WO2014168622A1 - Système et procédé de récupération de métaux précieux à partir de laitiers - Google Patents

Système et procédé de récupération de métaux précieux à partir de laitiers Download PDF

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Publication number
WO2014168622A1
WO2014168622A1 PCT/US2013/036157 US2013036157W WO2014168622A1 WO 2014168622 A1 WO2014168622 A1 WO 2014168622A1 US 2013036157 W US2013036157 W US 2013036157W WO 2014168622 A1 WO2014168622 A1 WO 2014168622A1
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WO
WIPO (PCT)
Prior art keywords
slag
leaching
solution
mineral acid
metal
Prior art date
Application number
PCT/US2013/036157
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English (en)
Inventor
Timothy Roy HYMER
Bruce David CHAMBERLAIN
Karl Friedrich SCHNEIDER
Massimo Giuseppe MACCAGNI
Original Assignee
Metals Technology Development Company, LLC
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 Metals Technology Development Company, LLC filed Critical Metals Technology Development Company, LLC
Priority to PCT/US2013/036157 priority Critical patent/WO2014168622A1/fr
Publication of WO2014168622A1 publication Critical patent/WO2014168622A1/fr

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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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • 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
    • C22B7/04—Working-up slag
    • 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

  • This invention relates to the recovery of metal values from slags, such as those produced in the pyrometallurgical production of metals from ores.
  • slags are often the subject of environmental regulation, as they are in the United States. In the United States most slags are deemed hazardous waste as defined RCRA (40 CFR Part 261 ), but benefit from the Bevill exclusion, an amendment to the Resource Conservation and Recovery Act (RCRA) which allows slags to be stored at certain permitted locations.
  • RCRA Resource Conservation and Recovery Act
  • Embodiments of the present invention provide for the economic recovery of metal values from slags.
  • Large quantities of easily recoverable slags are available at smelter sites around the world.
  • embodiments of this invention allow for the recovery of valuable metals, some of these methods can also reduce the metal content of the slags so that they are no longer categorized as hazardous materials, allowing the waste material to be used in construction of buildings and roads.
  • a method of recovering metal values from slag comprising pulverizing the slag in to fine particles of less than 100 ⁇ , and more preferably less than 10 ⁇ .
  • Metals are then leached from the pulverized slag in a solution of NH 4 CI, and alkali and alkali earth chlorides (preferably NaCI and KCI).
  • the pH is preferably adjusted to less than 1 through the addition of a mineral acid such as HCI or H 2 S0 4 .
  • the metals are leached at temperature of between 70 °C and 90 °C at atmospheric pressure, until sufficient dissolution of the metals has occurred (typically one to five hours).
  • the pH is adjusted to precipitate iron.
  • the pH is further adjusted and the solution is subjected to a sequential cementation recovery in which the addition of less noble metals are used to precipitate more noble metals (Ag, Cu, Pb, Co, Ni, Cd and other metals can be recovered in this manner). After the sequential recovery of these metals, zinc can be recovered from the solution by electrowinning.
  • Fig. 1 is a flow chart of a process for the recovery of metals from slag in accordance with the principles of this invention
  • FIG. 1 A preferred embodiment of a process for the recovery of metal values from slag is shown in Fig. 1 .
  • the slag is pulverized into small particles, preferably less than about 100 ⁇ , more preferably less about 75 ⁇ , and most preferably less than about 10 ⁇ .
  • the slag can be pulverized by grinding, or crushing, such as in a ball mill.
  • the slag particles are then leached in a solution of ammonium chloride (NH 4 CI) and alkali and alkali earth chlorides, preferably NaCI and KCI as well.
  • the pH of the solution is adjusted to less than about 3, and preferably to less than about 2, and more preferably to less than about 1 using a mineral acid such as HCI or H 2 S0 4 .
  • Oxidizing media such as cupric or ferric salts, such as, but not limited to, CuCI 2 or FeCI 3 can be added.
  • the leaching is preferably conducted above about 70 °C and below the boiling point of the solution, and more preferably between about 70 °C and about 100°C, and most preferably between about 85 °C and about 95 °C, at atmospheric pressure. Generally higher temperatures improve the leaching process, but it usually is desirable to stay well (5°C or more) below the boiling point of the leaching solution (approximately 1 10°C).
  • the leaching is continued until substantially all of the metal in the slag is dissolved. This can be detected by measuring the oxidation reduction potential (ORP), which plateaus when the reaction is completed and typically takes between one and five hours. Reaction time depends upon a number of factors, and generally can be decreased by increasing the temperature, decreasing the particle size, adjusting the addition of oxygen, and/or increasing agitation.
  • ORP oxidation reduction potential
  • the material is filtered, with the leachate at 28 being fed to a reactor in which the pH is raised to about 4, for example with the addition of lime, and air is bubbled to cause the precipitation of iron. It is desirable to remove this iron because if iron is present in the electrowinning cell, it can cause a local precipitation of ferric oxides that can be incorporated in the zinc plate thereby reducing its quality; and because the iron can cause a shuttle reaction (where ferric ion is reduced to ferrous at the cathode and ferrous is oxidize to ferric at the anode).
  • the solid material filtered at 26 typically has sufficient metal removed that it is no longer regarded as hazardous waste and can be used for construction and other purposes.
  • the solution is filtered to remove the precipitated iron and at 32 the filtrate is fed to a neutralization reactor where the pH is adjusted to between about 6.5 and about 7.
  • the solution is fed to a cementation reactor where the metals more noble that zinc are precipitated through the addition of metallic zinc powder. Depending upon the concentration of these metals, the cementation can be run to be selective for some or all of the metals.
  • Zinc powder does not have to be used and other metal powders can be used to precipitate more noble metals.
  • Zinc powder is preferred in many embodiments because it is relatively inexpensive, and because the zinc can all be subsequently recovered.
  • cementation also known as "chemical displacement precipitation”
  • cementation is the reaction through which a first metal is precipitated in the elemental state, from a solution containing it in dissolved form, by the addition to the solution of a second metal in the elemental state (precipitating metal) having a lower (or more negative) reduction potential with respect to the reduction potential of the first metal.
  • Cementation allows the leached metals present in the extraction solution to selectively precipitate one by one, suitably selecting the precipitating metal on the basis of its reduction potential.
  • the cement obtained generally also contains impurities of one or more of the other leached metals.
  • concentration of these impurities mainly depends on the difference between the reduction potential of the metals which form the impurities and that of the precipitating metal, in addition to the concentration of the respective ions in the solution subjected to cementation.
  • the cement typically contains the main metal precipitated in a highly pure form (higher than 95% by weight with respect to the weight of the cement; the remaining part consists of impurities of other metals in the elemental state).
  • the cements obtained can be re-used as such or they can be subjected to simple known purification processes, to obtain metals having an even higher purity.
  • the cementation is preferably effected in a plurality of steps in series (multi-step cementation), in each of which one or more of the leached metals precipitates.
  • the precipitating metal is added to the solution subjected to cementation in powder form, thus favoring the chemical displacement reaction which leads to the precipitation of the metallic cement.
  • the precipitating metal is generally added in an excess quantity with respect to that of the metal to be precipitated.
  • the metal added in each of the cementation steps is always the same.
  • the cementation is effected as follows:
  • a first quantity of precipitating metal is added to the extraction solution, obtaining the precipitation of the non-ferrous metal having the highest reduction potential among the metals present in solution.
  • the precipitating metal is added to the solution in an excess quantity with respect to the metal to be precipitated, so as to cause substantially complete precipitation of the metal to be recovered.
  • the excess precipitating metal is calculated in relation to the specific chemical displacement reaction which takes place in the cementation step.
  • the precipitating metal is typically added in an excess of 1 to 30% with respect to the stoichiometric quantity with respect to the metal to be precipitated.
  • the extraction solution is left to decant and the precipitated metal, in the elemental state, is subsequently separated from the supernatant solution by filtration.
  • the supernatant solution containing the remaining leached metals, (and possibly a residual quantity of ions of the first precipitated metal), is subjected to a second cementation step, wherein, by the addition of a second quantity of precipitating metal, the precipitation is caused of the non- ferrous metal having the highest reduction potential among the remaining metals present in the solution.
  • the precipitation of the second metal may be accompanied by the possible precipitation of a further quantity of the first metal.
  • the supernatant solution can be subjected to a third cementation step, in which a further non-ferrous metal is precipitated (the one having the highest reduction potential among those still in solution) by effecting the same operations as the previous cementation steps.
  • the precipitation of the cement of the third metal is accompanied by the possible precipitation of increasingly less significant quantities of the previous metals precipitated.
  • the supernatant solution is subjected to possible further cementation steps, analogously to the previous steps, until all the non-ferrous metals of interest present in the extraction solution have precipitated and been recovered.
  • the metal used as precipitating metal can be any metal having a reduction potential lower than the reduction potential of at least one of the leached metals present in solution.
  • the same precipitating metal is preferably used.
  • the precipitating metal must have a lower reduction potential with respect to the reduction potential of each of the leached metals present in solution.
  • a metal particularly suitable for the purpose is zinc, due to its low cost and greater tendency to oxidize with respect to the non-ferrous metals typically to be recovered.
  • the standard reduction potential of zinc for the pair Zn 2 7Zn is in fact equal to -0.76 V.
  • This cementation process can be used to recover silver, copper, lead, cobalt, nickel and cadmium. Typically copper and the silver are recovered together, and the cobalt and the nickel are recovered together.
  • the supernatant solution substantially only contains the ions of the metal used as precipitant in the various cementation steps (in addition to possible residues of ions of non-precipitated leached metals).
  • the supernatant solution can be advantageously subjected to electrolysis to recover the precipitating metal in elemental form, so that it can be re-used in subsequent recovery process cycles.
  • the electrolysis of the final extraction solution is effected in an open cell, with a titanium cathode and graphite anode, according to the process described in U.S. Patent No. 5,468,354, Process for Heavy Metal Electrowinning, and U.S. Patent No.
  • the overall chemical reaction of the electrolytic cell is:
  • the electrolytic process described above is particularly advantageous as it avoids the evolution of gaseous chlorine, which is a toxic gas, in favor of the evolution of gaseous nitrogen.
  • the zinc electrodeposited on the titanium cathode is finally recovered, for example, in the form of a metallic sheet which can be then melted into ingots. Pure zinc powder can be produced from the molten mass. The zinc powder thus recovered can be re-used in new recovery process cycles of non-ferrous metals according to the present invention.
  • a portion of the filtered solution is sent to a carbonization unit where alkali metal carbonates (chiefly of calcium, magnesium, and manganese) are formed.
  • the solution is filtered to remove precipitated alkali metal carbonates, including calcium carbonate, magnesium carbonate, and manganese carbonate. These elements can be problematic for plating above certain concentrations.
  • the solution is sent to a crystallization unit where water is removed to maintain the proper water balance of the circulating solution, and remaining leached alkali metals (including sodium and potassium) are crystallized and recovered as salts. A portion of these salts are produced by reagent additions for the pH changes.
  • Example 1 Example 1
  • the filtrate was 4.4 L, including the wash, and had the following composition:
  • ND indicates a level below the measurable threshold
  • Table 2 illustrates the both the metal values found in a typical slag, and the low level of metals remaining after treatment in accordance with the principles of this invention.

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

Abstract

La présente invention concerne un procédé de récupération de métaux précieux à partir de laitier, ledit procédé comprenant les étapes consistant à : pulvériser le laitier en particules inférieures à environ 100 μm; lixivier le laitier pulvérisé avec une solution de chlorure d'ammonium, de chlorure de sodium et de chlorure de potassium; récupérer de manière séquentielle au moins deux métaux contenus dans le lixiviat par l'addition de zinc au moyen d'un processus de cémentation séquentiel; et récupérer le zinc contenu dans la solution par extraction par voie électrolytique.
PCT/US2013/036157 2013-04-11 2013-04-11 Système et procédé de récupération de métaux précieux à partir de laitiers WO2014168622A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/US2013/036157 WO2014168622A1 (fr) 2013-04-11 2013-04-11 Système et procédé de récupération de métaux précieux à partir de laitiers

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3273997A (en) * 1964-02-28 1966-09-20 Wilson Lab Inc Wet process for the separation, isolation, and recovery of certain metallic and non-metallic constituents of waste slag from reverberatory refining of copper pyritic type ores
GB1401615A (en) * 1971-07-16 1975-07-16 Int Nickel Canada Roorda h j extraction of non-ferrous metals from iron-containing materials
US4043804A (en) * 1976-06-16 1977-08-23 The Anaconda Company Recovery of metal values from copper reverberatory slag
EP0551155A1 (fr) * 1992-01-10 1993-07-14 B.U.S. ENGITEC SERVIZI AMBIENTALI S.r.l. Procédé pour récupérer le zinc et le plomb des poussières provenant d'aciéries électriques et pour recycler ces métaux purifiés vers le four, et installation pour la mise en oeuvre de ce procédé
US5433931A (en) * 1990-09-19 1995-07-18 Union Oil Company Of California Recovery of cerium
US6264903B1 (en) * 1999-06-22 2001-07-24 Allan S. Myerson Method for recycling industrial waste streams containing zinc compounds
US6783744B2 (en) * 1992-01-15 2004-08-31 Allan S Myerson Method for the purification of zinc oxide controlling particle size
US6863873B1 (en) * 1999-09-27 2005-03-08 Chester W. Whitman Process to produce simonkolleite, zinc oxide and zinc hydroxide
US20110182786A1 (en) * 2010-01-22 2011-07-28 Molycorp Minerals, Llc Hydrometallurgical process and method for recovering metals

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3273997A (en) * 1964-02-28 1966-09-20 Wilson Lab Inc Wet process for the separation, isolation, and recovery of certain metallic and non-metallic constituents of waste slag from reverberatory refining of copper pyritic type ores
GB1401615A (en) * 1971-07-16 1975-07-16 Int Nickel Canada Roorda h j extraction of non-ferrous metals from iron-containing materials
US4043804A (en) * 1976-06-16 1977-08-23 The Anaconda Company Recovery of metal values from copper reverberatory slag
US5433931A (en) * 1990-09-19 1995-07-18 Union Oil Company Of California Recovery of cerium
EP0551155A1 (fr) * 1992-01-10 1993-07-14 B.U.S. ENGITEC SERVIZI AMBIENTALI S.r.l. Procédé pour récupérer le zinc et le plomb des poussières provenant d'aciéries électriques et pour recycler ces métaux purifiés vers le four, et installation pour la mise en oeuvre de ce procédé
US6783744B2 (en) * 1992-01-15 2004-08-31 Allan S Myerson Method for the purification of zinc oxide controlling particle size
US6264903B1 (en) * 1999-06-22 2001-07-24 Allan S. Myerson Method for recycling industrial waste streams containing zinc compounds
US6863873B1 (en) * 1999-09-27 2005-03-08 Chester W. Whitman Process to produce simonkolleite, zinc oxide and zinc hydroxide
US20110182786A1 (en) * 2010-01-22 2011-07-28 Molycorp Minerals, Llc Hydrometallurgical process and method for recovering metals

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