a container or tank.
  • the receptacle 42 is arranged with an inlet 44 for a supply of pH affecting matter as will be described below.
  • the base addition may also be controlled by a controller such as 22.
  • the receptacle 42 is further arranged with an outlet 46 connected to a metal recovery unit 48, that in the embodiment may be is an electro winning unit.
  • the electro winning unit 48 is arranged with an inlet 50 through which supply of pH affecting matter may be added. Recovered metal may be removed from the electro winning unit via plates or shards/flakes of the electro winning unit as will be described. Or alternative cathode shapes such as, baskets, rods, cylinders etc may also be used.
  • the electrowinning unit is further arranged with a control unit 52 capable of controlling the environment inside the electro winning unit as will be described.
  • the system is intended to work as follows. Pickling acid from a steel production plant that has been degraded with deposits to a degree that it cannot function properly is fed to the acid recovery and acid/metal separation unit 12. Here the acid solution is recovered and is fed back to the production plant.
  • metal cations are separated from free acids by a diffusion process utilizing a particle bed of a special ion exchange resin frequently also referred to as an acid-retardation resin, sometimes also a size exclusion resin can be used.
  • the metal cations will pass the resin bed while a large amount of the free acid is eluated from the resin by the use of water.
  • the efficiency of the separation unit should be at least 50%, preferably higher.
  • the metal rich solution separated from the acid solution is then fed to the precipitation unit 18.
  • the metal rich solution may contain 3-5 grams Ni/I and the solution may have a pH value in the order of 1-3. It is of course favourable if the Ni-content is even higher.
  • This solution is then fed to and fills up the precipitation unit 18.
  • the pH level of the solution is adjusted with an appropriate additive.
  • One preferred additive is NaOH that does not contaminate metal oxides that are not removed in this stage.
  • the additive may be added gradually and during stirring of the solution/additive. It is important that the stirring is thorough so that the additive, e.g. NaOH, is dissolved in the solution. If the additive is not dissolved properly, but there instead is a concentration of additives locally, that will cause local increase of pH levels which in turn may cause unwanted precipitation of material that should be extracted at a later stage and it might be difficult and/or time consuming to dissolve material that has been precipitated for treatment at later stages.
  • dosage rate of the additive and the stirring are optimised, which optimisation is dependent on the desired precipitation result.
  • a further important factor for the efficiency of the process is temperature control.
  • a temperature range between 0 - 65 ⁇ is desirable.
  • the aim of the optimisation generally is to have particle sizes of the precipitation that are easy to filtrate in later stages.
  • the pH level is preferably monitored and controlled by the controller 22.
  • the controller is preferably working dynamically controlling the pH level in the solution of the precipitation unit. If the controller detects that the pH level is outside the preferred range, control signals are sent to the previous step to adjust the acid solution for the next batch.
  • the controller could utilize a number of different techniques for controlling the process in the precipitation unit. For instance, pH level, conductivity, pe-level, spectrophotometric measurements, density, just to mention some.
  • the pH level could be chosen so that mainly Fe is precipitated, while Cr and Ni remains in the solution, or the pH level could be chosen such that both Fe and Cr are precipitated while Ni remains in the solution, and finally the pH level could be chosen such that both Fe, Cr, and Ni are precipitated. There could also be several different subsequent precipitations.
  • a redox measurement could be chosen where the redox potential (ORP, pe) is utilized for the monitoring of the separation of metal oxides along the titration curve of OFI- dosed versus ORP.
  • ORP redox potential
  • Another alternative is to use any ion-selective measurement system that follows the specific concentrations of the Fe, Cr, Ni and other metals ions, specifically. This can be done on one or multiple ions.
  • a photo spectrometer may be used. The slurry with precipitated metal oxides in the precipitation unit 18 is now fed from the precipitation unit to the dewatering unit 28.
  • the dewatering unit 28 solids are separated from the liquid in the slurry, forming a cake on the filter surface of a filter component if filters are used as dewatering units.
  • the aim should here to have as dry as possible cake of metal oxides and possibly hydroxides if hydroxides are used as pH affecting matter.
  • the cake is removed from the dewatering unit 28, for instance by scraping off a filter surface.
  • the recovered cake can then for example be re-used in the metal production plant.
  • the cake on the filter may be washed with cleaning liquids such as water by pressing water through the cake, for instance in order to wash away fluorides that may be present in the cake.
  • cleaning liquids such as water by pressing water through the cake
  • fluorides are the residues of the hydrofluoric acid previously mentioned often being part of the pickling acid.
  • the removal of fluorides is important if the resulting metal oxides and hydroxides are to be returned to the metal production plant.
  • the fluorides are sometimes unwanted in the smelt due to metallurgical reasons and may be seen as an impurity. It should be noted that in some steel making furnaces a small amount of fluoride containing inorganic chemical species are added as a flux component, but that this is controlled. In this present system this fluoride component could be optimised to assist the steel maker in controlled addition of such fluoride bearing material.
  • the liquid solution from the dewatering unit is then fed to the second separation unit 34, e.g. an ion exchange unit.
  • the second separation unit 34 e.g. an ion exchange unit.
  • the process of the ion exchange will make nickel in the solution to be separated from the rest of the solution because the nickel will bind to the resin of the ion exchange bed.
  • the process may be recirculating the solution through the bed until the bed is saturated or the solution is free of nickel.
  • the solution can be sent to a deposit facility for storage and after treatment from the first outlet 38, for instance water treatment. Should the solution still contain metal, which can occur if the bed is saturated before all nickel has been removed from the solution, the solution is kept in the second separation unit. When the bed has been saturated, it has to be regenerated. For this process, the solution needs to undergo an elution process with for example sulphuric acid, H2S04. After a water or weak acid rinse, the acid solution is added via inlet 36 and the elution process may be recirculating through the bed until the acid is saturated or there is no more Ni released from the bed, i.e. that the nickel concentration of the acid is constant. If the acid has reached a goal value, then it is sent to the subsequent step.
  • H2S04 sulphuric acid
  • the elution process is more effective at higher temperatures and should preferably be performed at around 45 - 65 ° C. This step is also important for removing NO3 and F because these ions affect a subsequent electro winning process. Also, the step of ion exchange concentrates the nickel content to above 20 grams/litre.
  • the solution from the ion exchange unit 34 now rich with nickel, is fed to a pre conditioning unit 42 where the pH value of the solution is raised above pH 4 by adding a base such as for instance NaOFI via inlet 44, because the eluate in the previous step is acidic.
  • the temperature may be increased for the subsequent step of electrowinning unit.
  • the nickel rich solution preferably at least 20 g Ni/I, is then fed to the electrowinning unit 48, in this process the nickel in the solution is recovered in that it is collected on the cathode of the electrowinning unit 48.
  • the cathode with the nickel is then removed from the electrowinning unit and the nickel is removed from the cathode.
  • the removed nickel can now be returned to the steel production plant.
  • the settings are such that the nickel is formed on or near the surface of the cathode, but instead of sticking to the surface it forms a powder or flakes or some other type of solid particle. These are then collected either through gravitational settling or through pumping with the liquid into some other particle separation means, for example a filter, centrifuge, cyclone, membrane or lamellar system.
  • some other particle separation means for example a filter, centrifuge, cyclone, membrane or lamellar system.
  • the electrowinning process is dependent on the pH levels, it is important that the pH is checked continuously, which may be done with a controller 52 much in the same way as for the precipitation unit. If the solution in the electrowinning unit becomes too acidic, then NaOH is added for raising the pH level of the solution, otherwise the electrowinning process will come to a halt.
  • the electrowinning process can be used for solutions containing nickel down to 5 grams/litre. At that level, the solution is brought back to the ion exchange unit 34 via a conduit 54 to be mixed with solutions coming from the dewatering unit.
  • a separate unit 60 may be arranged for example between the retardation unit and the precipitation unit that is capable of removing fluorides in the solution.
  • a further variant of the above system is to obtain nickel hydroxide Ni(OH)2 instead of nickel as metal, which Ni(OH)2 is a compound that can be utilized in many applications, such as for instance the manufacturing of batteries. If so, the electrowinning step is not used.
  • the solution from the dewatering unit 28 is instead led to an inlet 80 leading to a precipitation unit 82.
  • the precipitation unit 82 comprises an inlet 84 for adjusting the pH level, to a level where the nickel will be precipitated, preferably with NaOH to a level of between 8 - 8.5.
  • the precipitation unit is arranged with an outlet 86 wherein the precipitated Ni solution is fed to a dewatering unit 88.
  • a cake with solids is formed, containing Ni(OH)2 with high purity, up to 90%.
  • the obtained Ni(OH)2 may be treated further with different techniques for further drying and for increasing the purity further.
  • Cr as metal may also be obtained by electrowinning.
  • this requires a different voltage potential than electrowinning for Ni.
  • the same electrowinning unit may be used in different batches for recovery of different metals, or the system may comprise several electrowinning units for recovery of different metals working in parallel.
  • the precipitation unit 82 may be provided with means for adjusting the pH level, to a level where the nickel will be precipitated, preferably with NaOH to a level of between 8 - 8.5.
  • the precipitated Ni solution is then fed to a dewatering unit 88.
  • a cake with solids is formed, containing Ni(OH)2 with high purity, up to 90%.
  • the obtained Ni(OH)2 may be treated further with different techniques for further drying and for increasing the purity further. For instance, colling crystallisation may be used for further purification.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

La présente invention concerne un procédé de récupération de métaux à partir de solutions acides épuisées, lesdites solutions acides contenant des oxydes métalliques comprenant du fer, du chrome et du nickel, comprenant les étapes consistant à ajuster la solution, par addition d'agents de précipitation, à un niveau de pH où au moins du fer est précipité ; à déshydrater les solides précipités ; si nécessaire, à ajuster la solution jusqu'à un niveau de pH où le chrome est précipité, suivi de la déshydratation des solides précipités ; à traiter la solution liquide à partir de l'étape de déshydratation afin de récupérer le nickel. L'invention est caractérisée en ce que les agents de précipitation comprennent des agents qui ne contaminent pas les métaux à récupérer.
PCT/EP2020/083375 2019-11-28 2020-11-25 Procédé de récupération de métal Ceased WO2021105215A1 (fr)

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Application Number Priority Date Filing Date Title
SE1951361-3 2019-11-28
SE1951361 2019-11-28

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WO2021105215A1 true WO2021105215A1 (fr) 2021-06-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4575023A1 (fr) * 2023-12-20 2025-06-25 Fortum Battery Recycling Oy Procédé de récupération de métaux à partir de résidu acide de décapage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3800024A (en) 1970-11-03 1974-03-26 Nordstjernan Rederi Ab Process for neutralization and regeneration of aqueous solutions of acids and dissolved metals
GB1360809A (en) * 1970-11-03 1974-07-24 Sec Corp Electrowinning of nickel
WO2010051992A1 (fr) 2008-11-06 2010-05-14 Condoroil Impianti S.R.L. Récupération de métaux et d'acides à partir de solutions décapantes épuisées et/ou de boues de neutralisation
WO2011114000A1 (fr) * 2010-03-18 2011-09-22 Outotec Oyj Procédé de traitement de matériau brut nickélifère

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3800024A (en) 1970-11-03 1974-03-26 Nordstjernan Rederi Ab Process for neutralization and regeneration of aqueous solutions of acids and dissolved metals
GB1360809A (en) * 1970-11-03 1974-07-24 Sec Corp Electrowinning of nickel
WO2010051992A1 (fr) 2008-11-06 2010-05-14 Condoroil Impianti S.R.L. Récupération de métaux et d'acides à partir de solutions décapantes épuisées et/ou de boues de neutralisation
WO2011114000A1 (fr) * 2010-03-18 2011-09-22 Outotec Oyj Procédé de traitement de matériau brut nickélifère

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DUFOUR JAVIER ET AL: "Recovery of the Metals from pickling Liquors of Stainless Steel by Precipitation Methods", ISIJ INTERNATIONAL, vol. 41, no. 7, 31 July 2001 (2001-07-31), pages 801 - 806, XP055776199 *
REGEL-ROSOCKA ET AL: "A review on methods of regeneration of spent pickling solutions from steel processing", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 177, no. 1-3, 15 May 2010 (2010-05-15), pages 57 - 69, XP026928925, ISSN: 0304-3894, [retrieved on 20091216], DOI: 10.1016/J.JHAZMAT.2009.12.043 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4575023A1 (fr) * 2023-12-20 2025-06-25 Fortum Battery Recycling Oy Procédé de récupération de métaux à partir de résidu acide de décapage
WO2025133460A1 (fr) * 2023-12-20 2025-06-26 Fortum Battery Recycling Oy Procédé de récupération de métaux à partir d'un résidu d'acide de décapage

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