WO1984004759A1 - Extraction of metals from ores - Google Patents

Extraction of metals from ores Download PDF

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Publication number
WO1984004759A1
WO1984004759A1 PCT/AU1984/000094 AU8400094W WO8404759A1 WO 1984004759 A1 WO1984004759 A1 WO 1984004759A1 AU 8400094 W AU8400094 W AU 8400094W WO 8404759 A1 WO8404759 A1 WO 8404759A1
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WO
WIPO (PCT)
Prior art keywords
ore
metal fluorides
fluorides
cobalt
oxides
Prior art date
Application number
PCT/AU1984/000094
Other languages
French (fr)
Inventor
Robert Lloyd
Maxwell James Turner
Original Assignee
Oabrand Pty Ltd
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 Oabrand Pty Ltd filed Critical Oabrand Pty Ltd
Priority to BR8406916A priority Critical patent/BR8406916A/en
Publication of WO1984004759A1 publication Critical patent/WO1984004759A1/en
Priority to FI850334A priority patent/FI850334A0/en
Priority to DK37185A priority patent/DK37185A/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • C22B1/10Roasting processes in fluidised form
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/19Fluorine; Hydrogen fluoride
    • C01B7/191Hydrogen fluoride
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/06Halides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00Compounds of cobalt
    • C01G51/08Halides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/08Halides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/02Roasting processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/0423Halogenated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10Hydrochloric acid, other halogenated acids or salts thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • This invention relates to a method for. the extraction of metals from ores, and particularly to the recovery of nickel, cobalt and other associated minerals from various nickel and/or cobalt ores, in which they occur either singly or together.
  • the invention provides a process for the extraction of metals from ores, such as nickel, cobalt and associated minerals from ore which contains the nickel, cobalt and associated minerals as oxides or sulfides, which comprises contacting the ore with hydrogen fluoride, and/or with fluorosilicic acid to convert at least some of the metals such as nickel, cobalt and associated mineral oxides or sulfides to fluorides, and then separating and collecting the resulting metal fluorides.
  • the method of the present invention can be applied to a variety of different types of ores.
  • the present invention is applicable to a wide range of metal oxides such as nickel, copper, chromium, magnesium, silver, tin, and titanium.
  • the present process can be used with other minerals as well, provided they exist in a form in which acid action can transform the oxide (err sulfide) to a fluoride.
  • the process of the present invention may also be applied to ores where the metals occur as oxides or sulfides. Despite this however, in some ores the sulfides exist in a complex ore body, closely aggregated with iron or carbon, which can interfere in the transformation of the sulfides to the fluorides. Despite this however, some sulfide ores can be treated effectively using the present method.
  • Preferred types of ores with which the present extraction method can be used are the nickel-cobalt Lateritic ores which occur in large quantities in Australia and throughout the world. These Lateritic ores are considered to be untreatable by prior art processes for both economic and technical reasons.
  • a typical Laterite ore would have the following analysis: Analysis (by Weight)
  • the laterite contains 0.2% to 1.2% Co O or similar cobalt oxide and 1% to 2.5% NiO and 1% to 3% Mn 2 O 3 and 0.5% to 1.5% Cr 2 O 3
  • Figure 1 shows a flowchart detailing the extraction process using hydrogen fluoride and optionally fluorosilicic acid for hydrogen fluoride makeup.
  • Figure 2 shows a flowchart for an alternate embodiment of the invention, detailing the extraction process using fluorosilicic acid.
  • MODE(S) OF CARRYING OUT THE INVENTION The present invention is now described with reference to a preferred embodiment concerning recovering nickel, cobalt and associated minerals from the lateritic one described above.
  • a plant for carrying out the method of the invention can be designed and constructed in the usual manner.
  • the plant is constructed of mild steel and lined with heat transferring materials for temperatures under 150°C.
  • Such a material could be teflon ABS, carbon block, or natural hard rubber. All lines, valves, pipes, etc are lined with these materials which are unaffected by reagents at temperatures of 150°C. All other vessels and tubes where temperature is less than 150°C can be lined with polypropylene or polyethylene.
  • a preferred method according to the invention using HF gas is now described.
  • the ore is reduced in size to below 3/8 of an inch particle size by conventional means. These reduced particles are then dried to about 0.5% moisture. Both crushing and drying are preferably undertaken in order to reduce costs in the process. Crushed, dried ore is fed into the primary reaction chamber where a constant temperature of 105 C is maintained and which is at slightly above ambient pressure.
  • the design of the vessel is such that an even temperature distribution is achieved.
  • the ore is fluidised by the passage of HF gas counter current to the movement of the ore.
  • the gas reacts immediately on contact with all of the oxides other than iron (which it pacifies).
  • the other minerals react with the HF gas.
  • These metal fluorides have properties which differ slightly from each other. This allows for separation at a later stage.
  • Silica, (SiO 2 ) is a major constituent of the ore.
  • the SiO 2 structure will be attacked violently by the HF gas in an exothermic reaction forming SiF 4 . This vigorous reaction assists in separating the
  • SiF 4 out of the iron structure The silicon tetrafluoride and the HF both readily attack Al 2 O 3 and the other metal oxides causing the total conversion of the oxides to fluorides and at the same time so permeates the iron structure that most oxides are released from the iron structure, which itself does not react.
  • the oxygen liberated from the metal oxides combines with the hydrogen liberated from the HF gas forming water vapour, which under these conditions does not combine with the SiF 4 .
  • the SiF 4 is a gas and it travels with the gas stream of excess HF along with the water vapour which is produced in the process.
  • Exhaust from the reaction chamber will contain a small excess of HF but predominantly comprises water vapour and SiF 4 in stoichiometric amounts.
  • the water vapour would probably be slightly above the stoichiometric requirements according to the amount of residue moisture in the raw feed material.
  • the stream of SiF 4 , water vapour and minimum HF at 105°C is cooled so that the water condenses.
  • the condensed water will solubilise a small amount of HF and combine with the SiF 4 . to form H 2 SiF 6 , or fluorosilicic acid.
  • the reacted ore passing from the reaction chamber is free of silica. Substantially all the oxides other than the pacified iron oxide are converted to fluorides. A second vessel is then used to solubilise the reacted ores.
  • the liquid in this vessel is 15% to 20% HF in an aqueous solution. This is passed counter current through the ore body at slightly above ambient pressure and at a temperature at which none of the HF is evaporated out of the stream.
  • the metal fluorides which will be easily solubilised in this tank are primarily AlF 3 , NiF 2 , CoF 2 , CuF 2 ,
  • the Al 2 O 3 neutralizes the remaining HF to AlF. and water. This solution then passes to a crystallising tank in which AlF 3 is crystallised.
  • the other metal fluorides contained in the liquor are obtained by boiling off the water in a separate vessel leaving the residue of valuable metal fluorides. These are then taken for further treatment.
  • the rejected solids from the solubilising tank are mainly Fe 2 O 3 and MgF 2 and CaF 2 . These are passed to a second solubilizing vessel where the structure is washed in a weak solution of hydrochloric acid. This operation is strictly controlled to ensure the minimum reaction between HC1 and the iron structure thus maximising the amount of MgF 2 and CaF 2 solubilised.
  • the leach liquor stream is then taken to a separate vessel where the water is boiled off along with the excess HC1.
  • the residual solids are predominantly MgF 2 and CaF 2 plus some iron fluorides. These are then passed to a vessel to be reacted with H 2 SO 4 in order to regenerate HF.
  • the Fe 2 O 3 is now of high iron purity but will contain some residue of HC1. This can be removed by washing. The iron is then of commercial value.
  • the ore is reduced in size to below 3/8 of an inch maximum particle size and the moisture is reduced to .5% by conventional methods.
  • the main reason for preferably crushing and drying is to reduce costs in the process.
  • the ore is fed into the reaction vessel where a temperature of 70°C is maintained, at slightly above ambient pressure.
  • the ore is placed in a counter current flow of 20% to 22% H 2 SiF 6 (i.e. fluorosilicic acid).
  • the silica contained in this ore will not react and will remain in the structure. If the iron structure is very porous and these pores are blocked by the silica then the fluorosilicic acid cannot contact the complete structure and will, of course, convert less of the available metal oxides to fluorides. In ores where this becomes a problem, some aqueous HF can be added to the fluorosilicic acid stream.
  • the percentage of aqeous HF to be added is dependent on three factors: (1) The level of recovery required.
  • the H 2 SiF 6 on leaving the primary reaction vessel will contain excess H 2 SiF 6 plus, AlF 3 , NiF 2 , CoF 2 , CaF 2 , CrF 2 and H 2 O.
  • This stream passes into a stirred reaction vessel.
  • This then has Al 2 O 3 added to it, (which can come from a stage later in the process).
  • the aluminium will neutralize the acid, forming AlF 3 and silica and some H 2 O.
  • the silica will be released in this tank and can be removed separately to the liquor.
  • the liquor from this tank will then be passed to a crystalliser to form AlF. crystals.
  • Liquid which does not precipitate as aluminium fluoride crystals will pass on to a distillation vessel for the recovery of metal fluorides. HF and H 2 O can be recovered from this vessel.
  • the AlF crystals formed in the crystalliser pass on to a pyrohydrolization process where HF and H 2 O are boiled off and may be recovered, and Al 2 O 3 is formed. This can be used in the process and may be of high enough quality to be saleable.
  • the solid ore which passes through the main reaction vessel contains Fe 2 O 3 , CaF 2 , and MgF 2 and some SiO 2 which is trapped in the pores of the iron.
  • the iron because of the silica content, will be of less commercial value. This process is represented in the flowchart in Figure 2.
  • HF gas can be added to the reaction stage as make up for loss out of the system, or aqueous HF can be added to the solubility stage as make up.
  • fluorosilicic acid can be added to the silica recovery circuit after the removal of the SiO 2 formed by the condensing of the gases from the reactor. This is indicated in Figure 1.
  • the fluorine in the fluorosilicic acid can be returned to the start as gas, or condensed and returned in aqueous form to the solubilising tanks.

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

Abstract

Metals are extracted from ores which exist in the form of oxides or sulphides, by treating the ore with hydrogen fluoride and/or fluorosilicic acid. There are two preferred forms. When hydrogen fluoride is used, the ore is initially crushed, dried and then contacted with HF gas at temperatures above 105oC to produce metal fluorides. The metal fluorides are then contacted with aqueous HF solution and the resulting insoluble metal fluorides and iron oxides are separated from the solution, and metal fluorides preferably including nickel and cobalt fluorides are recovered. When fluorosilicic acid is used, the crushed and dried ore is directly contacted with an aqueous solution of fluorosilicic acid at temperatures above 70oC and the resulting insoluble metal fluorides and iron oxides are separated and metal fluorides preferably including nickel and cobalt fluorides are recovered. Preferred ores are cobalt-nickel lateritic ores.

Description

"EXTRACTION OF METALS FROM ORES" TECHNICAL FIELD This invention relates to a method for. the extraction of metals from ores, and particularly to the recovery of nickel, cobalt and other associated minerals from various nickel and/or cobalt ores, in which they occur either singly or together.
BACKGROUND ART Most of the nickel and cobalt in the world today has come from ores in which the metals are found as sulfides. Sulfide ores make up about 2/3 of the world's deposit of these metals. In the other 1/3 of the world's deposit, these metals are found as oxides, and to date, there has been little development of methods for the recovery of nickel or cobalt from oxide ores. In addition, it has been found uneconomical to extract nickel and cobalt from low grade ores, either sulfide or oxide ores.
It is an object of the present invention to provide a method of extracting metals from ores containing the metals as oxides or sulfides. It is a further object of the present invention to provide a method of extracting nickel, cobalt and other associated minerals from ores in which they are found as oxides or sulfides.
DISCLOSURE OF INVENTION The invention provides a process for the extraction of metals from ores, such as nickel, cobalt and associated minerals from ore which contains the nickel, cobalt and associated minerals as oxides or sulfides, which comprises contacting the ore with hydrogen fluoride, and/or with fluorosilicic acid to convert at least some of the metals such as nickel, cobalt and associated mineral oxides or sulfides to fluorides, and then separating and collecting the resulting metal fluorides.
The method of the present invention can be applied to a variety of different types of ores. For example, the present invention is applicable to a wide range of metal oxides such as nickel, copper, chromium, magnesium, silver, tin, and titanium. The present process can be used with other minerals as well, provided they exist in a form in which acid action can transform the oxide (err sulfide) to a fluoride. The process of the present invention may also be applied to ores where the metals occur as oxides or sulfides. Despite this however, in some ores the sulfides exist in a complex ore body, closely aggregated with iron or carbon, which can interfere in the transformation of the sulfides to the fluorides. Despite this however, some sulfide ores can be treated effectively using the present method.
Preferred types of ores with which the present extraction method can be used are the nickel-cobalt Lateritic ores which occur in large quantities in Australia and throughout the world. These Lateritic ores are considered to be untreatable by prior art processes for both economic and technical reasons.
A typical Laterite ore would have the following analysis: Analysis (by Weight)
40 - 50 % Fe2O3
16 - 35 % SiO2
8 - 25 % Al2O3
5 - 25 % MgO Normally under 1 % CaO and Na2O
The laterite contains 0.2% to 1.2% Co O or similar cobalt oxide and 1% to 2.5% NiO and 1% to 3% Mn2O3 and 0.5% to 1.5% Cr2O3
BRIEF DESCRIPTION OF DRAWINGS The present invention is now discussed with reference to the drawings in which:
Figure 1 shows a flowchart detailing the extraction process using hydrogen fluoride and optionally fluorosilicic acid for hydrogen fluoride makeup. Figure 2 shows a flowchart for an alternate embodiment of the invention, detailing the extraction process using fluorosilicic acid. MODE(S) OF CARRYING OUT THE INVENTION The present invention is now described with reference to a preferred embodiment concerning recovering nickel, cobalt and associated minerals from the lateritic one described above.
One embodiment of the process of the invention utilizing hydrogen fluoride is now discussed, as represented in the flowchart shown in Figure 1.
A plant for carrying out the method of the invention can be designed and constructed in the usual manner. The plant is constructed of mild steel and lined with heat transferring materials for temperatures under 150°C. Such a material could be teflon ABS, carbon block, or natural hard rubber. All lines, valves, pipes, etc are lined with these materials which are unaffected by reagents at temperatures of 150°C. All other vessels and tubes where temperature is less than 150°C can be lined with polypropylene or polyethylene.
A preferred method according to the invention using HF gas is now described. The ore is reduced in size to below 3/8 of an inch particle size by conventional means. These reduced particles are then dried to about 0.5% moisture. Both crushing and drying are preferably undertaken in order to reduce costs in the process. Crushed, dried ore is fed into the primary reaction chamber where a constant temperature of 105 C is maintained and which is at slightly above ambient pressure.
The design of the vessel is such that an even temperature distribution is achieved. Inside the chamber the ore is fluidised by the passage of HF gas counter current to the movement of the ore. The gas reacts immediately on contact with all of the oxides other than iron (which it pacifies). The other minerals react with the HF gas. These metal fluorides have properties which differ slightly from each other. This allows for separation at a later stage. Silica, (SiO2) is a major constituent of the ore. The SiO2 structure will be attacked violently by the HF gas in an exothermic reaction forming SiF4. This vigorous reaction assists in separating the
SiF4 out of the iron structure. The silicon tetrafluoride and the HF both readily attack Al2O3 and the other metal oxides causing the total conversion of the oxides to fluorides and at the same time so permeates the iron structure that most oxides are released from the iron structure, which itself does not react.
As the chemical reactions are exothermic and occur in a body of ore which is maintained at a temperature in excess of 105°C and just above ambient pressure, the oxygen liberated from the metal oxides combines with the hydrogen liberated from the HF gas forming water vapour, which under these conditions does not combine with the SiF4. The SiF4 is a gas and it travels with the gas stream of excess HF along with the water vapour which is produced in the process.
It is possible to vary the quantity of HF gas introduced to the reaction chamber so that almost all the HF is converted to water vapour or SiF4 prior to reaching the outlet of the reaction chamber so that there is minimum of excess HF.
Exhaust from the reaction chamber will contain a small excess of HF but predominantly comprises water vapour and SiF4 in stoichiometric amounts. The water vapour would probably be slightly above the stoichiometric requirements according to the amount of residue moisture in the raw feed material.
The stream of SiF4, water vapour and minimum HF at 105°C is cooled so that the water condenses. The condensed water will solubilise a small amount of HF and combine with the SiF4. to form H2SiF6, or fluorosilicic acid.
At this stage about one third of the silica, less the amount which has reacted with excess HF in the solution to form fluorosilicic acid, will be precipitated. This silica is removed physically and the fluorosilicic acid is piped to a re-boiler where it is brokendown, and HF and silica are recovered.
The reacted ore passing from the reaction chamber is free of silica. Substantially all the oxides other than the pacified iron oxide are converted to fluorides. A second vessel is then used to solubilise the reacted ores.
The liquid in this vessel is 15% to 20% HF in an aqueous solution. This is passed counter current through the ore body at slightly above ambient pressure and at a temperature at which none of the HF is evaporated out of the stream.
The metal fluorides which will be easily solubilised in this tank are primarily AlF3, NiF2, CoF2, CuF2,
CrF2, and MnF2 and various other trace metal fluorides. Two metal fluorides will remain inside the iron structure and will not be solubilised by the passage of HF. These are MgF2 and CaF2. The aqueous HF solution now containing the metal fluoride is taken to a stirred reaction chamber in which Al2O3 is added. (The Al2O3 can be obtained from a later stage in the process if this is desired.)
The Al2O3 neutralizes the remaining HF to AlF. and water. This solution then passes to a crystallising tank in which AlF3 is crystallised. The other metal fluorides contained in the liquor are obtained by boiling off the water in a separate vessel leaving the residue of valuable metal fluorides. These are then taken for further treatment. The rejected solids from the solubilising tank are mainly Fe2O3 and MgF2 and CaF2. These are passed to a second solubilizing vessel where the structure is washed in a weak solution of hydrochloric acid. This operation is strictly controlled to ensure the minimum reaction between HC1 and the iron structure thus maximising the amount of MgF2 and CaF2 solubilised.
The leach liquor stream is then taken to a separate vessel where the water is boiled off along with the excess HC1. The residual solids are predominantly MgF2 and CaF2 plus some iron fluorides. These are then passed to a vessel to be reacted with H2SO4 in order to regenerate HF.
The Fe2O3 is now of high iron purity but will contain some residue of HC1. This can be removed by washing. The iron is then of commercial value.
Another embodiment of the invention using fluorosilicic acid is now discussed, as represented in the flow chart shown in Figure 2. The plant for this second process method would be constructed using mild steel with linings of polypropylene or polyethylene.
The ore is reduced in size to below 3/8 of an inch maximum particle size and the moisture is reduced to .5% by conventional methods. The main reason for preferably crushing and drying is to reduce costs in the process. The ore is fed into the reaction vessel where a temperature of 70°C is maintained, at slightly above ambient pressure. The ore is placed in a counter current flow of 20% to 22% H2SiF6 (i.e. fluorosilicic acid).
The silica contained in this ore will not react and will remain in the structure. If the iron structure is very porous and these pores are blocked by the silica then the fluorosilicic acid cannot contact the complete structure and will, of course, convert less of the available metal oxides to fluorides. In ores where this becomes a problem, some aqueous HF can be added to the fluorosilicic acid stream.
The percentage of aqeous HF to be added is dependent on three factors: (1) The level of recovery required.
(2) The amount of silica in the structure in comparison to the other elements.
(3) The physical porosity of the iron structure.
The H2SiF6 on leaving the primary reaction vessel will contain excess H2SiF6 plus, AlF3, NiF2, CoF2, CaF2, CrF2 and H2O.
This stream passes into a stirred reaction vessel. This then has Al2O3 added to it, (which can come from a stage later in the process). The aluminium will neutralize the acid, forming AlF3 and silica and some H2O. The silica will be released in this tank and can be removed separately to the liquor. The liquor from this tank will then be passed to a crystalliser to form AlF. crystals. Liquid which does not precipitate as aluminium fluoride crystals will pass on to a distillation vessel for the recovery of metal fluorides. HF and H2O can be recovered from this vessel. The AlF crystals formed in the crystalliser pass on to a pyrohydrolization process where HF and H2O are boiled off and may be recovered, and Al2O3 is formed. This can be used in the process and may be of high enough quality to be saleable. The solid ore which passes through the main reaction vessel contains Fe2O3, CaF2, and MgF2 and some SiO2 which is trapped in the pores of the iron. The iron, because of the silica content, will be of less commercial value. This process is represented in the flowchart in Figure 2.
One of the problems in the past of using HF for the reduction of minerals has been the cost of HF and the disposal of HF mineral residues. In this invention the HF used is converted at the end of the process to metal fluorides such as MnF2, CuF2, MgF2 and Ni F2.
These can be pyrohydrolized thereby converting them to oxides and regenerating the HF as a gas or liquid which is then returned to the reaction or solubility stages as make up, or used in any other way. As further options, and as represented in Figure 1, in the first of the two preferred processs described above the HF gas can be added to the reaction stage as make up for loss out of the system, or aqueous HF can be added to the solubility stage as make up. However, make up with fluorosilicic acid is a further preferred option to both these options. Fluorosilicic acid can be added to the silica recovery circuit after the removal of the SiO2 formed by the condensing of the gases from the reactor. This is indicated in Figure 1.
The fluorine in the fluorosilicic acid can be returned to the start as gas, or condensed and returned in aqueous form to the solubilising tanks.

Claims

1. A process for the extraction of metals from ores containing metals in the form of oxides or sulfides comprising the steps of contacting the ore with hydrogen fluoride and/or fluorosilicic acid to convert the metal oxides or sulfides to metal fluorides, and separating and collecting the metal fluoridies.
2. The process as defined in claim 1 wherein nickel, cobalt and associated minerals are extracted from ore containing the nickel, cobalt and associated minerals as oxides or sulfides, and also containing iron oxides and silica.
3. The process as defined in claim 2 which comprises the steps of:
(a) crushing and substantially drying the ore,
(b) contacting the ore with HF gas in a reactor at a temperature above about 105°C to produce metal fluorides, and gaseous products comprising SiF4 and water,
(c) removing the gaseous products and treating them using conventional methods to recover HF gas and silica and recycling the HF gas to the process,
(d) contacting the metal fluorides from step (b) with aqueous HF solution, and separating insoluble metal fluorides and iron oxides from the resulting solution, and
(e) recovering the metal fluorides, including nickel and cobalt fluorides, from the resulting solution.
4. The process as defined in claim 3 wherein alumina is added to the resulting solution from step (d) to neutralize dissolved HF to form AlF3, separating and treating the AlF using conventional methods to recover HF gas which is recycled to the process, and then proceeding with step (e).
5. The process as defined in claim 3 wherein the aqueous HF solution in step (d) is at a concentration of 15% to 20%.
6. The process as defined in claim 3 wherein fluorosilicic acid is added to the process as makeup.
7. The process as defined in claim 2 which comprises the steps of:
(a) crushing and substantially drying the ore,
(b) contacting the ore with an aqueous solution of fluorosilicic acid at a temperature above about 70°C,
(c) separating insoluble products including iron oxides, silica and insoluble metal fluorides from the resulting solution, and
(d) recovering metal fluorides, including nickel and cobalt fluorides, from the resulting solution.
8. The process as defined in claim 7 wherein alumina is added to the solution from step (σ) to neutralize dissolved HF to form AlF3 and precipitating silica which is separated, crystallizing the AlF3 from the resulting solution, separating and treating the AlF3 using conventional methods to recover HF gas, and then proceeding with step (d).
9. The process as defined in claim 7 wherein the concentration of fluorosilicic acid in step (b), is about 20% to 26%.
10. The process as defined in claim 7 wherein hydrogen fluoride is added with the fluorosilicic acid in step (b).
11. The process as defined in claim 1 or claim 3 or claim 7 wherein the metal fluorides produced are treated using conventional methods to convert them to metal oxides and to recover hydrogen fluoride.
12. The process as defined in claim 2 wherein the ore is nickel-cobalt Lateritic ore.
PCT/AU1984/000094 1983-05-25 1984-05-25 Extraction of metals from ores WO1984004759A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR8406916A BR8406916A (en) 1983-05-25 1984-05-25 EXTRACTION OF METALS FROM ORES
FI850334A FI850334A0 (en) 1983-05-25 1985-01-25 FOERFARANDE FOER EXTRAHERING AV METALLER UR MALM.
DK37185A DK37185A (en) 1983-05-25 1985-01-25 PROCEDURE FOR THE EXTRACT OF METAL FROM ORE.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
AUPF952883 1983-05-25

Publications (1)

Publication Number Publication Date
WO1984004759A1 true WO1984004759A1 (en) 1984-12-06

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PCT/AU1984/000094 WO1984004759A1 (en) 1983-05-25 1984-05-25 Extraction of metals from ores

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EP (1) EP0145728A4 (en)
JP (1) JPS60501508A (en)
BR (1) BR8406916A (en)
DK (1) DK37185A (en)
FI (1) FI850334A0 (en)
WO (1) WO1984004759A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1987002068A1 (en) * 1985-09-27 1987-04-09 Extramet Method for separation and recovery of metals from mixtures of metal sulfides such as lead ores
US4753033A (en) * 1985-03-24 1988-06-28 Williams Technologies, Inc. Process for producing a clean hydrocarbon fuel from high calcium coal
WO1990002823A1 (en) * 1988-09-06 1990-03-22 Institut National De Recherche Chimique Appliquee IMPROVED PROCESS FOR OBTAINING IMPURITY-FREE COMPOUNDS OF Ta AND/OR Nb FROM MATERIALS CONTAINING THESE METALS
WO2004057043A1 (en) * 2002-12-20 2004-07-08 Advortech Holdings Pty Ltd Process for purifying inorganic materials

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US1380458A (en) * 1920-05-25 1921-06-07 Charles W Woodruff Process for purifying graphite and carbon
AU1191943A (en) * 1943-11-18 1945-08-02 Pilkington Brothers Limited Improvements in or relating to processes for reducing iron impurities inground calcite, dolomite, magnesite or cryolite
GB1085504A (en) * 1965-01-06 1967-10-04 Western Titanium N L Improvements in or relating to the treatment of heavy mineral concentrates
FR2106518A1 (en) * 1970-09-14 1972-05-05 Mitsui Mining & Smelting Co Nickel recovery - using a halide and solid reducing agent roasting then flotating with sulphur dioxide
FR2253097A1 (en) * 1973-11-29 1975-06-27 Ferodo Sa Separating silicate minerals from ore - by hydrogen fluoride treatment followed by electrostatic treatment
SU572509A1 (en) * 1976-04-07 1977-09-15 Сибирский Государственный Проектный И Научно-Исследовательский Институт Цветной Металлргии Method of segregating roasting of ferrous materials
AU4566179A (en) * 1978-04-04 1979-10-11 Krofchak, D. Recovering metal valves from incinerated sewage sludge ash
EP0016624B1 (en) * 1979-03-16 1983-05-25 Kinneret Enterprises Limited Coal de-ashing process

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FR819874A (en) * 1936-12-08 1937-10-28 Manufacturing process of salts and alloys
FR845666A (en) * 1937-11-24 1939-08-30 Seri Holding Process for extracting bases of rare elements contained in ores or rocks
GB1066016A (en) * 1962-12-24 1967-04-19 Roche George Bousquet L Recovery of tantalum, niobium and titanium from low grade sources
US3607013A (en) * 1969-02-10 1971-09-21 Fmc Corp Production of nickel fluoride
AU8223375A (en) * 1974-06-21 1976-12-23 Univ Melbourne Benefication of titaniferous ores
NZ181123A (en) * 1975-06-30 1979-12-11 Univ Melbourne Treatment of mineralcontaining materials with an acid in the presence of fluoride ion

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1380458A (en) * 1920-05-25 1921-06-07 Charles W Woodruff Process for purifying graphite and carbon
AU1191943A (en) * 1943-11-18 1945-08-02 Pilkington Brothers Limited Improvements in or relating to processes for reducing iron impurities inground calcite, dolomite, magnesite or cryolite
GB1085504A (en) * 1965-01-06 1967-10-04 Western Titanium N L Improvements in or relating to the treatment of heavy mineral concentrates
FR2106518A1 (en) * 1970-09-14 1972-05-05 Mitsui Mining & Smelting Co Nickel recovery - using a halide and solid reducing agent roasting then flotating with sulphur dioxide
FR2253097A1 (en) * 1973-11-29 1975-06-27 Ferodo Sa Separating silicate minerals from ore - by hydrogen fluoride treatment followed by electrostatic treatment
SU572509A1 (en) * 1976-04-07 1977-09-15 Сибирский Государственный Проектный И Научно-Исследовательский Институт Цветной Металлргии Method of segregating roasting of ferrous materials
AU4566179A (en) * 1978-04-04 1979-10-11 Krofchak, D. Recovering metal valves from incinerated sewage sludge ash
EP0016624B1 (en) * 1979-03-16 1983-05-25 Kinneret Enterprises Limited Coal de-ashing process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0145728A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4753033A (en) * 1985-03-24 1988-06-28 Williams Technologies, Inc. Process for producing a clean hydrocarbon fuel from high calcium coal
WO1987002068A1 (en) * 1985-09-27 1987-04-09 Extramet Method for separation and recovery of metals from mixtures of metal sulfides such as lead ores
WO1990002823A1 (en) * 1988-09-06 1990-03-22 Institut National De Recherche Chimique Appliquee IMPROVED PROCESS FOR OBTAINING IMPURITY-FREE COMPOUNDS OF Ta AND/OR Nb FROM MATERIALS CONTAINING THESE METALS
FR2636939A1 (en) * 1988-09-06 1990-03-30 Inst Nat Rech Chimique IMPROVED PROCESS FOR OBTAINING TA AND / OR NB COMPOUNDS FREE OF IMPURITIES FROM MATERIALS CONTAINING THESE METALS
WO2004057043A1 (en) * 2002-12-20 2004-07-08 Advortech Holdings Pty Ltd Process for purifying inorganic materials

Also Published As

Publication number Publication date
FI850334L (en) 1985-01-25
DK37185A (en) 1985-03-25
DK37185D0 (en) 1985-01-25
EP0145728A4 (en) 1985-09-25
EP0145728A1 (en) 1985-06-26
BR8406916A (en) 1985-05-21
JPS60501508A (en) 1985-09-12
FI850334A0 (en) 1985-01-25

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