WO2015192234A1 - Récupération de zinc et de manganèse à partir de résidus ou de boues de pyrométallurgie - Google Patents

Récupération de zinc et de manganèse à partir de résidus ou de boues de pyrométallurgie Download PDF

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Publication number
WO2015192234A1
WO2015192234A1 PCT/CA2015/050547 CA2015050547W WO2015192234A1 WO 2015192234 A1 WO2015192234 A1 WO 2015192234A1 CA 2015050547 W CA2015050547 W CA 2015050547W WO 2015192234 A1 WO2015192234 A1 WO 2015192234A1
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WIPO (PCT)
Prior art keywords
leaching
precipitation
solution
matrix
enriched
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PCT/CA2015/050547
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English (en)
Inventor
Guy Mercier
Julien Mocellin
Marie-Odile Simonnot
Jean-Louis Morel
Jean-François BLAIS
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Institut National De La Recherche Scientifique (Inrs)
Université De Lorraine
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Application filed by Institut National De La Recherche Scientifique (Inrs), Université De Lorraine filed Critical Institut National De La Recherche Scientifique (Inrs)
Priority to EP15809510.9A priority Critical patent/EP3172348A4/fr
Publication of WO2015192234A1 publication Critical patent/WO2015192234A1/fr

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    • 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
    • C22B47/00—Obtaining manganese
    • 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
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • 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
    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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 technical field relates to the treatment of pyrometallurgical sludge or residues, and more particularly to the recovery of components from such materials.
  • sewage sludge of smokes of blast furnaces can be very rich in manganese, zinc and lead (between 5 and 40%). These materials have generally been deposited in periphery of the sites of steel industry.
  • Zn is an important metal in metallurgical, chemical and textile industries. It mainly extracted from sulphide ores including Zn. Portions of Zn can be recovered from secondary sources such as electric furnace dust containing different levels of impurities depending on the source (Jha et al. 2001). Pyrometallurgical and hydrometallurgical processes are usually used to recover Zn in the ore or from secondary sources. Nevertheless, the pyrometallurgical processes consume significant energy and require process gas treatment during Zn recovery. The majority of studies have leached zinc with sodium hydroxide (Charpentier et al., 2007), ammonium chloride (Olper et al., 1993) and sulfuric acid (Dvorak et al., 2005).
  • Mn0 2 Pyrolusite
  • IV Extraction of Mn (IV) must be carried out under reducing conditions (Naik et al. 2000).
  • Various techniques for leaching ores or nodules have been studied for the last 20 years.
  • sulfuric acid as a reducing agent, such as sulfuric acid leaching, coupled hydrogen peroxide (Allen et al, 1988; Jiang et al, 2004), to oxalic acid (Sahoo et al, 2001.), ferrous sulfate (Brantley et al, 1968), pyrite (Vracar et al, 2000) and aqueous sulfur dioxide (S0 2 ) Chow et al, 2012b, Ward (2005a), and Ward (2005b).
  • sulfuric acid leaching coupled hydrogen peroxide (Allen et al, 1988; Jiang et al, 2004), to oxalic acid (Sahoo et al, 2001.), ferrous sulfate (Brantley et al, 1968), pyrite (Vracar et al, 2000) and aqueous sulfur dioxide (S0 2 ) Chow et al, 2012b, Ward (2005a), and Ward (2005b).
  • HCI hydrochloric acid
  • Ni Chen et al, 1992
  • hydrogen peroxide El Hazek et al, 2006.
  • Solution can contain impurities that can affect the production of pure Mn compounds. Purification is usually required to remove impurities present in aqueous solutions before proceeding to the recovery of the metal.
  • the precipitation of the metals as hydroxides or sulfides are the main purification techniques used to recover the Mn and Zn in the solution.
  • One challenge is to precipitate unwanted metals and to keep in solution Zn and Mn with a cost as low as possible.
  • cementation is also a technique commonly used in hydrometallurgy. This technique includes the precipitation of a metal from an aqueous solution of a salt thereof with another metal. This redox reaction connects a more electropositive metal which is deposited on a less electropositive metal from solution. This technique is used in zinc hydrometallurgy to precipitate the metals present in the solution as Cu by adding Zn powder (Rizet et al, 2000).
  • Techniques described herein relate selective extraction of zinc and manganese from metal sludge or dust by utilizing acidic leaching (e.g., using sulfuric acid) and generating a high-concentration lead slag.
  • acidic leaching e.g., using sulfuric acid
  • Various implementations are well suited to treating pyrometallurgic sludge or residue, and particularly to recover valuable constituents from sludge or residue, such manganese, zinc and lead in particular
  • the techniques enable steel residues to be treated by selectively and sequentially leaching the zinc and manganese, followed by effective purification to produce marketable product of each these metals.
  • the techniques include selectively leaching Zn, Mn and Pb in order to obtain a concentrate of Mn, a concentrate of Zn and residue rich in Pb.
  • a process for treating a matrix comprising zinc (Zn), manganese (Mn) and lead (Pb), comprising: leaching the matrix to generate a leaching solution enriched in Zn and a fraction enriched in Mn and Pb; subjecting the leaching solution to Zn-precipitation to produce Zn-based precipitates and a Zn-depleted fraction comprising Mn compounds; leaching the fraction enriched in Mn and Pb to produce a Mn-enriched leaching solution and a Pb-enriched fraction; and subjecting the Zn-depleted fraction and/or the Mn-enriched leaching solution to Mn-precipitation to produce Mn-based precipitates.
  • the leaching of the matrix is performed using an aqueous acidic solution.
  • the aqueous acidic solution comprises H 2 S0 4 .
  • the leaching of the matrix comprises multiple leaching runs with the aqueous acidic solution and multiple rinsing runs with an aqueous rinsing solution.
  • the leaching of the matrix comprises at least three leaching runs and/or at least three rinsing runs.
  • the process also includes, prior to the Zn-precipitation, removing additional metal components from the leaching solution enriched in Zn.
  • the additional metal components include aluminum (Al).
  • the additional metal components include iron (Fe).
  • the removing of the additional metal components comprises precipitating the additional metal components.
  • precipitating of the additional metal components comprises adding a hydroxide of a divalent cation.
  • the hydroxide of a divalent cation comprises Ca(OH) 2 or NaOH.
  • the Zn-precipitation comprises adding NaOH or Na 2 S to produce ZnO or ZnS as the Zn-based precipitates.
  • the process also includes, prior to the Mn-precipitation, removing additional metallic impurities from the Zn-depleted fraction and/or the Mn- enriched leaching solution, including aluminum, iron, lead, zinc or a combination thereof.
  • precipitating of the additional metal components prior to the Mn-precipitation comprises adding NaOH and Na 2 S to the Zn-depleted fraction and/or the Mn-enriched leaching solution.
  • the Mn-precipitation comprises adding a carbonate compound to produce Mn-carbonates as the Mn-based precipitates.
  • the carbonate compound comprises Na 2 C0 3 to produce MnC0 3 .
  • the process also includes, prior to the leaching of the matrix, a step of determining a composition of the matrix.
  • determining the composition of the matrix comprises determining the concentrations of Zn and Mn.
  • determining the composition of the matrix comprises determining the concentration of Pb.
  • determining the composition of the matrix includes determining the concentrations of Al and/or Fe.
  • the process also includes treating the Pb-enriched fraction to recover Pb therefrom.
  • the process also includes subjecting the Zn-depleted fraction to Mn-precipitation in a first reactor to produce a first stream of Mn-based precipitates; and subjecting the the Mn-enriched leaching solution to Mn-precipitation in a second reactor to produce a second stream of Mn-based precipitates.
  • the process further includes producing a Mn-depleted stream in the second reactor; and subjecting at least a portion of the Mn-depleted stream to further Mn-precipitation.
  • the further Mn-precipitation of the Mn- depleted stream is conducted in the first reactor.
  • the process further includes recycling a portion of the Mn- depleted stream from the second reactor for addition to the matrix before or during the leaching thereof.
  • the process further includes recovering a metals-depleted liquid from the Mn-precipitation in the first reactor and adding at least a portion of the metals-depleted liquid to the matrix before or during the leaching thereof.
  • the leaching of the matrix is performed in atmospheric pressure conditions.
  • one or more of the leaching steps are performed in a counter- current reactor.
  • one or more of the leaching steps are performed in an agitated tank reactor.
  • one or more of the leaching steps are performed in a batch reactor or a continuous.
  • the leaching reactors can use recirculated streams derived from other units of the process.
  • the recirculated streams can include leaching solutions from which one or more metals (e.g., valuable metal components) have been removed, such as streams that have been subjected to Mn-precipitation.
  • the recirculation can be done at various points in the overall process, using different recycle streams depending on various factors, such as economic considerations, make-up water availability, build-up of certain components in the recycled streams, and so on.
  • the matrix comprises a powder or dust. In some implementations, the matrix comprises a by-product or waste stream derived from metals processing. In some implementations, the matrix comprises steel plant dust.
  • a method for the hydrometallurgical treatment of a matrix comprising manganese (Mn), zinc (Zn), lead (Pb), iron (Fe), aluminum (Al), and at least one of calcium, chlorides, sodium and potassium as impurities, the method comprising: a first leaching step comprising: leaching the matrix at atmospheric pressure in a reactor using a first leaching solution to product a first leach liquor and a first leach residue, the first leaching solution comprising a sulfuric acid solution; and separating the first leach liquor from the first leach residue after the first leaching; a second leaching step comprising: leaching the first leach residue at atmospheric pressure using a second leaching solution to form a second leach liquor and a second leach residue, the second leaching solution comprising sulfuric acid and a reducing agent; and separating the second leach liquor from the second leach residue; a Mn-precipitation step wherein Mn compounds are precipitated from the first and second leach liquors, including
  • the process also includes selecting a quantity of the carbonate to adjust the pH of the first and second leach liquor sufficiently to precipitate out Mn carbonate compounds.
  • the pH of the second leaching is between about 3 and about 5.
  • the reducing agent used in the second leaching step comprises Na 2 S 2 0 5 .
  • the process further includes subjecting the first liquor to Zn- precipitation prior to Mn-precipitation.
  • the Zn-precipitation includes electroplating Zn as Zn metal.
  • the Zn-precipitation includes forming Zn sulfide and/or Zn oxide precipitates that are precipitated out of the solution.
  • the process includes separating the Zn sulfide and/or Zn oxide precipitates from the solution to form a Zn sulfide and/or Zn oxide containing residue, and a Zn-depleted first liquor that is subjected to the Mn-precipitation step.
  • the Zn-precipitation comprises adding alkali or sulfide to the first liquor to precipitate Zn compounds; and then preforming a solid-liquid separation to produce a Zn sulfide and/or oxide cake.
  • the process includes subjecting the first liquor to a Fe, silicate and Al precipitation step to form Fe, silicate and Al hydroxide compounds and a depleted liquor; separating the Fe, silicate and Al hydroxide compounds from the depleted liquor; and subjecting the depleted liquor to the Zn-precipitation.
  • the Fe, silicate and Al precipitation step comprises adding alkali to increase the pH between about 4 and about 5; and then preforming a solid-liquid separation to produce a mixed Fe, silicate and Al hydroxide cake.
  • the Mn-precipitation step comprises adding the carbonate to the first and second liquors to increase the pH to between about 7.5 and about 8.5; and then performing a solid-liquid separation to produce a Mn-carbonate cake.
  • the second leach residue contains between 10 wt% and 30 wt% of Pb.
  • a leaching period of mixing the sulfuric acid solution for the first and/or second leaching steps is between about 10 minutes and about 24 h.
  • the temperature of the sulfuric acid solution is between about 20°C and about 40°C.
  • the process includes one or more features of claims 1 to 34.
  • a system for treating a matrix comprising zinc (Zn) and manganese (Mn), comprising: a leaching unit for leaching the matrix to generate a Zn-enriched leaching solution, and a fraction enriched in Mn and Pb; a Zn-precipitation unit for subjecting the Zn-enriched leaching solution to Zn- precipitation to produce Zn-based precipitates and a Zn-depleted fraction comprising Mn compounds; and a leaching unit for leaching the fraction enriched in Mn and Pb to produce a Mn- enriched leaching solution and a Pb-enriched fraction; and a Mn-precipitation system for subjecting the Zn-depleted fraction and/or the Mn- enriched leaching solution, or streams derived therefrom, to Mn-precipitation to produce Mn-based precipitates.
  • Zn zinc
  • Mn manganese
  • the Mn-precipitation system comprises a first Mn-precipitation unit for subjecting the Zn-depleted fraction to Mn-precipitation; and a second Mn- precipitation unit for subjecting the Mn-enriched leaching solution to Mn-precipitation.
  • the systems includes an additional precipitation unit for receiving the Zn-enriched leaching solution and removing at least one of aluminum (Al), iron (Fe) and silicate therefrom, to produce a liquor for supplying to the Zn-precipitation unit.
  • a system for the hydrometallurgical treatment of a matrix comprising manganese (Mn), zinc (Zn), lead (Pb), iron (Fe), aluminum (Al), and at least one of calcium, chlorides, sodium and potassium as impurities
  • the system comprising: a first leaching unit for leaching the matrix at atmospheric pressure in a reactor using a first leaching solution to product a first leach liquor and a first leach residue, the first leaching solution comprising a sulfuric acid solution; a first separation unit for separating the first leach liquor from the first leach residue after the first leaching; a second leaching unit for leaching the first leach residue at atmospheric pressure using a second leaching solution to form a second leach liquor and a second leach residue, the second leaching solution comprising sulfuric acid and a reducing agent; a second separation unit for separating the second leach liquor from the second leach residue; and a Mn-precipitation system for precipitating Mn compounds from the first and second leach residue
  • the Mn-precipitation system comprises a first Mn-precipitation unit for subjecting the first leach liquor to Mn-precipitation; and a second Mn-precipitation unit for subjecting the second leach liquor to Mn-precipitation.
  • the system includes an additional precipitation unit for receiving the first leach liquor and removing at least one of aluminum (Al), iron (Fe) and silicate therefrom, to produce a metals depleted liquor comprising Zn and Mn; and a Zn- precipitation unit for receiving the metals depleted liquor and producing Zn precipitates and a Zn-depleted fraction, wherein the first precipitation unit is configured to receive the Zn-depleted fraction to be subjected to the Mn-precipitation.
  • Al aluminum
  • Fe iron
  • silicate silicate
  • system also includes one or more operational or structural features of the processes described in the description or drawings.
  • Figure 1 is a graph showing Zn concentration (mg/L) during electrolysis.
  • Figure 2 is a diagrammatic representation of a flow sheet depicting a method for the leaching of a metallic sludge.
  • Figure 3 is a diagrammatic representation of a process for treating a metallic sludge.
  • Figure 4 is a diagrammatic representation of another process for treating a metallic sludge.
  • the process begins with metallic sludge 10, which may be obtained from "brownfield” or elsewhere.
  • the metallic sludge 10 can contain between 1 and 40 percent of Zn, between 0.5 and 28 % of Mn and between 1 and 20 % of Pb, for example.
  • the source material that is treated can be a mixture of metallic sludge streams from multiple sources and/or a pre-treated metallic sludge stream or another stream derived from metallic sludge.
  • Such metallic sludges may contain at least one of the following elements: iron, aluminum, calcium, silicates, sodium and magnesium.
  • the metallic sludge 10 is reacted at ambient temperature with sulfuric acid at step 1 1 , referred to as Zn leaching step.
  • the resource material pulp density can be between 5 and 15% by weight.
  • Aqueous sulfuric acid reacts with zinc oxide according the following equation:
  • Equation 1 ZnO + H 2 S0 4 -> Zn 2+ + H 2 0 + S0 4 2"
  • Equation 2 MnO + H 2 S0 4 Mn 2+ + H 2 0 + S0 4 2"
  • the removal of impurities from leach liquor (“LL” which may also be referred to as pregnant leach solution “PLS”) can be accomplished in one stage.
  • the pH of the solution is changed from about 4.25 to about 4.75 to precipitate silicate, iron and aluminum at a mix tank, shown at step 14, referred to as Al and Fe precipitation step.
  • This pH may be achieved in various way, including the addition to the solution of alkaline earth hydroxides or alkaline salt, such as NaOH, Mg(OH) 2 or Ca(OH) 2 .
  • the precipitated solid can be separated from the treated leach liquor in a thickener or a filter in a solid-liquid separation step 15.
  • the pH of the solution can then be raised; for example, sodium sulfide or Na 2 S can be added to the solution to precipitate zinc as sulfides, the pH of the leach liquor can be about 4.25 to about 4.75.
  • Zinc can also be precipitated and recovered as zinc oxide with a stoichiometric addition of sodium hydroxide, the pH of the leach liquor would be changed to about 7.0 to about 10.0, at step 16, referred to as Zn precipitation step.
  • Zinc can also be recovered through electroplating with specific conditions.
  • the sulphides or oxides precipitates can be separated from the treated leach liquor in a thickener or a filter in another solid-liquid separation step 17.
  • the pH of the solution can then be raised to about 8.5 with Na 2 C0 3 to precipitate and recover manganese carbonate, at step 18, referred to as Mn precipitation step
  • Mn precipitation step The solid manganous carbonate is separated from the solution by a thickener or a filter, in another solid-liquid separation step 19.
  • the leached residue (from the first step 11 of Zn leaching) can be reacted in a stirred tank at ambient temperature with sulfuric acid and sodium metabisulfite to reduce manganese dioxide, at step 12, referred to as Mn leaching step.
  • Mn leaching step there can be 2 steps of leaching and 2 steps of rinsing.
  • Equation 3 2Mn0 2 + H 2 S0 4 + Na 2 S 2 0 5 -> 2Mn 2+ + H 2 0 + 3S0 4 2" + 2Na +
  • the pH of the solution can be between about 3.0 and about 5.0 to leach manganese without leaching iron or aluminum.
  • additional removal of impurities from leach can be accomplished in one stage.
  • the pH of the solution can be changed from about 4.80 to about 5.60 to precipitate aluminum, iron, lead and zinc in a mix tank, shown in step 21 , referred to as Al, Fe, Pb and Zn precipitation step.
  • Achievement of the desired pH may include the addition to the solution of sodium hydroxide and sulfide, such Na 2 S, to precipitate impurities as sulfides.
  • the precipitated solid can be separated from the treated leach liquor in a thickener or a filter in a solid- liquid separation step 22.
  • the pH of the solution is then raised to about 8.5 with Na 2 C0 3 to precipitate and recover manganese carbonate, at step 23, referred to as another Mn precipitation step.
  • the solid manganous carbonate can be separated from the solution by a thickener or a filter in another solid- liquid separation step 24.
  • Final residues can contain a high proportion of lead, between 10 and 30% for example, which can be revalorize by hydrometallurgical and/or pyrometallurgical methods.
  • a leaching test was performed using steel dust.
  • the composition of the dust is given in Table 1.
  • 400 g of dust was lixiviated (i.e., leached) with 4 liters of water (10% pulp density by weight) in a stirred plastic reactor with baffle.
  • the sulfuric acid concentration used for each leaching is 0.25 M, about 97% of the zinc and 13% of manganese is extracted.
  • Mn0 2 the first leaching step preferentially leaches Zn and not much Mn or Pb. Leaching times did not exceed 30 minutes and rinsing times did not exceed 10 minutes.
  • the weight of dry residue after leaching was 252 g.
  • a second leaching step included leaching the first leach residue in a second leaching solution with sulfuric acid and reductant such as sodium metabisulfite.
  • the elements concentration in the leach liquors are shown in the Table 3.
  • the leach liquor purification is performed using a technique such as precipitation.
  • the aim of precipitation is to remove iron and aluminum from the leach liquor after the zinc leaching test.
  • the compositions of the leach liquor and the initial pH are in Table 11. For each precipitation step, 1 liter of leach liquor has been used.
  • the pH of the solution is changed to about 4.25 and 4.75 to precipitate silicate, iron and aluminum in a mix tank using lime or sodium hydroxide as precipitation agent.
  • After pH stabilization and decantation the purified leach liquor and residues are analyzed.
  • the compositions of the purified leach liquors, the final pH and the quantity of lime used in each precipitation are shown in Table 12. Table 12 shows that the majority of iron and aluminum have been precipitated without zinc and manganese.
  • compositions of the precipitates are shown in Table 13.
  • Table 12 Elements concentration in the purified leach liquor (mg/L) pH Ca(OH) 2 Mn Pb Al K Ca Fe Mg Sn Zn S Na
  • Zinc oxide was precipitated from leach liquors after the zinc leaching (see EXAMPLE II) using stoichiometric quantity of NaOH as a precipitation agent (considering the concentration of Zn) at pH between 9.0 and 1 1.0.
  • 1000 mL of leach liquor L1 Zn with 9339 mg Zn/L is precipitated with 114 mL of 100 g NaOH/L.
  • the results are in Table 14.
  • Zinc sulphide was precipitated from purified leach liquors using Na 2 S as a precipitation agent at pH between about 4.5 and about 5.5.
  • the Mn and Zn concentration after and before the precipitation are in Table 16.
  • Table 16 shows that most of zinc is precipitated in sulphides without manganese which will be precipitated as carbonate in another stage.
  • Manganese carbonate was precipitated from purified leach liquors using stoichiometry of Na 2 C0 3 as a precipitation agent (considering the concentration of Mn) at pH between about 7.5 and 8.5. Before manganese carbonate precipitation, impurities like Al, Fe, Pb and Zn are removed as sulfide from the leach liquor. The pH of the solution is changed to about 4.80 and 5,80 to precipitate aluminum, iron, lead and zinc in a mix tank using sodium hydroxide and sodium sulfide as precipitation agent. After pH stabilization and decantation the purified leach liquor is filtrated, manganese carbonate is then precipitated with Na 2 C0 3 . Manganese precipitation is very fast at ambient temperature. In the test, 1000 ml_ of leach liquor L1 Mn with 10125 mg Mn/L is precipitated with 23.4 g of Na 2 C0 3 . The results are shown in Table 17.
  • manganous carbonate precipitates After the precipitation, it is preferred to wash the manganous carbonate precipitates to eliminate the sodium and sulfides.
  • 20 g of manganous carbonate was rinsed with 200 ml_ of water (10% pulp density by weight), the results are shown in Table 20.
  • the concentration of Mn in the cake is 44.6 % for L1 and 43.0 % for L2.
  • Zn metal was electrodeposited from leach liquor using an electroplating cell.
  • An electrical power source is connected to four cathodes and four anodes.
  • the cathodes are made of stainless steel and the anodes are made of Ti0 2 .
  • the area of each cathode is 220 cm 2 .
  • the solution is fed into electrolytic tank of 2 liters where zinc metal is deposited on the stainless steel cathodes during electrolysis.
  • At the Ti0 2 anodes an oxidation reaction occurs, generating oxygen gas, protons and giving electrons.
  • the current is fixed of 15 A and every 60 minutes the cathodes full of Zn metal are replaced by news cathodes.
  • Zinc metal was electrolysed from the mixture of leach liquors L1 and L2 after the zinc leaching (see EXAMPLE II). The results are shown in Table 21 and Figure 1 shows the Zn concentration during the electrolysis. Table 21 : Concentration of elements in leach liquors (mg/L)
  • Waste streams from the metals processing industry may be processed to extract compounds such as Zn, Mn and/or Pb, in particular when the concentration of such compounds is economically significant.
  • Waste streams can include electric arc furnace (EAF) dust, various pyrometallurgical residues, and materials derived therefrom.
  • EAF electric arc furnace
  • Waste streams from the metals processing industry or other matrices can also be tested to determine the composition and extractability of desired components, prior to subjecting the waste streams to an implementation of the techniques described herein.
  • Various other matrices, such as mining residues can also be treated with techniques described herein.

Abstract

Des techniques hydrométallurgiques pour la récupération sélective de Zn, Mn et Pb dans cet ordre à partir de boues ou de divers résidus métallurgiques peuvent comprendre des étapes de lixiviation pour extraire le zinc et le manganèse ; les étapes consistant à éliminer le fer, l'aluminium et la silice des solutions de lixiviation ; et la récupération du manganèse et du zinc par précipitation. Mn peut être précipité à partir d'une solution de lixiviation initiale ainsi que d'une solution de lixiviation secondaire obtenue par lixiviation de la suspension de l'étape de lixiviation initiale. Divers autres flux de déchets peuvent également être traités.
PCT/CA2015/050547 2014-06-18 2015-06-12 Récupération de zinc et de manganèse à partir de résidus ou de boues de pyrométallurgie WO2015192234A1 (fr)

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CA2,854,778 2014-06-18

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CN110436721A (zh) * 2019-08-12 2019-11-12 江苏荣信环保科技有限公司 一种金属表面酸洗污泥和废酸综合处理工艺
EP3555327A4 (fr) * 2016-12-15 2020-08-12 Teknologian Tutkimuskeskus VTT OY Traitement de déchets industriels contenant des métaux
CN113061736A (zh) * 2021-03-30 2021-07-02 攀钢集团攀枝花钢铁研究院有限公司 烧结机头灰中钾、铅、铁的分离方法

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Publication number Priority date Publication date Assignee Title
EP3555327A4 (fr) * 2016-12-15 2020-08-12 Teknologian Tutkimuskeskus VTT OY Traitement de déchets industriels contenant des métaux
CN110436721A (zh) * 2019-08-12 2019-11-12 江苏荣信环保科技有限公司 一种金属表面酸洗污泥和废酸综合处理工艺
CN113061736A (zh) * 2021-03-30 2021-07-02 攀钢集团攀枝花钢铁研究院有限公司 烧结机头灰中钾、铅、铁的分离方法
CN113061736B (zh) * 2021-03-30 2022-03-22 攀钢集团攀枝花钢铁研究院有限公司 烧结机头灰中钾、铅、铁的分离方法

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