[go: up one dir, main page]

US20180282837A1 - Method for extracting metals from concentrated sulphurated minerals containing metals by direct reduction with regeneration and recycling of the reducing agent, iron, and of the flux, sodium carbonate - Google Patents

Method for extracting metals from concentrated sulphurated minerals containing metals by direct reduction with regeneration and recycling of the reducing agent, iron, and of the flux, sodium carbonate Download PDF

Info

Publication number
US20180282837A1
US20180282837A1 US15/768,630 US201615768630A US2018282837A1 US 20180282837 A1 US20180282837 A1 US 20180282837A1 US 201615768630 A US201615768630 A US 201615768630A US 2018282837 A1 US2018282837 A1 US 2018282837A1
Authority
US
United States
Prior art keywords
ferrous
iron
metals
flux
reducing agent
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.)
Abandoned
Application number
US15/768,630
Other languages
English (en)
Inventor
Francisco Javier CÁRDENAS ARBIETO
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of US20180282837A1 publication Critical patent/US20180282837A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C01B17/24—Preparation by reduction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/04—Ferrous oxide [FeO]
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B15/00—Other processes for the manufacture of iron from iron compounds
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets
    • 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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry 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
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/023—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
    • 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
    • C22B13/02—Obtaining lead by dry 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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—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
    • C22B15/00—Obtaining copper
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/001—Preliminary treatment with modification of the copper constituent
    • C22B15/0021—Preliminary treatment with modification of the copper constituent by reducing in gaseous or solid state
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/0052—Reduction smelting or converting
    • 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
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • 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
    • C22B23/02—Obtaining nickel or cobalt by dry 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • 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
    • C22B34/34—Obtaining molybdenum
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • 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
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2200/00—Recycling of non-gaseous waste material
    • 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
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • 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
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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 relevant to apply the developed invention is mining and metallurgy, since it allows extracting ferrous and non-ferrous metals from sulphurated minerals bearing them by applying an improved direct reduction process, with no emissions of sulphur dioxide and without producing slag, which is commonly produced by conventional pyrometallurgical plants, thus minimizing environmental pollution.
  • the proposed regeneration and recycling of iron as reducing agent and sodium carbonate as flux the operating costs of the process are substantially reduced.
  • coal or metallurgical coke and/or carbon monoxide and/or hydrogen gas and/or natural gas are required as reducing agents; limestone and dolomite are required as alkaline fluxes, where, at the same time as the main process occurs, the reduction of other elements takes place in the same reactor, elements such as silicon, titanium, manganese, chromium, vanadium, among others, always from its oxidized compounds.
  • elements such as silicon, titanium, manganese, chromium, vanadium, among others, always from its oxidized compounds.
  • the presence of hydrogen gas in the percentage composition of reducing gases should correspond to a range between 20% and 35%, which can be achieved if natural gas is used in a complementary manner, with a reaction to water vapor at high temperatures of:
  • coal gas by-product of blast-furnace coke furnaces contains hydrogen sulphide gas, which is one of the components that should be removed before its usage.
  • An alternative is to pass the hydrogen sulphide gas through a mass of hydrated iron oxide to obtain the following reaction (5):
  • the technological innovation developed allows extracting, in addition to iron, metals such as, but not limited to, lead, silver, zinc, copper, molybdenum, antimony, arsenic, with or without associated iron, and with gold that could be hosted as inclusion in certain cases, from sulphurated minerals containing them.
  • metals such as, but not limited to, lead, silver, zinc, copper, molybdenum, antimony, arsenic, with or without associated iron, and with gold that could be hosted as inclusion in certain cases, from sulphurated minerals containing them.
  • an improved direct reduction process is applied to the metals to be extracted, which is achieved without sulphur dioxide emissions nor producing slags commonly generated by conventional pyrometallurgical plants, thus minimizing environmental pollution.
  • the proposed regeneration and recycling of iron as reducing agent and sodium carbonate as flux the operating costs of the process are substantially reduced.
  • This technology can be also applied to the remediation of tailings deposits containing various ferrous and non-ferrous metal sulphides.
  • metallic sulphides with commercial value, such as argentiferous galena: PbS bearing Ag, chalcopyrite: CuFeS 2 bearing Au, and sphalerite: ZnS, leaving great amounts of iron sulphides in the tailings, such as pyrite, pyrrhotite, and arsenopyrite, which are depressed in flotation cells together with non-metallic minerals extracted from mine, mainly quartz (SiO 2 ) and other silicates, which are stockpiled in tailings deposits under inadequate conditions in most cases. This is one of the main reasons the abovementioned tailings deposits are very likely to generate pollutants such as arsenical and acidic water in rainy seasons, due to the high amount of arsenic and iron sulphides they contain.
  • the concentrated sulphurated minerals, bearing the metal or metals to be extracted are smelted, as the case may be.
  • iron is used as reducing agent and sodium carbonate as flux, resulting in smelted or powdered metal or metals, depending on their physical properties, a slag of controlled composition formed by ferrous oxide and sodium sulphide, and gaseous emissions of carbon dioxide.
  • general reactions are established for the cases below, considering the following general definitions:
  • FIG. 1 Metallurgical Extraction Process
  • FIG. 2 Dissolving and Filtering Slag Components
  • FIG. 3 Regeneration of Sodium Carbonate for Recycling
  • FIG. 4 Removal of Hydrogen sulphide Gas and extraction of elemental Sulphur
  • FIG. 5 Sintering:
  • FIG. 6 Generation of Reducing Gases
  • FIG. 7 Regeneration of Iron as Reducing Agent for Recycling
  • FIG. 8 Comprehensive Process for Extracting Ferrous and Non-Ferrous Metals, and Gold as an Inclusion where Applicable, Through the Smelting of Concentrated Sulphurated Minerals Bearing them, with the Regeneration and Recycling of Metallurgical Inputs
  • the present invention includes a new technological process of seven stages, which are schematized in detail in the following diagrams.
  • the amount of flux that must be added to the reactor should be appropriate so that Ferrous Sulphide (FeS) does not appear in the slag.
  • FeS Ferrous Sulphide
  • the reaction begins to occur from 1100° C., and should preferably be completed at 1350° C.
  • the number of moles of Sodium Carbonate (Na 2 CO 3 ), or its equivalent in weight, which must be considered as a reactant flux in the aforementioned process, is also directly related to the amount of Sulphur atoms existing in the chemical formula of Chalcopyrite or other copper-containing sulphurated minerals such as Chalcocite, Bornite, Enargite, Carrotite and Tenantite, according to the corresponding chemical reactions specified that follow:
  • the extraction of the lead metal from the Galena (PbS), or from the sulphurated mineral that contains it, is based on the appropriate use of both Iron (Fe) as a reducing agent as well as Sodium Carbonate (Na 2 CO 3 ) as flux, and the products of the chemical reaction that occurs between the aforementioned reactants are the following: Cast metal lead, a slag formed by Ferrous Oxide (FeO) and Sodium Sulphide (Na 2 S), and gaseous emissions of Carbon Dioxide (CO 2 ).
  • the chemical formula established for the Galena or Lead Sulphide is used: PbS, a sulphurated mineral from which metal lead is to be extracted.
  • PbS a sulphurated mineral from which metal lead is to be extracted.
  • the slag obtained from the metal lead extraction in smelting furnace only consists of the insoluble compound Ferrous Oxide (FeO) and the water-soluble compound Sodium Sulphide (Na 2 S), which requires full control of the formation of Ferrous Sulphide (FeS) in the slag, and can be achieved if the main reaction of the direct reduction process using Iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux is the following:
  • the aforementioned reaction begins to occur at 950° C. and should preferably be completed by 1400° C.
  • the aforementioned reaction begins to occur at 775° C. and should preferably be completed by 1425° C.
  • Galena PbS
  • Ag 2 S sulphide Silver minerals
  • the number of gram-atoms of Iron (Fe), or its equivalent in weight, that will need to be considered as a reactive reducing agent in the process is directly related to the number of gram-moles of Ferrous Oxide (FeO) that will be obtained and, as it depends on the number of gram-moles of Oxygen (O 2 ) released as such in the chemical reaction, it is inferred that the required amount of gram-atoms of Iron (Fe) atoms will depend on the number of moles of Sodium Carbonate (Na 2 CO 3 ) considered as a flux and also on the number of Sulphur atoms (S) contained in the Galena or Lead Sulphide (PbS).
  • FeO Ferrous Oxide
  • S Sulphur atoms
  • Zinc and Silver Extraction by Smelting Concentrated Sulphurated Minerals of Zinc, Such as Sphalerite, and Silver, Such as Acanthite, Alone or Associated:
  • the extraction of Zinc metal from the Sphalerite (ZnS) or the sulphurated mineral that contains is done by applying the improved direct reduction process, which is based on the proper use of both Iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, and the products of the chemical reaction between the reactants are the following: metal gaseous Zinc (later liquefied by condensation), a light and fluid slag formed by Ferrous Oxide (FeO) and Sodium Sulphide (Na 2 S), and gaseous emissions of Carbon Dioxide (CO 2 ). Given its importance, it is also necessary to have an effective control during the formation of the slag during the direct reduction process.
  • the improved direct reduction process which is based on the proper use of both Iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, and the products of the chemical reaction between the reactants are the following: metal gaseous Zinc (later liquefied
  • the Iron (Fe) is added as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, specifying that the use of these metallurgical inputs must be done in stoichiometric proportions, so that the regeneration and recycling of both the reducing agent and the flux is possible from the products obtained from the chemical reaction.
  • the slag is mainly formed not by three or more compounds, but only by two, and one of them should be soluble in Water.
  • the slag obtained from the metal Zinc extraction in the smelting furnace consists only of the insoluble compound Ferrous Oxide (FeO) and the water-soluble compound Sodium Sulphide (Na 2 S), which implies full control of the non-formation of Ferrous Sulphide (FeS) in the slag, for which it is necessary that the chemical reaction of the process complies with the following:
  • the reaction begins at 1000° C. and is preferably completed at 1850° C.
  • Silver when presented in association with the zinc sulphides in the form of Acanthite or Ag 2 S, contributes one more Sulphur (S) atom to the reactants, which will affect the quantities required from the reducing agent Iron and the flux Sodium Carbonate. According to chemical thermodynamics, the reaction begins at 950° C. and should preferably be completed at 1150° C.
  • the number of gram-atoms of Iron (Fe), or its equivalent in weight, which must be considered as a reactive reducing agent in the process is directly related to the number of gram-moles of Ferrous Oxide (FeO) obtained as a product and, as it depends on the number of gram-moles of Oxygen (O 2 ) released as such in the chemical reaction, it is inferred that the required gram-atoms of Iron (Fe) will depend on the number of moles of Sodium Carbonate (Na 2 CO 3 ) considered as a flux and also on the number of Sulphur atoms (S) contained in the Sphalerite (ZnS).
  • FeO Ferrous Oxide
  • S Sulphur atoms
  • the extraction of Gold (Au), Silver (Ag) and Iron (Fe) contained in the sulphurated minerals of the latter such as Pyrite (FeS 2 ), Pyrrhotite (FeS), Marcasite (FeS 2 ), is carried out by applying the improved direct reduction, using the Sodium Carbonate flux in an appropriate way and the Iron in a complementary way as a facilitator of the atomic exchange, which depends on the mineralogical species.
  • the iron content in these is sufficient to cause the chemical reactions between the reactants that allow the extraction of Gold and Silver.
  • the metal Lead the same one that is added to the smelting furnace together with the reactants, is obtained as a cast metal product carrying the metals Gold and Silver, which are also cast.
  • the iron sulphide concentrate smelting as in the case of the gold pyrites, which is introduced in the furnace together with the additional Iron (Fe) required and the indispensable Sodium Carbonate (Na 2 CO 3 ) as a flux, is made considering the appropriate stoichiometric amounts of these metallurgical inputs, not only to obtain the maximum recoveries of Gold and Silver, but also to meet the need to have a controlled composition of the slag to be produced, so that the regeneration and recycling of both the reducing agent Iron (Fe) and the flux of Sodium Carbonate (Na 2 CO 3 ) is possible in the subsequent processes.
  • the temperature range in which the reaction preferentially occurs is between 775° C.-950° C.
  • the above chemical reaction is merely an example, since it is known that the mineralogical species contained in Silver appear in much lower quantities (Ounces/Ton) than the percentage amounts contained in Pyrite.
  • Silver is associated with iron sulphides in the form of Acanthite Ag 2 S (Argentite above 177° C.) and, therefore, contributes one more atom of Sulphur (S) to the reactants, which will affect the quantities required of the reducing agent Iron and the flux Sodium Carbonate.
  • S Sulphur
  • the amount of flux that must be added to the reactor must be correct so that Ferrous Sulphide does not form in the slag (FeS).
  • the temperature range in which the reaction preferentially occurs is between 750° C.-950° C.
  • the gold extraction process from gold pyrite or Iron disulphide (FeS 2 ) is characterized by, on the one hand, the number of gram-atoms of iron (Fe), or its equivalent in weight, which will need to be considered as a reactive reducing agent in the process, is directly related to the number of atoms of Sulphur (S) contained in the Pyrite or Iron disulphide (FeS 2 ), exceptionally the gram-atoms of Iron or its equivalent in weight that are contained in the gold pyrite must be deducted in this calculation.
  • the number of moles of Sodium Carbonate (Na 2 CO 3 ), or its equivalent in weight, that should be considered as a reactant flux in the Gold extraction process is also directly related to the amount of existing Sulphur atoms in the chemical formula of Pyrite or Iron Disulphide (FeS 2 ).
  • the extraction of the Antimony metal from the sulphurated mineral that contains it is done by applying the direct reduction improved with regeneration and recycling of the metallurgical inputs involved, which is based on the proper use of both Iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, and the products of the chemical reaction between the reagents are the following: metal Antimony, a slag formed mainly by the insoluble compound Ferrous Oxide (FeO) and by the water-soluble compound Sodium Sulphide (Na 2 S), and, gaseous emissions formed mainly by Carbon Dioxide (CO 2 ).
  • FeO Ferrous Oxide
  • Na 2 S water-soluble compound Sodium Sulphide
  • CO 2 Carbon Dioxide
  • the concentrated minerals Stibnite or Antimony Trisulphide (Sb 2 S 3 ), which is a sulphurated mineral extracted from metal Antimony, should be inside the smelting furnace. Then, the reducing agent Iron (Fe) and the flux Sodium Carbonate (Na 2 CO 3 ) are added to the reactor in stoichiometric proportions that allow the regeneration and recycling of the mentioned metallurgical inputs in the subsequent processes; for such purpose, the formation of the slag should be controlled, taking care that the latter is constituted not by three or more compounds, but only by two, and one of them should be soluble in Water.
  • the slag obtained from the smelting furnace during the metallic antimony extraction is only composed of Ferrous Oxide (FeO) and Sodium Sulphide (Na 2 S), which implies that the formation of Ferrous Sulphide (FeS) in the slag must be controlled, for which it is necessary for the reaction of the direct reduction process using Iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux to be the following:
  • chemical thermodynamics state that the reaction begins at 300° C. and should preferably be completed at 625° C.
  • the number of gram-atoms of iron (Fe), or its equivalent in weight, which will need to be considered as a reactive reducing agent in the process, is directly related to the number of gram-moles of Ferrous Oxide (FeO) to be obtained as product and, since it depends on the number of gram-moles of Oxygen (O 2 ) released as such in the chemical reaction, it is concluded that the required gram-atoms of Iron (Fe) atoms will depend on the number of moles of Sodium Carbonate (Na 2 CO 3 ) considered as a flux and also on the number of Sulphur atoms (S) contained in the concentrated mineral of Stibnite or Antimony Trisulphide (Sb 2 S 3 ).
  • the extraction of molybdenum metal from the sulphurated mineral that contains it is carried out by applying the improved direct reduction process, which is based on the appropriate use of both iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, and the products of the chemical reaction between the reactants are the following: Powdered metallic molybdenum due to its high smelting point, a light and fluid slag formed by Ferrous Oxide (FeO) and Sodium Sulphide (Na 2 S), and gaseous emissions of Carbon Dioxide (CO 2 ).
  • the improved direct reduction process which is based on the appropriate use of both iron (Fe) as a reducing agent and Sodium Carbonate (Na 2 CO 3 ) as a flux, and the products of the chemical reaction between the reactants are the following: Powdered metallic molybdenum due to its high smelting point, a light and fluid slag formed by Ferrous Oxide (FeO) and Sodium Sulph
  • the slag obtained from the molybdenum metal extraction in the smelting furnace is only composed of the insoluble compound Ferrous Oxide (FeO) and the water-soluble compound Sodium Sulphide (Na 2 S), which implies that the non-formation of Ferrous Sulphide (FeS) in the slag must be controlled at the same time, for which the following chemical reaction is necessary in the main process:
  • reaction begins at 1175° C. and should preferably be completed at 1375° C.
  • the number of gram-atoms of Iron (Fe), or its equivalent in weight, which will need to be considered as a reactive reducing agent in the process is directly related to the number of gram-moles of Ferrous Oxide (FeO) that will be obtained as a product and, since it depends on the number of gram-moles of Oxygen (O 2 ) released as such in the chemical reaction, it is inferred that the required gram-atoms of Iron (Fe) will depend on the number of moles of Sodium Carbonate (Na 2 CO 3 ) considered as flux, and also on the number of Sulphur atoms (S) contained in the concentrated mineral Molybdenite or Molybdenite Bisulphide (MoS 2 ).
  • the previous reaction begins at 825° C., and the reaction must be completed preferably at 1325° C., considering reasonable energy costs.
  • the previous reaction begins at 770° C., and the reaction must be completed preferably at 900° C.
  • the above reaction begins at 875° C., and it must be completed preferably at 975° C. considering reasonable energy costs. It must have been verified that it is possible to extract all the Arsenic contained in the aforementioned gold Arsenopyrite concentrate at the most appropriate stoichiometric conditions and at a temperature of 1000° C.
  • the metal Lead As an additional reactant in the previous reactions, so that it can be at the end the carrier of the Gold in the products of the reaction, not only because of the affinity that exists between the two metals, but also because, together with Lead and Gold, they form a cast metal product of high specific weight, which is easily separated from the slag constituted by sodium sulphide and ferrous oxide in order to obtain a proper casting.
  • iron sulphurated minerals such as Fe 2 S in the case of Pyrites, specifying that the smelting of one gram-mole of Pyrite with a gram-atom of Iron (Fe) and one gram of the Sodium Carbonate (Na 2 CO 3 ) flux must be made considering the appropriate stoichiometric quantities in order to fully control the composition of the slag to be produced, so that the reduction and recycling of both the sodium carbonate (Na 2 CO 3 ) and the iron (Fe) flux that should be added, in the case of having iron disulphides as reactant, is possible in the subsequent processes.
  • the above reaction occurs at 750° C., and should preferably be completed at 950° C., considering reasonable energy costs.
  • the control over the composition of the slag allows to take advantage of the high solubility of Sodium Sulphide (Na 2 S) in Water (H 2 O) and, for the purposes of having the Ferrous Oxide (FeO) compound as the only solid residue, it is indispensable that the slag, which is obtained in the smelting furnace for iron sulphide concentrates, is mixed in the Solution reactor with the amount of liquid water necessary, considering the solubility of Sodium Sulphide (Na 2 S), so that the following electrochemical dissociation reaction occurs:
  • the resulting solution is filtered, and only solid waste formed by Ferrous Oxide (FeO) is separated.
  • the agglomeration and subsequent sintering of the solid waste is carried out in the respective furnace, at a controlled temperature, so that the agglomerated Ferrous Oxide (FeO) products, appropriately sintered and converted into “pellets”, acquire the mechanical property of compressive resistance required inside the Iron Reduction Furnace, where the FeO “pellets” will be finally sent.
  • the sintered “pellets” are introduced and accumulated in the Iron Reduction Furnace in order to be subjected, for the necessary period, to the appropriate flow of the Carbon Monoxide (CO) and Hydrogen (H 2 ) reducing gases from the combustion furnace, which causes the oxidation state +2 of Iron to be reduced to zero, thus making possible the extraction of metal iron (Fe) using the following chemical reactions:
  • Sulphides the number of gram-atoms of iron (Fe), or its equivalent in weight, which will have to be considered as a reactant in the process, is directly related to the number of atoms of sulphur (S) contained in Pyrite and/or Marcasite (FeS 2 ), with the exception that the gram-atoms of Iron, or its equivalent in weight, that are contained in the Pyrite and/or Marcasite to be cast must be deducted in this calculation.
  • the number of moles of Sodium Carbonate (Na 2 CO 3 ), or its equivalent in weight, which must be considered as a reactant flux in the Iron extraction process is also directly related to the amount of Sulphur atoms existing in the chemical formula of Pyrite and/or Marcasite (Iron Bisulphides: FeS 2 ). It is specified that, in the case that the cast of one mole gram of Pirotite (FeS) is desired, only one mole gram of sodium carbonate will be required as a flux. It is necessary to consider the previous indications so as to have control over the composition of the slag, which must be composed of Ferrous Oxide (FeO) and Sodium Sulphide (Na 2 S).
  • FeO Ferrous Oxide
  • Na 2 S Sodium Sulphide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Processing Of Solid Wastes (AREA)
US15/768,630 2015-10-16 2016-08-15 Method for extracting metals from concentrated sulphurated minerals containing metals by direct reduction with regeneration and recycling of the reducing agent, iron, and of the flux, sodium carbonate Abandoned US20180282837A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PE002185-2015/DIN 2015-10-16
PE2015002185A PE20170608A1 (es) 2015-10-16 2015-10-16 Proceso para extraer metales a partir de sus minerales sulfurados mediante reduccion directa con regeneracion y reciclaje del agente reductor hierro y del fundente carbonato de sodio
PCT/PE2016/000014 WO2017065622A1 (es) 2015-10-16 2016-08-15 Proceso para extraer metales a partir de los concentrados de minerales sulfurados que los contienen aplicando reducción directa con regeneración y reciclaje del agente reductor hierro y del fundente carbonato de sodio

Publications (1)

Publication Number Publication Date
US20180282837A1 true US20180282837A1 (en) 2018-10-04

Family

ID=58518224

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/768,630 Abandoned US20180282837A1 (en) 2015-10-16 2016-08-15 Method for extracting metals from concentrated sulphurated minerals containing metals by direct reduction with regeneration and recycling of the reducing agent, iron, and of the flux, sodium carbonate

Country Status (17)

Country Link
US (1) US20180282837A1 (ru)
EP (1) EP3363918A4 (ru)
JP (1) JP6896713B2 (ru)
KR (1) KR20180069012A (ru)
CN (1) CN108350523A (ru)
AR (1) AR106224A1 (ru)
AU (1) AU2016339723A1 (ru)
BR (1) BR112018007360B1 (ru)
CA (1) CA3000805A1 (ru)
CL (1) CL2017001257A1 (ru)
CO (1) CO2017004902A2 (ru)
EC (1) ECSP17031013A (ru)
MX (1) MX2017007017A (ru)
PE (1) PE20170608A1 (ru)
RU (1) RU2768798C2 (ru)
WO (1) WO2017065622A1 (ru)
ZA (1) ZA201803064B (ru)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111809058A (zh) * 2019-04-10 2020-10-23 中国瑞林工程技术股份有限公司 一步挥发还原处理冶炼尾渣的方法
CN112609092A (zh) * 2020-12-29 2021-04-06 云南驰宏锌锗股份有限公司 一种从砷酸钙/亚砷酸钙沉淀物中综合回收钙、砷的方法
CN112725629A (zh) * 2020-12-30 2021-04-30 北京光明橡塑制品厂 一种从钢渣中提炼有色金属及还原铁的制备方法
CN114941078A (zh) * 2022-06-06 2022-08-26 国投金城冶金有限责任公司 一种含锑金精矿碱法浸锑时抑制金浸出的方法
CN116855731A (zh) * 2023-06-29 2023-10-10 鞍钢股份有限公司 一种稳定烧结矿氧化亚铁含量的调整方法
WO2024243519A3 (en) * 2023-05-24 2025-04-24 The Trustees Of Columbia University In The City Of New York Systems and methods to remove waste contaminants from ore concentrates

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102326860B1 (ko) * 2019-09-04 2021-11-16 주식회사 포스코 몰드 플럭스 및 주조 방법
CN112831665A (zh) * 2020-12-31 2021-05-25 山东金创金银冶炼有限公司 一种高硒高银烟道灰处理工艺
CN113201654A (zh) * 2021-04-29 2021-08-03 江西金德铅业股份有限公司 一种铜浮渣反射炉冶炼新工艺法
CN114150156B (zh) * 2021-11-30 2023-10-13 西安建筑科技大学 一种低品位含锌粉尘提锌以及纳米氧化锌制备工艺
CN114917932B (zh) * 2022-05-12 2023-05-09 浙江师范大学 一种用于co2光还原合成co和h2的催化剂、制备方法及应用
CN114920245B (zh) * 2022-07-04 2023-10-03 重庆大学 一种用于二氧化碳封存的矿化物及其应用
CN115558794B (zh) * 2022-10-31 2023-11-28 西安建筑科技大学 一种利用红土镍矿酸浸渣从退役三元催化剂中富集贵金属的方法
CN116976737A (zh) * 2023-08-02 2023-10-31 大湾区科技创新服务中心(广州)有限公司 企业科创能力的评价方法、系统及计算机可读存储介质
WO2025120065A1 (en) * 2023-12-06 2025-06-12 Umicore Sulfur injection in lead slags

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA442713A (en) * 1947-07-08 American Smelting And Refining Company Process of treating tin sulphide concentrates
US4101314A (en) * 1976-04-08 1978-07-18 The Curators Of The University Of Missouri Process for recovery of lead from lead sulfide concentrates
LU75732A1 (ru) * 1976-09-06 1978-04-27
US4164416A (en) * 1976-12-20 1979-08-14 Rockwell International Corporation Metal recovery process
US5443614A (en) * 1994-07-28 1995-08-22 Noranda, Inc. Direct smelting or zinc concentrates and residues
RU2154117C2 (ru) * 1998-02-25 2000-08-10 Сидоренко Юрий Александрович Способ извлечения металлов платиновой группы из концентратов на основе сульфидов железа
RU2156820C1 (ru) * 1999-03-29 2000-09-27 Акционерное общество "Иргиредмет" Способ переработки концентратов гравитационного обогащения, содержащих благородные металлы
CN1215184C (zh) * 2000-02-22 2005-08-17 中南工业大学 有色金属硫化矿及含硫物料的还原造锍冶炼方法
RU2194781C2 (ru) * 2000-11-28 2002-12-20 Московский государственный институт стали и сплавов (технологический университет) Способ переработки сырья, содержащего цветные металлы и железо
RU2219264C2 (ru) * 2002-03-11 2003-12-20 Открытое акционерное общество "Иргиредмет" Способ переработки концентратов, содержащих цветные и благородные металлы
GB0313886D0 (en) * 2003-06-16 2003-07-23 Jha Animesh Extraction route for Ti02 and alumina from bauxite and bauxitic residues,and titaniferrous deposits and wastes
CN101143290B (zh) * 2006-09-13 2010-04-21 宝山钢铁股份有限公司 一种常温氧化铁脱硫剂、其制备方法及应用
CN101323905B (zh) * 2007-06-15 2010-07-21 西安华英实业有限公司 铜铅锌混合精矿的火法冶金工艺
CN102557300B (zh) * 2012-01-13 2013-10-16 宁波中一石化科技有限公司 一种用于液化气碱渣脱硫及中和的装置及处理方法
CN104498731B (zh) * 2014-12-04 2016-08-24 扬州市华翔有色金属有限公司 一种富氧侧吹低温碱性固硫熔炼的方法及设备
CN105400963B (zh) * 2015-11-18 2017-05-31 金川集团股份有限公司 一种复杂金精矿直接还原‑熔分高效富集贵金属的方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111809058A (zh) * 2019-04-10 2020-10-23 中国瑞林工程技术股份有限公司 一步挥发还原处理冶炼尾渣的方法
CN112609092A (zh) * 2020-12-29 2021-04-06 云南驰宏锌锗股份有限公司 一种从砷酸钙/亚砷酸钙沉淀物中综合回收钙、砷的方法
CN112725629A (zh) * 2020-12-30 2021-04-30 北京光明橡塑制品厂 一种从钢渣中提炼有色金属及还原铁的制备方法
CN114941078A (zh) * 2022-06-06 2022-08-26 国投金城冶金有限责任公司 一种含锑金精矿碱法浸锑时抑制金浸出的方法
WO2024243519A3 (en) * 2023-05-24 2025-04-24 The Trustees Of Columbia University In The City Of New York Systems and methods to remove waste contaminants from ore concentrates
CN116855731A (zh) * 2023-06-29 2023-10-10 鞍钢股份有限公司 一种稳定烧结矿氧化亚铁含量的调整方法

Also Published As

Publication number Publication date
BR112018007360B1 (pt) 2021-11-23
CO2017004902A2 (es) 2017-10-10
RU2768798C2 (ru) 2022-03-24
WO2017065622A9 (es) 2017-06-15
JP2018532047A (ja) 2018-11-01
WO2017065622A1 (es) 2017-04-20
CL2017001257A1 (es) 2018-01-05
CN108350523A (zh) 2018-07-31
RU2018112130A3 (ru) 2019-10-07
RU2018112130A (ru) 2019-10-07
CA3000805A1 (en) 2017-04-20
ZA201803064B (en) 2019-01-30
PE20170608A1 (es) 2017-05-24
ECSP17031013A (es) 2018-04-30
BR112018007360A2 (pt) 2018-10-23
AR106224A1 (es) 2017-12-27
EP3363918A1 (en) 2018-08-22
KR20180069012A (ko) 2018-06-22
JP6896713B2 (ja) 2021-06-30
EP3363918A4 (en) 2019-06-12
AU2016339723A1 (en) 2018-04-19
MX2017007017A (es) 2017-11-07

Similar Documents

Publication Publication Date Title
US20180282837A1 (en) Method for extracting metals from concentrated sulphurated minerals containing metals by direct reduction with regeneration and recycling of the reducing agent, iron, and of the flux, sodium carbonate
US6770249B1 (en) Process to selectively recover metals from waste dusts, sludges and ores
Habashi Copper metallurgy at the crossroads
US20250084503A1 (en) Treatment of zinc leach residue
CN111118303A (zh) 一种氧压浸出锌冶炼固废渣制备次氧化锌的方法
WO1998036102A1 (en) Refining zinc sulphide ores
Shamsuddin et al. Constitutive Topics in Physical Chemistry of High-Temperature Nonferrous Metallurgy-A Review: Part 1. Sulfide Roasting and Smelting
JP2023503237A (ja) 改善された銅製錬方法
CN110777264A (zh) 一种适用于各种类型复杂金精矿独立冶炼的方法
US5372630A (en) Direct sulphidization fuming of zinc
CN106756059B (zh) 一种从含砷烟尘回收有价金属及沉淀转化法合成固砷矿物的方法
AU2004257842B2 (en) Method for smelting copper concentrates
KR101113631B1 (ko) 정광의 제조방법
WO2014022946A1 (es) Procedimiento para procesar polvos de fundición mediante acido tricarboxílico
CN102618730B (zh) 含铟铅银铜铋物料的分离工艺
CN101932739A (zh) 镍的生产
Tan Challenges to Treat Complex Zinc Concentrate and Latest Technical Development
Hara et al. Carbothermic processing of copper–cobalt mineral sulphide concentrates and slag waste for the extraction of metallic values
Hovestadt et al. Hydrogen reduction of entrapped metal oxides from fayalitic copper slags
US134457A (en) Improvement in reducing lead ores and collecting precious metals
WO2025120190A1 (en) Treatment of lead slags
Копылов et al. PROCESSING OF SOLID ARSENIC-CONTAINING MATERIALS (analytical review)
Atzeni Aspects of ancient metallurgy
WANG et al. A review of arsenic reaction behavior in copper smelting process and its disposal techniques
Taylor The development of an alternative process for the recovery of lead from sulphide ores

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

STCC Information on status: application revival

Free format text: WITHDRAWN ABANDONMENT, AWAITING EXAMINER ACTION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE