WO2019175838A1 - Régulation du fer dans des solutions de traitement contenant du cuivre et du zinc - Google Patents

Régulation du fer dans des solutions de traitement contenant du cuivre et du zinc Download PDF

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Publication number
WO2019175838A1
WO2019175838A1 PCT/IB2019/052099 IB2019052099W WO2019175838A1 WO 2019175838 A1 WO2019175838 A1 WO 2019175838A1 IB 2019052099 W IB2019052099 W IB 2019052099W WO 2019175838 A1 WO2019175838 A1 WO 2019175838A1
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WO
WIPO (PCT)
Prior art keywords
solution
iron
hydromet
copper
zinc
Prior art date
Application number
PCT/IB2019/052099
Other languages
English (en)
Inventor
David J. Chaiko
Frank Baczek
Original Assignee
Flsmidth A/S
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 Flsmidth A/S filed Critical Flsmidth A/S
Publication of WO2019175838A1 publication Critical patent/WO2019175838A1/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
    • C22B3/20—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
    • 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

  • Embodiments of the invention relate to hydrometallurgical processing and more particularly, to novel iron control techniques and methods for selectively removing iron from hydromet solutions.
  • Prior art iron control processes involve the synthesis of goethite to remove iron from solution via precipitation. Formation of goethite involves high temperatures (e.g., 80-100 °C) which cause metal value losses and increase overall operating expenditures (OPEX).
  • high temperatures e.g. 80-100 °C
  • a process for controlling iron within a hydromet solution and/or removing iron from a hydromet solution containing a dissolved metal value is disclosed.
  • the process may comprise the step of seeding the hydromet solution with a seed precipitate material comprising iron. Seeding may be performed at a temperature less than 80 degrees Celsius, and preferably at a pH which is below 3.
  • the process may further comprise the step of precipitating iron out of the hydromet solution to form an iron precipitate and a substantially iron-free solution.
  • the process may further comprise the step of extracting a metal value from the substantially iron- free solution.
  • the metal value may be selected from copper, zinc, gold, silver, or a combination thereof, without limitation.
  • the seed precipitate material comprising iron may comprise a material selected from Fe 2 0 3 , basic iron sulfate, jarosite, goethite, and schwertmannite, without limitation.
  • the process may further comprise removing produced gypsum from the hydromet solution prior to the step of seeding the hydromet solution, without limitation.
  • at least 90% of the iron in the hydromet solution may be removed from the hydromet solution during the step of precipitating iron out of the hydromet solution, without limitation.
  • the hydromet solution may have a residence time of less than
  • the hydromet solution may comprise a copper and zinc pregnant leach solution; wherein and virtually no co-absorption of copper and zinc may occur during the process.
  • iron removed from the hydromet solution may comprise iron produced by leaching an iron- containing metal sulfide, such as FeS 2 or CuFeS 2 , without limitation.
  • FIG. 1 suggests an iron control/removal process according to some non-limiting embodiments.
  • FIG. 2 schematically illustrates preferred residence times of a hydromet solution during iron precipitation/removal steps discussed herein.
  • FIG. 3 schematically illustrates a non-limiting system or flowsheet which may be used to perform embodiments of the process disclosed herein.
  • FIGS. 4 and 5 schematically illustrate where embodiments may be employed within a leach circuit.
  • embodiments of a process for removing iron from hydromet solutions and/or for controlling iron buildup within a hydromet solution which can take place during the leaching of a metal sulfide.
  • Some embodiments involve iron control and/or selective removal of iron from hydromet solutions which contain copper and/or zinc. It is envisaged that described embodiments may work equally well for pregnant leach solutions comprising other target metal values including, but not limited to, silver and/or gold.
  • Embodiments of the process may involve the step of controlling the pH level of the hydromet solution by adding a base or acid over time.
  • Preferred pH values are below 3.0, for example, at or around 2.5, without limitation.
  • the process may further involve the step of controlling temperature by heating or cooling the hydromet solution as needed, for example, using a jacketed reactor or a reactor equipped with a thermocouple and a controllable heating element, heat exchanger, or the like, without limitation.
  • the process may involve the step of controlling temperature of the hydromet solution to be less than what is traditionally used to form goethite in conventional iron control processes (e.g., 80-100 degrees Celsius). More preferably, temperature of the hydromet solution may be controlled to be less than 80 degrees Celsius, but greater than 20 degrees Celsius.
  • the process may involve the step of controlling temperature of the hydromet solution to be within the range of between 30 °C and 70 °C, and more preferably, between approximately 40 °C and 60 °C, without limitation.
  • the hydromet solution may be maintained at approximately 45 degrees Celsius or 50 degrees Celsius, without limitation.
  • Temperatures higher than 80 degrees Celsius which are used in prior art goethite and jarosite precipitation processes may lead to co-absorption of metal values in solution (e.g., copper, zinc, and Ag), and may lead to losses thereof during downstream recovery.
  • a gypsum separation stage may be advantageously included prior to a final Cu precipitation step, prior to a final Zn precipitation step, or prior to the iron precipitation via seeding, without limitation.
  • the process may further comprise adding a particulate seed comprising iron as an Fe(III) oxide or an Fe(III) sulfate to the hydromet solution.
  • the particulate seed may comprise Fe Ch, without limitation.
  • the particulate seed may comprise basic iron sulfate (Fe(0H)S0 4 ), without limitation.
  • the particulate seed may comprise jarosite (MeFe 1+ 3 (0H) 6 (S0 4 ) 2 ), without limitation, wherein Me is known to be a +1 charged cation such as Na + or K + .
  • the particulate seed may comprise hematite (Fe 3 0 4 ), without limitation.
  • the hematite may be provided from iron ore, hematite concentrate, and/or autoclave leach residue comprising hematite, without limitation.
  • the particulate seed may comprise goethite (FeOOH), without limitation.
  • the particulate seed may comprise schwertmannite (FesOsiOFI SiT -nFbO; or, Fe 3+ 16 0 16 ( O H , S O 4 ) 12- 13 ⁇ 10- 12 H 2 O ) , without limitation.
  • the particulate seed may comprise a combination of two or more of the following, without limitation: Fe 2 0 3 , basic iron sulfate, jarosite, hematite, goethite, schwertmannite.
  • the inventors have discovered that the rate of Fe(III) precipitation may be a key determining factor in producing either goethite or schwertmannite as the precipitated iron product. Slow precipitation for Fe(III) seems to give goethite. Fast precipitation seems to yield setmannite.
  • the process may facilitate
  • the iron removal steps e.g., seeding a hydromet solution, precipitating an iron product from the hydromet solution, and filtering the hydromet solution to remove iron solids therefrom
  • a residence time window which is less than 1/2 hour to avoid substantial losses of target metals from solution.
  • a shorter window or slightly larger window may be expected.
  • the step of precipitating iron from a hydromet solution is performed within a residence time window that is less than about 15 minutes, or less than about 20 minutes, or less than about 25 minutes, or less than about 35 minutes, or less than about 40 minutes, without limitation.
  • the iron control/removal process discussed herein may be able to handle ferric concentrations which are well-above established limitations of methods involving conventional iron removal via the formation of goethite.
  • embodiments of the iron control/removal process discussed herein may be used with hydromet solutions which contain soluble iron levels exceeding 1 gram per liter. The inventors unexpectedly were able to demonstrate that with embodiments of the present invention, seeding solutions having above 1 g/L iron therein still results in goethite precipitation - even though literature evidences the complete contrary - i.e., that ferric concentrations must be less than 1 g/L iron.
  • embodiments of the iron control/removal process discussed herein may be used in conjunction with many different types of hydromet solutions including those which contain metal values such as copper (Cu), zinc (Zn), silver (Ag), gold (Au), or a combination thereof, if present.
  • process condition changes may be made in order to form an iron precipitate that is easily filterable (e.g., for example, using an industrial filter such as a horizontal filter press or equivalent, without limitation).
  • iron precipitate formed using embodiments of the invention may come in various forms and/or mineral phases, depending on process conditions used.
  • a hydromet solution may comprise a pregnant leach solution (PLS) formed using acid, such as (preferably) sulfuric acid.
  • PLS pregnant leach solution
  • acid such as (preferably) sulfuric acid.
  • a leach can be performed in other acids, such as hydrochloric acid, the inventors do not believe that a chloride series of iron precipitates may be present when practicing the herein-described steps. If hydrochloric acid is used to leach a metal sulfide, embodiments of the iron removal process might produce sulfate that would then allow the formation of iron sulfate phases, without limitation.
  • a base e.g., limestone, lime, calcium carbonate, calcium hydroxide, or the like
  • the gypsum may be precipitated and filtered out of the hydromet solution, without limitation. Since gypsum is a solubility product between calcium and sulfate that is dependent on concentrations of calcium sulfate and temperature, actual pH values of the gypsum formation/precipitation steps may vary depending on solution composition and other process control variables.
  • the pH of the hydromet solution can be raised again to the point where iron hydrolyses and precipitates (e.g., at a pH between approximately 2 and 2.5). Slightly higher pH values are anticipated; however, they are not recommended since pH values greater than 2.5 substantially increase the risk of losing other transition metals which may be present in the hydromet solution (e.g., copper and/or zinc metal values).
  • the aforementioned sequential process steps aim and generally serve to remove a bulk of the gypsum from the iron product; however, some gypsum may be present in the latter-precipitated iron product.
  • adsorption becomes significant and prohibitive if the residence time of the Cu/Zn PLS hydromet solution within a precipitation tank exceeds 30 minutes during iron removal.
  • preferred embodiments employ an iron precipitation step wherein a hydromet solution residence time is no greater than about a half hour during seeding and iron sulfate precipitation. It is anticipated that the limiting residence time will be a function of the process temperature, i.e., the higher the temperature the shorter the residence time needs to be in order to minimize co-precipitation of metal values.
  • process chemistry may involve maintaining pH within the range of 2.0 - 2.5, at a temperature of approximately 50°C, without limitation.
  • process chemistry involving neutralization of sulfuric acid e.g., pH adjustment to a maximum of 2.5
  • process chemistry involving ferrous iron oxidation may be done using H2O2 via the following chemistry: 2Fe 2+ + H2O2 + 40H 2FeOOH + 23 ⁇ 40, without limitation.
  • process chemistry may involve Fe(II) Oxidation and FeOOH precipitation according to the following chemistry:
  • process chemistry may involve adjusting the hydromet solution pH to 0.9 with CaC0 3 , without limitation.
  • process chemistry may involve adding FeOOH seed at rate of 1 gram per g Fe to be removed from the hydromet solution, without limitation.
  • process chemistry may involve adding H2O2 to oxidize remaining Fe(II) to Fe(III), without limitation.
  • process chemistry may involve adding limestone slurry to the hydromet solution, as needed, to maintain the hydromet solution at a pH of approximately 2.0, without limitation.
  • process chemistry may involve increasing the pH of the hydromet solution to 2.5 using CaC0 3 , without limitation.
  • process chemistry may involve FeOOH precipitation for 1 hr.
  • Fe and Cu precipitation rates may be determined through periodic sampling of reactor liquor, without limitation.
  • process chemistry may involve an operating temperature (50°C) and pH (1-2.5) during the precipitation process, wherein the iron product reports as goethite instead of Fe(OH) 3 , without limitation.
  • process chemistry may involve copper and zinc remaining substantially un-hydrolyzed; wherein any incidental losses may be due to physical adsorption onto the goethite particles, without limitation.
  • the hydromet solution is a copper PLS
  • process chemistry may involve relatively slow Cu adsorption kinetics. In such cases, controlling residence times within the iron precipitation and removal process may become a very important factor affecting downstream copper recoveries from the copper PLS. For example, in some embodiments, it may be necessary that residence times which are less than approximately 30 minutes be used during iron precipitation/removal.
  • metal value losses in a hydromet solution may be minimal or negligible.
  • zinc loss due to precipitation and/or physical adsorption onto goethite may be minimal (i.e., ⁇ 0.5%) for a copper/zinc PLS, without limitation.
  • the particular iron to be removed from the hydromet solution is primarily Fe(III)
  • the reaction between H2O2 and Fe 2+ may be essentially stoichiometric (e.g., 90+% efficient).
  • hydromet solution may comprise any solution within a hydrometallurgical process, including, but not limited to, a“pregnant leach solution (PLS)”, “raffinate”,“lixivian’,“electrolyte”,“catalyst”,“additive”, or the like, without limitation.
  • PLS pregnant leach solution

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

Abstract

Cette invention concerne un procédé de régulation du fer à l'intérieur d'une solution d'hydrométallurgie et/ou d'élimination du fer à partir d'une solution d'hydrométallurgie contenant une valeur de métal dissous, comprenant les étapes consistant à amorcer la solution d'hydrométallurgie avec un matériau de précipité d'amorce comprenant du fer. L'amorçage se produit de préférence à une température inférieure à 80 degrés Celsius, et à un pH qui est inférieur à 3 (par exemple, 2,5). Le procédé implique la précipitation de produits de fer hors de la solution d'hydrométallurgie et la formation d'une solution sensiblement exempte de fer. Des valeurs de métaux peuvent être extraites de la solution sensiblement exempte de fer à des pourcentages de récupération élevés.
PCT/IB2019/052099 2018-03-14 2019-03-14 Régulation du fer dans des solutions de traitement contenant du cuivre et du zinc WO2019175838A1 (fr)

Applications Claiming Priority (2)

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US201862642960P 2018-03-14 2018-03-14
US62/642,960 2018-03-14

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985857A (en) * 1972-10-20 1976-10-12 Asturiana De Zinc, S.A. Process for recovering zinc from ferrites
WO2009003240A1 (fr) * 2007-07-03 2009-01-08 Commonwealth Scientific And Industrial Research Organisation Lixiviation maîtrisée du fer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985857A (en) * 1972-10-20 1976-10-12 Asturiana De Zinc, S.A. Process for recovering zinc from ferrites
WO2009003240A1 (fr) * 2007-07-03 2009-01-08 Commonwealth Scientific And Industrial Research Organisation Lixiviation maîtrisée du fer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CLAASSEN J O ET AL: "Particle growth parameters in the precipitation of metastable iron phases from zinc-rich solutions", HYDROMETALLURGY, ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, NL, vol. 84, no. 3-4, 1 November 2006 (2006-11-01), pages 165 - 174, XP027884180, ISSN: 0304-386X, [retrieved on 20061101] *
MASAMBI SAVIOUR ET AL: "Comparing iron phosphate and hematite precipitation processes for iron removal from chloride leach solutions", MINERALS ENGINEERING, PERGAMON PRESS , OXFORD, GB, vol. 98, 12 July 2016 (2016-07-12), pages 14 - 21, XP029747760, ISSN: 0892-6875, DOI: 10.1016/J.MINENG.2016.07.001 *

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