WO2011114000A1 - Method of processing nickel bearing raw material - Google Patents
Method of processing nickel bearing raw material Download PDFInfo
- Publication number
- WO2011114000A1 WO2011114000A1 PCT/FI2011/050222 FI2011050222W WO2011114000A1 WO 2011114000 A1 WO2011114000 A1 WO 2011114000A1 FI 2011050222 W FI2011050222 W FI 2011050222W WO 2011114000 A1 WO2011114000 A1 WO 2011114000A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- solution
- leaching
- chloride
- copper
- Prior art date
Links
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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- 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
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction 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
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a hydro metallurgical method of processing nickel containing raw material such as sulphidic nickel concentrate or sulphidic nickel ore where the raw material is leached in chloride-based leaching media in a process integrated with solvent extraction and electrowinning process stages for obtaining metallic nickel.
- the solvent extraction stage comprises a nickel solvent extraction stage, where nickel is extracted from an aqueous solution containing high concentration of chloride.
- nickel resources are divided into two major categories, sulphide ore and oxidized ore (laterite ore).
- the conventional exploitation of nickel sulphide ore essentially comprises a pyrometallurgical process step followed by hydrometallurgical process steps, where the ore is first finely ground, and then the nickel sulphide minerals are concentrated by froth flotation into a nickel concentrate.
- the concentrate is treated further by smelting and reduction to produce a nickel bearing matte, which also contains copper, cobalt, and iron.
- the matte is then refined by known hydrometallurgical processes, which might include oxidative leaching or pressure leaching, followed by impurity removal and hydrogen reduction or electrowinning.
- a drawback of the smelting process is the generation of sulphur dioxide, which has to be treated in an acid plant to produce sulphuric acid, a product that is not always easy to dispose of from the smelter location. Losses of nickel and cobalt into smelter slag are significant, and there can be problems in dealing with some of the minor elements in concentrates, such as magnesium and arsenic.
- the Activox process that is described for example in the EP patent 1 303 641 comprises the grinding of nickel concentrate into a very fine ground material, where after it is subjected to oxidative leaching at a high pressure for separating nickel into the sulphate solution, and subsequently impurities are removed by known methods, and metallic nickel is recovered.
- a drawback of the above described hydrometallurgical processes is that a large part of the sulphur contained in the sulphide is oxidized into sulphuric acid, which results in high expenses caused by neutralization reagents, and the creation of large waste quantities that must be removed, such as ammonium sulphate and gypsum. It can be estimated that the high expenses resulting from these two factors when combined make said processes commercially less attractive.
- the WO patent application 96/41029 "Chloride assisted hydrometallurgical extraction of nickel and cobalt from sulphide ores" describes oxidative pressure leaching of nickel and cobalt sulphide ores in the presence of oxygen and likewise an acidic leaching containing halide, copper and sulphate ions.
- the obtained solution is subjected to solids separation and solution purification, precipitation of the mixed nickel and cobalt hydroxide, re-leaching of the precipitate in an ammoniacal solution, where after the metals are separated by solvent extraction and recovered by electrowinning.
- the process suffers similar limitations as the sulphate-based hydrometallurgical processes described above.
- US patent 3,880,653 describes the recovery of metallic nickel from a nickel matte containing copper and precious metals.
- the leaching of the nickel matte is realized as a concurrent process, where the nickel matte is first suspended to a chloride solution obtained from nickel electrowinning and containing monovalent copper.
- the chloride solution is conducted to a leaching step, where also chlorine created in electrolysis is fed. Chlorine oxidizes the monovalent copper, which in turn dissolves the nickel and is at the same time reduced back to monovalent form and precipitated as copper sulphide.
- the sulphur contained in the dissolving sulphides is precipitated as element sulphur.
- the precious metals remain undissolved in the leaching.
- the whole batch of slurry is conducted to a second step, where the dissolved divalent copper is precipitated by means of nickel matte.
- the solution and the solid material are separated, and the solution is conducted to nickel electrowinning.
- JP patent application 10-140257 describes the recovery of nickel by means of chlorine leaching and electrolysis from materials, such as nickel matte, containing nickel, cobalt, copper and sulphur.
- Nickel matte is leached in concurrent leaching into a chloride solution that contains monovalent copper, and chlorine is supplied into the solution for leaching nickel and other metals.
- chlorine is supplied into the first steps of the leaching process, the sulphur contained in the nickel matte also is partly dissolved and forms sulphuric acid in the solution.
- the leaching is carried out by means of the oxygen contained in the air and sulphuric acid.
- the nickel chloride bearing solution is conducted to electrolysis for recovering the metallic nickel, and the chlorine created in the electrolysis is used for leaching the raw material. Also the recycled solution obtained from electrolysis is used for leaching the raw material.
- the latter two deal with nickel mattes that are produced by first processing the nickel concentrate pyrometallurgically.
- the large quantity of sulphur dioxide created in the process, which sulphur dioxide is generally processed further into sulphuric acid, can be regarded as a drawback in the pyrometallurgical treatment.
- the use and commercial marketing of sulphuric acid is difficult, particularly when the smelter location is far from the location where sulphuric acid should be used.
- WO publication WO2007/039665 discloses a method of producing a nickel product from nickel-bearing sulphide raw materials, such as nickel sulphide concentrate or ore or scrap.
- the raw material is leached in atmospheric conditions to an aqueous solution of sodium chloride and copper (II) chloride.
- Chlorine, hydrogen and sodium hydroxide needed in the process are produced in a chlorine-alkali electrolysis cell that is integrated as a process stage in the overall process.
- the nickel-enriched pregnant leach solution is subjected to a precipitation of dissolved iron and sulphates, and the precipitate is fed into the final step of the leaching process.
- Nickel is precipitated as nickel hydroxide Ni(OH) 2 from the pregnant leach solution by means of sodium hydroxide.
- WO publication WO2007/039664 discloses a method of recovering nickel from a nickel sulphide containing material including the steps of: providing a nickel sulphide containing material; oxidative leaching of the nickel sulphide containing material with a sodium chloride leach solution containing cupric chloride and hydrochloric acid in an oxidising atmosphere at atmospheric pressure and temperature to form a pregnant leach solution containing dissolved nickel; treating the pregnant leach solution containing dissolved nickel to separate copper and recycle it at least partly back to the leaching stage (b); purification of the nickel pregnant leach solution by the use of solvent extraction to remove cobalt, zinc and residual copper; recovering nickel from the pregnant leach solution to form a nickel depleted leach solution; and electrolytically treating the depleted leach solution in chlorine alkali electrolysis to recover chlorine, hydrogen, and sodium hydroxide.
- WO2007/039664 does not refer to a possibility of recovering nickel from a sulphate solution in electrowinning after nickel solvent extraction stage.
- a cobalt solvent extraction from chloride environment is known where cobalt is extracted from very high chloride environment using an anionic extractant to extract a cobalt-chloride complex.
- a cationic extractant for cobalt extraction from chloride containing sulphate solutions is known. In the known applications the chloride concentrations relatively low.
- the object of the present invention is to overcome disadvantages of the prior art processes and to provide a new and advantageous hydrometallurgical process for producing nickel metal.
- the invention provides method where the advantages of atmospheric leaching are utilized and recycling and regeneration of leaching chemicals are arranged through chlorine-alkali electrolysis.
- the method is particularly suitable for recovering metals from poor nickel concentrates and ores.
- the recycling of reagents within the process makes the method particularly advantageous.
- a special advantage of the present invention is that it provides a hydrometallurgical method for recovering metallic nickel where the metallic nickel is won on a cathode of an electrowinning cell from a sulphate electrolyte.
- the present invention provides a method of handling and recovering impurities of the raw material.
- impurities are for example magnesium and halides which, when treated according to the present invention, can be treated without disturbing the recovery of nickel.
- the invention relates to a method for producing nickel metal from nickel- bearing sulphide raw materials, such as nickel sulphide concentrate or ore or scrap.
- Nickel bearing feed material such as nickel sulphide concentrate or ore or scrap, particularly poor nickel concentrates and ores can be successfully treated in according to the method of the present invention. Even low-grade nickel feed materials (Ni ⁇ 1 -10%) can be processed and number of impurities, such as cobalt, iron, magnesium, zinc, copper and arsenic, can be treated without disturbing the recovery of nickel. Generally nickel sulphide bearing raw material always contains a certain amount of copper, iron, cobalt and magnesium
- a method according to the present invention comprises the steps of:
- the leaching of the nickel raw material is carried out in chloride-based aqueous solution.
- the leaching step preformed in the leaching stage produces a process liquid containing very high amount of chlorides.
- cobalt and other minor metals are separated from the very high chloride content solution in a solvent extraction process using a cationic extractant.
- the raffinate from the minor metal removal stage (MM SX) is fed to a nickel solvent extraction stage (Ni SX) where nickel is selectively extracted from a very high chloride solution and stripped to a sulphate liquid to form a nickel sulphate electrolyte.
- Ni SX nickel solvent extraction stage
- the nickel electrolyte is conducted to a nickel electrowinning stage.
- the reagents such as chlorine, hydrogen and sodium hydroxide, needed in the leaching stage and in other processing steps, are obtained from chlorine-alkali electrolysis that is integrated as a step in the process.
- the raw material is preferably leached in atmospheric conditions to an aqueous solution containing sodium chloride and copper (II) chloride.
- the pregnant leach solution (PLS) from the leaching stage is lead to solvent extraction stages.
- the chloride content of the PLS is over 100 g/l.
- the production method of a nickel product contains the following steps: a) nickel bearing raw material is leached in two or more steps by a solution containing sodium chloride and copper (II) chloride as a countercurrent leach in atmospheric conditions, so that the first leaching step when observed in the proceeding direction of the concentrate is non-oxidative, and the next steps are oxidative with respect to forming a nickel enriched nickel chloride - sodium chloride pregnant leach solution (PLS) and leach residue,
- the nickel-enriched pregnant leach solution is subjected to a liquid purification for a precipitation of dissolved iron and sulphates, and the precipitate is fed into the final step of the leaching process,
- cobalt and other minor metals are separated from the very high chloride containing liquid with cationic extractants in a cobalt solvent extraction unit.
- the cobalt depleted raffinate is conducted to a nickel solvent extraction (Ni SX) unit, d) cobalt is recovered from cobalt solvent extraction unit in an aqueous solution and precipitated,
- nickel is extracted from the cobalt solvent extraction raffinate in a nickel solvent extraction unit with cationic extractants
- nickel sulphate electrolyte from the nickel solvent extraction stage is conducted to a nickel electrowinning plant, where nickel is won to cathodes
- magnesium hydroxide Mg(OH) 2 magnesium hydroxide
- the concentrated NaCI solution is conducted to chlorine-alkali electrolysis, where part of the solution is by electrolysis processed into chlorine, hydrogen and sodium hydroxide that are used as reagents in the method, k) the NaCI solution that was depleted in the electrolysis is fed to the final leaching step of the concentrate and/or ore.
- the leaching of nickel sulphide bearing concentrate and/or ore is carried out in two steps.
- raw material is leached in non-oxidative conditions by means of copper (II) chloride, so that part of the sulphides contained in the concentrate are dissolved, and copper is precipitated as copper sulphide.
- the pH is within the range 0.5 - 3.0.
- the raw material is advantageously leached by means of copper (II) chloride for dissolving sulphides, and in the first leaching step the precipitated copper sulphide is made to be dissolved into copper (II) chloride.
- the pH is adjusted within the range 1 .7 - 2.8, preferably within the range 2.0 - 2.5.
- the oxidative reagent employed in the oxidative leaching steps of concentrate and/or ore is oxygen-bearing gas, which is oxygen, oxygen-enriched air or air, and hydrochloric acid is fed into the leaching process.
- the oxidative reagent employed in the oxidative leaching steps of concentrate and/or ore is chlorine formed in chlorine-alkali electrolysis.
- a nickel-enriched pregnant leach solution there is fed a calcium compound and sodium hydroxide for removing the dissolved sulphates and iron.
- the created iron/gypsum precipitate is conducted to the final leaching step.
- cobalt is removed from the pregnant leach solution by a cationic solvent extraction reagent, the raffinate from the cobalt extraction is fed to a nickel solvent extraction, where nickel is extracted by a cationic organic extractant and sulphate based nickel solution suitable as an electrolyte for nickel electrowinning stage is produced.
- the nickel electrolyte from the nickel solvent extraction plant is advanced to a nickel electrowinning plant, where nickel is won to cathodes in a conventional manner.
- Ni EW electrolyte quality requirements further purification of the nickel electrolyte can be done for example with an ionic exchange process, where small amounts for example copper, cadmium, iron and zinc can be removed from the produced advance electrolyte.
- the nickel depleted NaCI solution, the raffinate from the nickel solvent extraction, which has become poor in nickel is subjected to Mg precipitation in order to remove dissolved magnesium prior to the electrowinning stage.
- the magnesium precipitation is advantageously carried out at the pH value 9-10.
- the hydrochloric acid that is used as the leach reagent of raw material is advantageously made of the hydrogen and chlorine created in the chlorine- alkali electrolysis.
- a nickel bearing raw material may contain gold and/or other precious metals (PGM).
- PGM precious metals
- the gold is dissolved in the final leaching step and recovered from the solution of the final leaching step; the gold-free solution is conducted to the preceding leach step, when observed in the proceeding direction of the concentrate.
- Other precious metals are recovered from the leach residue.
- part of the depleted solution created in the concentration of sodium chloride is conducted to a concentrate leaching process. LIST OF DRAWINGS
- Figure 1 represents a schematic flow sheet of one preferred embodiment of the invention.
- figure 2 represents a schematic drawing of another embodiment of the invention.
- each leaching step typically consists of a series of several reactors, where the suspension of solution and solids is transferred as overflow from one reactor to the next.
- the reactors are provided with agitators. In between the process steps, there is performed thickening, so that the solution and the solids are transferred to different steps in the countercurrent leaching.
- the description of the invention describes a two-step leaching process, but it may turn out to be necessary to apply several steps.
- the notion of atmospheric conditions means that the operations are carried out at the pressure of the environment and at a temperature, which is within the range of 90° C - the boiling point of the solution - i.e. roughly 1 10° C.
- the alkaline chloride can be sodium or potassium chloride.
- the leaching of nickel sulphide bearing raw material (nickel concentrate in Figs. 1 and 2) is carried out in countercurrent leaching 1 1 , 21 in two or more steps.
- the raw material is fed into the first leaching step, and the chloride solutions and oxidative reagents used in the leaching process are fed into the second step.
- the first leaching step the conditions are adjusted such that part of the nickel and iron contained in the raw material are dissolved, owing to the influence of divalent copper, and the monovalent copper created in the leaching process is precipitated as copper sulphide.
- the leaching takes place in the pH range 0.5 - 3.0, depending on the raw material.
- the principal reaction that takes place in this step can be illustrated by the leaching reaction of pentlandite:
- the reaction (1 ) can be described as an exchange reaction where divalent copper is reduced to monovalent and at the same time dissolves the iron and nickel contained in the concentrate.
- Other nickel and iron minerals such as violarite, millerite and pyrrhotite, are also dissolved according to the same principle, and respectively copper sulphide and element sulphur are precipitated.
- the magnesium contained in the nickel raw material is dissolved, thus forming magnesium chloride.
- the copper contained in the raw material does not dissolve in the first leaching step conditions, but only in the second step, or if there are several leaching steps, only in the last step. If the copper content of the raw material is not sufficient for efficient leaching, more copper is brought to the leaching process in some suitable way, for instance in the form of copper concentrate or copper sulphate.
- the copper content in the solution is of the order 5-50 g/l.
- the nickel-enriched NiCI 2 -NaCI solution, PLS, obtained from the leaching step 1 1 , 21 contains an amount of dissolved iron and sulphates.
- the removal of iron and sulphates is carried out in a solution purification step 22.
- Sulphates are advantageously precipitated by means of a calcium compound, such as limestone, or other calcium compound, so that when calculated as sulphur, their content left in the solution is at the most 2 g/l.
- lye (NaOH) in the solution in which case iron is precipitated from the solution.
- the precipitate can be fed back to the final step of the concentrate leaching process, from where iron precipitate and gypsum are removed along with the leach residue.
- the nickel-enriched NaCI solution still contains divalent copper.
- the copper can be removed in a separate copper recovery step, which is advantageously cobalt solvent extraction 12, 23 or a minor metal removal 23 according to the present invention.
- Feed solution from solution purification stage is fed to the minor metals solvent extraction process 12 ,23 (MM SX).
- minor impurity metals like Co, Cu, Zn and Mn are extracted from the feed solution with a cationic extractant in a very high chloride environment.
- Multiple extraction stages are used. Before the extraction stages a separate organic and/or crud removal circuit can be installed if needed. pH control can be done in the mixer-settlers or in the organic tank (pre-neutralization) or a combination of these neutralization systems can be used.
- Loaded organic from the extraction stages can be scrubbed (chemical impurity removal) or washed (physical impurity removal) from the entrained nickel, chloride or some other impurity component. Need for the scrubbing and/or washing stages is determined by the feed quality to the MM SX process and the desired product quality from the MM SX process. One or more scrubbing/washing stages can be used.
- Loaded organic from the extraction or scrubbing and/or washing stages is fed to the stripping stages, where metals from the organic phase are stripped with an acidic solution to the aqueous phase.
- Metals from the organic phase can be stripped in one or more solutions.
- Selective strip where two or more stripping solutions are produced, are normally preferred solution, because selective strip increases the stripping liquid qualities.
- metals from a single strip solution can also be separated after the MM SX process for example with a selective precipitation process as carbonates, hydroxides or sulphides.
- One or more stripping stages can be used.
- Loaded organic from the extraction stages can be scrubbed (chemical impurity removal) or washed (physical impurity removal) from the entrained impurities like chloride, magnesium and calcium.
- One or more scrubbing and/or washing stages are used.
- Loaded organic from the scrubbing and/or washing stages is fed to the stripping stages, where nickel from the organic phase is stripped with an acidic solution to the aqueous phase.
- Produced stripping liquid, advance electrolyte is used as a feed solution for a nickel electrowinning (Ni EW) process 13, 26.
- Used acid can be sulphuric or hydrochloride acid. Normally at this stage chloride based process is converted to a sulphate phase process and thus sulphuric acid is used for stripping.
- further purification of the advance electrolyte can be done for example with an ionic exchange process, where small amounts for example copper, cadmium, iron and zinc can be removed from the produced advance electrolyte.
- the quantity of magnesium is generally largest, and the dimensioning of the final solution purification such as ion exchange according to the Mg quantity becomes fairly expensive.
- One advantageous method according to the invention is to remove the magnesium from the solution in the Mg precipitation step 5 by using sodium hydroxide NaOH, formed in the chlorine- alkali electrolysis 8, as the precipitation reagent.
- the solution pH is raised to within the range 9-10, in which case Mg is precipitated as magnesium hydroxide Mg(OH) 2 .
- the hydroxide precipitate is subjected to thickening, and the underflow of the thickening is recycled to the precipitation step advantageously for improving the quality of the precipitate.
- Ion exchange (brine purification 28 in Fig 2).
- Ion exchange is preferably carried out by means of a chelating ion exchange resin. Ion exchange functions according to known technique, so that the impurities bound in the resin are removed by means of hydrochloric acid, and the resin is regenerated with a NaOH solution. Consequently, the reagents needed in ion exchange are advantageously obtained from the chlorine-alkali electrolysis that forms part of the process.
- the content of the NaCI solution, obtained from the brine treatment 14, 28, can be of the order 150-240 g/L NaCI, preferably 200 g/L. However, for the chlorine-alkali electrolysis it is necessary to raise the NaCI content in the solution up to the order of 160-300 g/L, preferably 280-300 g/L.
- the content increase is carried out in some suitable way, for example by means of a vacuum evaporator or immersion evaporator in the evaporation step.
- the depleted NaCI solution created in the evaporation step can be conducted to the concentrate leaching process (not in the figure).
- the purified and concentrated sodium chloride solution is conducted to chlorine-alkali electrolysis 14, 29 for producing the chlorine, hydrogen and sodium hydroxide needed in different steps of the nickel product process.
- the chlorine-alkali electrolysis functions in a known fashion.
- the NaCI saline solution is in the electrolysis conducted to the anode side, where the electric current disintegrates it, thus forming chlorine gas.
- Sodium ions proceed through a membrane placed in between the anode and cathode sides to the cathode side, where the electric current disintegrates water to hydrogen gas, thus forming sodium hydroxide.
- the NaCI solution conducted to electrolysis is depleted in the electrolysis in the proportion of the gases and lye produced there from.
- the NaCI content of the solution removed from electrolysis is of the order 150 - 240 g/L, preferably 200 g/L, and it is recycled back to the raw material leaching process.
- the sodium hydroxide formed in the chlorine-alkali electrolysis 14, 29 is used at least in the precipitation of magnesium hydroxide.
- Sodium hydroxide is also needed in the ion exchange regeneration, and when necessary, it can also be used in the removal of sulphates.
- An advantageous method for leaching nickel bearing raw material is to feed oxygen to the final leaching step and to adjust the leach conditions by feeding hydrochloric acid therein according to reaction 3.
- the required hydrochloric acid is advantageously made of the hydrogen and chlorine created in the electrolysis of the hydrochloric acid production process.
- Nickel bearing feed material e.g. nickel sulphide concentrate or ore or bulk concentrate containing mainly nickel and copper sulphides, scrap or matte
- sodium chloride solution 50-200 g/l NaCI
- Leaching is conducted in two or more counter-current leaching stages. The first leaching stage is operated in non-oxidative conditions and the subsequent stages in oxidative conditions.
- Nickel and iron are transferred in solution while copper is precipitated in solid phase. Sulphide sulphur is converted mainly to elemental sulphur. Slurry from the first leaching stage is treated in a solid-liquid separation step. Solids are transferred to the subsequent oxidative leaching stage(s) and liquid is recovered as PLS, which is sent to solution purification stages. Temperature and pH in the first leaching stage is 80-1 10° and 0.5-3.0, respectively.
- Solids from the first leaching stage are mixed with depleted brine from the chlor-alkali electrolysis and further leached in oxidative leaching stages.
- Leach is oxidised with hydrochloric acid and oxidising gas such as oxygen, air, oxygen enriched air or chlorine.
- oxidising gas such as oxygen, air, oxygen enriched air or chlorine.
- copper sulphide precipitated in the first leaching stage is leached.
- Copper is released in solution as divalent copper ions, which in turn are consumed in nickel and iron sulphide leaching according to reaction (2).
- Copper(l) chloride produced in the reaction (2) is re-oxidised according to reaction (3) back to copper(ll) chloride.
- leached iron is oxidised and precipitated as iron oxides or hydroxides.
- reactions (4) and (5) iron oxidation and precipitation as goethite is shown as an example.
- iron and sulphur are also leached. Iron and sulphates are removed in solution purification. Oxidising gas (O 2 , air, oxygen enriched air, chlorine) is injected in PLS in order to oxidise iron and the pH of the solution is adjusted with sodium hydroxide and/or calcium carbonate/hydroxide to precipitate iron as iron hydro-oxides and sulphur as gypsum. Resulting solids are separated from PLS and recycled to oxidative leaching stages. Treated PLS is transferred to cobalt solvent extraction.
- Oxidising gas O 2 , air, oxygen enriched air, chlorine
- Sulphidic nickel concentrate was leached according to the method of the invention.
- the major part of the nickel contained in the concentrate was bound in pentlandite.
- Other main minerals were antigorite, millerite and pyrrhotite.
- the chemical analysis of the concentrate was:
- Nickel concentrate (690g) was leached in a solution (2500 ml), the initial content of which was:
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2792401A CA2792401C (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
AP2012006513A AP3220A (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
EP11755747.0A EP2547802A4 (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
BR112012023479A BR112012023479A2 (en) | 2010-03-18 | 2011-03-16 | Nickel-containing raw material processing method. |
EA201290869A EA020759B1 (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
CN201180020087.3A CN102859012B (en) | 2010-03-18 | 2011-03-16 | The method of process nickel-bearing raw material |
AU2011228956A AU2011228956B2 (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
ZA2012/06935A ZA201206935B (en) | 2010-03-18 | 2012-09-14 | Method of processing nickel bearing raw material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20100121 | 2010-03-18 | ||
FI20100121A FI122188B (en) | 2010-03-18 | 2010-03-18 | Hydrometallurgical process for the production of metallic nickel |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011114000A1 true WO2011114000A1 (en) | 2011-09-22 |
Family
ID=42074299
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI2011/050222 WO2011114000A1 (en) | 2010-03-18 | 2011-03-16 | Method of processing nickel bearing raw material |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP2547802A4 (en) |
CN (1) | CN102859012B (en) |
AP (1) | AP3220A (en) |
AU (1) | AU2011228956B2 (en) |
BR (1) | BR112012023479A2 (en) |
CA (1) | CA2792401C (en) |
EA (1) | EA020759B1 (en) |
FI (1) | FI122188B (en) |
WO (1) | WO2011114000A1 (en) |
ZA (1) | ZA201206935B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014188077A1 (en) | 2013-05-23 | 2014-11-27 | Outotec (Finland) Oy | Method for recovering metals |
AU2013263848A1 (en) * | 2013-11-29 | 2015-06-18 | Lifezone Limited | Treatment process for extraction of metals from ores |
WO2019100159A1 (en) * | 2017-11-22 | 2019-05-31 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
WO2021105215A1 (en) * | 2019-11-28 | 2021-06-03 | Scanacon Ab | Metal recovery method |
US11254582B2 (en) | 2012-05-30 | 2022-02-22 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
CN114212806A (en) * | 2022-01-18 | 2022-03-22 | 贵州红星电子材料有限公司 | Recovery method of nickel cobalt manganese sulfide slag |
US11519081B2 (en) | 2014-02-24 | 2022-12-06 | Nemaska Lithium Inc. | Methods for treating lithium-containing materials |
US11697861B2 (en) | 2013-10-23 | 2023-07-11 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
WO2023213919A1 (en) | 2022-05-05 | 2023-11-09 | Umicore | Process for the oxidative leaching of a metal |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109321746A (en) * | 2018-12-03 | 2019-02-12 | 北京矿冶科技集团有限公司 | A method of nickel is extracted by copper nickel Whote-wet method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4067952A (en) * | 1974-09-06 | 1978-01-10 | Anglo-Transvaal Consolidated Investment Company Limited | Leaching of copper-nickel concentrates |
WO2007039664A1 (en) * | 2005-10-03 | 2007-04-12 | Outotec Oyj. | Sodium chloride processing of nickel sulphide ore or concentrates |
WO2009050334A1 (en) * | 2007-10-16 | 2009-04-23 | Outotec Oyj | Method for the hydrometallurgical processing of sulphidic material containing zinc and copper |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN85105504B (en) * | 1985-07-19 | 1987-10-14 | 清华大学 | Method of separating and purifying ni and co with solvent extraction process |
US5650057A (en) * | 1993-07-29 | 1997-07-22 | Cominco Engineering Services Ltd. | Chloride assisted hydrometallurgical extraction of metal |
FI97154C (en) * | 1994-11-15 | 1996-10-25 | Outokumpu Eng Contract | Method for dissolving nickel copper rock |
FI98073C (en) * | 1995-08-14 | 1997-04-10 | Outokumpu Eng Oy | Process for the hydrometallurgical recovery of nickel from two different types of nickel stone |
JPH10140257A (en) * | 1996-11-07 | 1998-05-26 | Sumitomo Metal Mining Co Ltd | Wet refining method of nickel by chlorine leaching electrolytic extracting method |
US6428604B1 (en) * | 2000-09-18 | 2002-08-06 | Inco Limited | Hydrometallurgical process for the recovery of nickel and cobalt values from a sulfidic flotation concentrate |
-
2010
- 2010-03-18 FI FI20100121A patent/FI122188B/en not_active IP Right Cessation
-
2011
- 2011-03-16 BR BR112012023479A patent/BR112012023479A2/en not_active IP Right Cessation
- 2011-03-16 EA EA201290869A patent/EA020759B1/en not_active IP Right Cessation
- 2011-03-16 AU AU2011228956A patent/AU2011228956B2/en not_active Ceased
- 2011-03-16 EP EP11755747.0A patent/EP2547802A4/en not_active Withdrawn
- 2011-03-16 WO PCT/FI2011/050222 patent/WO2011114000A1/en active Application Filing
- 2011-03-16 CN CN201180020087.3A patent/CN102859012B/en not_active Expired - Fee Related
- 2011-03-16 AP AP2012006513A patent/AP3220A/en active
- 2011-03-16 CA CA2792401A patent/CA2792401C/en not_active Expired - Fee Related
-
2012
- 2012-09-14 ZA ZA2012/06935A patent/ZA201206935B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4067952A (en) * | 1974-09-06 | 1978-01-10 | Anglo-Transvaal Consolidated Investment Company Limited | Leaching of copper-nickel concentrates |
WO2007039664A1 (en) * | 2005-10-03 | 2007-04-12 | Outotec Oyj. | Sodium chloride processing of nickel sulphide ore or concentrates |
WO2009050334A1 (en) * | 2007-10-16 | 2009-04-23 | Outotec Oyj | Method for the hydrometallurgical processing of sulphidic material containing zinc and copper |
Non-Patent Citations (1)
Title |
---|
See also references of EP2547802A4 * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11634336B2 (en) | 2012-05-30 | 2023-04-25 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
US11254582B2 (en) | 2012-05-30 | 2022-02-22 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
US10174400B2 (en) | 2013-05-23 | 2019-01-08 | Outotec (Finland) Oy | Method for recovering metals |
WO2014188077A1 (en) | 2013-05-23 | 2014-11-27 | Outotec (Finland) Oy | Method for recovering metals |
US11697861B2 (en) | 2013-10-23 | 2023-07-11 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
AU2013263848A1 (en) * | 2013-11-29 | 2015-06-18 | Lifezone Limited | Treatment process for extraction of metals from ores |
AU2013263848B2 (en) * | 2013-11-29 | 2016-02-18 | Lifezone Limited | Treatment process for extraction of metals from ores |
US11519081B2 (en) | 2014-02-24 | 2022-12-06 | Nemaska Lithium Inc. | Methods for treating lithium-containing materials |
WO2019100159A1 (en) * | 2017-11-22 | 2019-05-31 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
US11542175B2 (en) | 2017-11-22 | 2023-01-03 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
US11142466B2 (en) | 2017-11-22 | 2021-10-12 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
US12006231B2 (en) | 2017-11-22 | 2024-06-11 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
WO2021105215A1 (en) * | 2019-11-28 | 2021-06-03 | Scanacon Ab | Metal recovery method |
CN114212806A (en) * | 2022-01-18 | 2022-03-22 | 贵州红星电子材料有限公司 | Recovery method of nickel cobalt manganese sulfide slag |
CN114212806B (en) * | 2022-01-18 | 2023-08-18 | 贵州红星电子材料有限公司 | Recovery method of nickel-cobalt-manganese sulfide slag |
WO2023213919A1 (en) | 2022-05-05 | 2023-11-09 | Umicore | Process for the oxidative leaching of a metal |
Also Published As
Publication number | Publication date |
---|---|
AP3220A (en) | 2015-04-30 |
AU2011228956B2 (en) | 2013-11-21 |
AU2011228956A1 (en) | 2012-11-08 |
EP2547802A1 (en) | 2013-01-23 |
EA020759B1 (en) | 2015-01-30 |
CN102859012A (en) | 2013-01-02 |
EP2547802A4 (en) | 2016-07-13 |
CA2792401C (en) | 2015-08-18 |
CN102859012B (en) | 2015-11-25 |
CA2792401A1 (en) | 2011-09-22 |
FI122188B (en) | 2011-09-30 |
BR112012023479A2 (en) | 2016-05-24 |
ZA201206935B (en) | 2013-05-29 |
FI20100121A0 (en) | 2010-03-18 |
EA201290869A1 (en) | 2013-05-30 |
AP2012006513A0 (en) | 2012-10-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1931807B1 (en) | Method for processing nickel bearing raw material in chloride-based leaching | |
CA2792401C (en) | Method of processing nickel bearing raw material | |
FI125027B (en) | Method of metal recycling from materials containing them | |
US9039806B2 (en) | Recycling of solids in oxidative pressure leaching of metals using halide ions | |
US6746512B1 (en) | Hydrometallurgical extraction of copper and other valuable metals | |
WO2015192234A1 (en) | Recovery of zinc and manganese from pyrometallurgy sludge or residues | |
ZA200501592B (en) | Method for the recovery of metals using chloride leaching and extraction | |
CA2949036C (en) | Hydrometallurgical process for the recovery of copper, lead and/or zinc | |
EP3739069B1 (en) | Method of extracting metals from polymetallic sulphide ores or concentrates | |
AU2003254729B2 (en) | Hydrometallurgical extraction of copper and other valuable metals | |
AU5499099A (en) | Hydrometallurgical extraction of copper and other valuable metals | |
WO2013030449A1 (en) | Method for recovering metals from sulphidic concentrate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180020087.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11755747 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2792401 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 201290869 Country of ref document: EA |
|
REEP | Request for entry into the european phase |
Ref document number: 2011755747 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011755747 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2011228956 Country of ref document: AU Date of ref document: 20110316 Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012023479 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012023479 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120918 |