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
  • C22B23/00—Obtaining nickel or cobalt
  • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
• • 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
• • 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
• • 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
  • 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
  • C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B23/00—Obtaining nickel or cobalt
  • C22B23/04—Obtaining nickel or cobalt by wet processes
  • C22B23/0476—Separation of nickel from cobalt
• • 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 method for processing laterite ores so that the metals contained in the laterites are turned into water-soluble form for the recovery of valuable metals, such as nickel and cobalt.
• metals such as nickel and cobalt.
• Different types of nickel laterites are processed at the same time without being separated according to their iron and/or magnesium content.
• laterites are pre- treated with concentrated mineral acid so that the metals contained in the laterites react to form water-soluble salts, the silicates contained in the laterites are partially decomposed and post-leaching liquid-solid separation becomes easier than it was previously.
• the water vapour generated in the ore and acid reaction stage is utilised in ore drying and the unreacted mineral acid is recycled to the front end of the process.
• a method is disclosed in US patent 4125588 in which nickel laterite ore is pre-treated with concentrated acid before nickel leaching.
• laterite ore is dried so that the moisture content of the ore is less than 1 %.
• the dried ore is ground to a particle size range of 65 - 100 mesh.
• the ground ore is mixed into concentrated acid at a mass ratio of about 1 :1.
• the metal sulphation reactions are initiated by adding water to the mixture containing laterite and acid in a ratio of 3 - 40% of the mass of the laterite.
• the sulphated metals are leached into water.
• US patent application 2006/0002835 describes a method in which laterite leaching takes place in two stages.
• the laterite ore is mixed with concentrated sulphuric acid.
• the ore/acid mixture is slurried with water and then leached, so that the nickel and cobalt dissolve.
• the amount of sulphuric acid used in pre- treatment is stoichimetric with regard to the non-ferrous metals in the ore, but not the iron. According to example 5, the acid/ore ratio is 0.65. A little excess acid is advantageous so that a small amount of iron also dissolves, because this achieves the maximal dissolution of nickel and cobalt.
• the leaching stage of the method is implemented either at a temperature of 95 - 105° C or in an autoclave at a temperature which is a maximum of 150° C and in which the pressure corresponds to the saturated steam pressure.
• some suitable reductant is added to the leaching stage, such as sulphur dioxide.
• sulphur dioxide is added to the leaching stage.
• the effectiveness of the method requires that there is a significant proportion of easily-soluble saprolitic laterite in the laterite, so that it can function in the ferric iron precipitation range.
• the purpose of the invention presented here is to eliminate the problems that have arisen in earlier methods and to achieve a method for leaching laterites in a way that in particular solids separation from the solution does not cause problems.
• the invention also aims to improve the economics of the laterite process by utilising the heat generated in the reactions and recovering the acid that is not consumed in the reactions.
• the invention relates to a method for processing nickel laterite ore to facilitate the recovery of nickel and cobalt and liquid-solid separation.
• a) crushed laterite ore is dried using the steam from a later process stage, b) the dried ore is subjected to dry grinding, c) the fine ore is routed to an acid treatment mixing stage that takes place using concentrated mineral acid, in which the ore is mixed homogenously into the acid, the amount of which is at least stoichiometric with regard to the metals contained in the ore, d) the mixture of ore and acid is fed to the acid treatment reaction stage, which takes place at ambient pressure and a temperature of between 15O 0 C and the boiling point of the acid, whereby the acid and ore react with each other; the water vapour formed in the reaction is recovered and recycled for use in ore drying, e) the acid-treated laterite ore is routed to acid recovery, where the acid that remained unreacted in the reactions of the acid treatment mixing stage is recovered by evaporation,
• the particle size of the crushed laterite ore is in the region of 90% below 10 mm.
• the acid and laterite are mixed into a homogenous mixture at a temperature where the metals do not yet substantially react with the acid.
• the metals of the laterite ore are made to form water-soluble salts of the mineral acid.
• the mineral acid is at least one of the following: sulphuric acid, nitric acid, or hydrochloric acid, or a mixture of at least two of them.
• the concentration of the mineral acid is preferably in the order of 70 - 98 wt.%.
• the reaction stage is sulphation.
• the mixture of acid and ore fed to the reaction stage is heated at the front section of the stage.
• the unreacted acid is evaporated from the acid-treated laterite. Evaporation takes place for example by heating the acid-treated laterite to the boiling point of the acid at normal pressure or using negative pressure.
• the slurry exiting the water leaching stage is routed to a neutralisation stage, in which iron is precipitated by neutralising the slurry.
• the slurry formed in water leaching is routed directly to ion exchange treatment, where the ion exchange resin is selective with regard to nickel and cobalt.
• the waste slurry is routed to neutralisation for the precipitation of other metals.
• the slurry formed in water leaching is routed to a cementation stage, where the valuable metals nickel and cobalt are cemented from the solution by means of iron powder. After the cementation and magnetic separation of valuable metals, the waste slurry is routed to neutralisation for the precipitation of other metals.
• a neutralising agent is fed to the water leaching stage of the acid-treated material in order to precipitate the iron as a hydroxide, while the nickel and cobalt remain as water-soluble salts.
• the neutralising agent is preferably lime and/or lime milk. After the leaching and iron precipitation stage, the precipitation of nickel and cobalt as hydroxide, sulphide, or carbonate is performed.
• the mineral acid used is sulphuric acid
• at least some of the acid-treated material is routed to thermal treatment, in which the iron sulphates are broken down into sulphur oxides and hematite.
• the sulphur oxides are routed to the sulphuric acid plant to manufacture sulphuric acid, which is used for the acid treatment of laterite ore.
• the material exiting thermal treatment containing hematite and water-soluble metal salts is routed to water leaching.
• Figure 1 is a flow diagram of one embodiment of the invention.
• FIGS. 2 - 5 are flow diagrams of other embodiments of the invention.
• nickel laterites such as limonite, saprolite and nontronite or their compounds
• concentrated mineral acid 70-98% so that the metals contained in the laterites form water-soluble salts of the mineral acid.
• the metals contained in laterites are mostly nickel, cobalt, manganese, magnesium, aluminium, chromium and iron, of which nickel and cobalt are mainly considered to be the valuable metals.
• Mineral acid refers mostly to sulphuric acid, hydrochloric acid or nitric acid, or a mixture of them.
• liquid-solid separation has proved problematic in the atmospheric leaching of laterites.
• the object of this invention is to achieve a method whereby the liquid/solid separation properties are good and thus it is possible to make the method an economic one.
• the laterite is dry and sufficiently fine in particle size.
• normal concentrate coarseness is enough for the laterite grinding degree, in other words the method does not require actual fine grinding.
• the grain size is too coarse, the acid will not be able to penetrate inside the laterite grains, and as a result the formation of water-soluble salts, i.e. in the case of sulphuric acid sulphation, will be slow and will often remain incomplete.
• moist laterite causes the activation of the sulphation reaction due to the solvation heat of the acid, which hampers the mixing together of the laterite and acid.
• laterite ore is crushed to a grain size of 90 % under 10 mm.
• the crushed ore is dried in a drying stage 1 utilising the water vapour generated in the sulphation reactions of the later reaction stage 4.
• Dried laterite ore is routed to a dry grinding stage 2, where it is ground typically to a grain size of 90 % under 500 ⁇ m, preferably 90 % under 150 ⁇ m, using for instance a ball mill.
• the laterite is routed to the acid treatment mixing stage 3, in which laterite ore and concentrated sulphuric acid are mixed with each other homogenously in some suitable equipment, such as for example a screw mixer, drum-type reactor, or some other kind of reactor. Acid is added in such a quantity that it is at least in stoichiometric ratio with regard to the metals in the laterite.
• the temperature of the mixing stage is adjusted preferably to be below 100 0 C, so that the generated mixture does not harden and complicate further processing.
• the purpose is to operate at a temperature at which sulphation does not yet take place.
• the mixture is transferred to the reaction stage 4, in which the process temperature is raised first by means of external heating, after which the reactions between the laterite and acid begin to produce heat, and the process becomes largely autothermal.
• the reaction stage occurs at ambient pressure and at a temperature of around 150-300° C. Heat may be added in the early stages of the process, e.g. by means of internal or external heating such as burners, in order to optimize the desired chemical reactions.
• the process temperature may be a maximum of the boiling point of the acid, i.e. the operating temperature is below 339 0 C when sulphuric acid is concerned. Laterites typically include a lot of crystalline water and in addition, for example in sulphation reactions, a considerable amount of water is generated, which evaporates during heating.
• the water vapour generated is recovered and utilised in laterite drying, as mentioned above.
• water is added to the sulphation stage, but in the method accordant with this invention water is not added to the reaction stage. Both the mixing and reaction stage like the later leaching stage all occur at ambient pressure, in other words the system is atmospheric.
• the material exiting acid treatment is solid and powdery in nature and is thus easy to process.
• the solid fine material that contains the water-soluble salts of the acid is routed to the actual leaching stage 6, where water is routed to the solids.
• the water leaching stage takes place in atmospheric conditions, i.e. at a temperature of 80 - 105 0 C and under ambient pressure.
• the duration of the leaching stage depends on the grain size and composition of the laterite ore and is typically between 1 - 2 h.
• all the sulphated metals contained in the laterite dissolve.
• iron which is mostly trivalent, is separated from the metal-containing solution, by neutralising the solution in the neutralisation stage 7 with some suitable neutralising agent, so that the iron is precipitated but the nickel and cobalt salts remain water-soluble.
• Preferred neutralising agents are limestone and/or limestone milk, whereby iron is precipitated as hydroxide. If it is wished to precipitate the iron as jarosite for example, other known precipitation agents are used in addition, such as sodium sulphate. Aluminium and the majority of the chromium are precipitated at the same time as the iron, whereby they enter the leach residue.
• solids separation 8 is performed, in which the solids are separated from the liquid in typical separation ways, such as thickening and/or filtering, whereby the substances left in the solids, such as iron and silicates, are made to separate from the solution.
• All the dissolved metals and particularly the solution containing valuable metals (PLS) is routed to the following stage for further treatment of the solution, where the dissolved ions are made to separate effectively and routed to the next process stages (not shown in detail in the chart).
• PLS valuable metals
• the removal of magnesium and manganese from the solution occurs at a high pH value, typically in the range of 9 -1 1 , using lime or a corresponding neutralising agent, whereby Mg and Mn are precipitated, mostly as hydroxides.
• Figure 2 presents a second alternative embodiment of the invention for treating the residue that exits the water leaching stage 6.
• the initial stages of the method are performed as described above. It is typical of this alternative that no liquid-solid separation is carried out at all after leaching, but the entire amount of slurry is routed to ion exchange treatment 9, in which valuable metals such as nickel and cobalt are recovered by means of the ion exchange resin directly from the slurry in accordance with what is known as the resin-in-pulp concept. After adsorption to the ion exchange resin, the resin is routed to the elution stage 10, where it is eluted with acid or an equivalent eluent and the valuable metal containing elution solution is routed to further treatment.
• the resin is recycled back to the ion exchange stage 9.
• the valuable metals are recovered from the elution solution for example by means of sulphide precipitation or liquid-liquid extraction, which are not described in detail.
• the waste sludge exiting the ion exchange stage, containing iron and silicates, is routed to the neutralisation stages, in which iron, aluminium, manganese and magnesium, etc. are precipitated out of the solution.
• Figure 3 shows a third alternative embodiment of the invention for treating the residue that exits water leaching 6.
• the desired valuable metals such as nickel and cobalt
• the slurry is not subjected to liquid-solid separation before valuable metal recovery in this case either.
• the iron powder is separated from the slurry in a magnetic separation stage 12, for instance by means of a weak magnetic separator.
• the mixture of iron powder and valuable metals is routed to a valuable metals leaching stage 13, in which the mixture is leached with acid and the solution is routed to further treatment to recover nickel and cobalt.
• the waste sludge generated during the cementation of valuable metals which contains iron and silicates, is routed to the neutralisation stages, where iron, aluminium, manganese and magnesium, etc. are precipitated out of the solution.
• the process accordant with the invention as disclosed in Figure 1 may also be modified in accordance with Figure 4, where it is shown that the water leaching stage 6 following acid treatment may also be carried out as a combined leaching stage 14, in which the acid-treated laterite ore is treated directly with a neutralising solution by adding the amount of limestone required for the aqueous phase.
• the leaching of the water- soluble salts of the laterite, solution neutralisation, and the precipitation of the resulting iron all take place in the same stage.
• only one solids and liquid separation stage 15 is required, in which both the leach residue and the gypsum and iron precipitate that are formed are separated from the solution.
• the PLS solution containing nickel and cobalt goes to further treatment, for instance sulphide precipitation 16, and the end solution goes to a magnesium and manganese removal stage 17, in which the metals are precipitated from the solution by neutralisation.
• the end solution is mostly water, which can be recycled back to the leaching stage (not shown in detail in the drawing).
• FIG. 5 Yet another alternative embodiment of the invention for the further treatment of acid-treated laterite is disclosed in Figure 5.
• the material exiting the mixing and reaction stages is fed after the acid recovery stage 5 either wholly or partially into a thermal treatment stage 18, which may take place for example in a drum or fluidised bed furnace.
• Thermal energy is required in the thermal treatment stage, which is obtained for example by burning coal.
• the acid is sulphuric acid
• the iron in the laterite reacts to form iron sulphate, which is now broken down in thermal treatment into hematite and sulphur oxide.
• Sulphur oxide gases SO 2 and SO 3
• the hematite-containing material is routed to water leaching 6, in which nickel, cobalt and magnesium dissolve and are recovered by the methods described above.
• the free acid remaining in the acid-treated laterite may be evaporated as described earlier before thermal decomposition.
• the advantages of the procedure are a waste material that is easy to treat and reduced acid costs.
• EXAMPLES The operating method is illustrated with the following examples.
• the laterite ore used in the examples is nontronitic and its composition is presented in Table 1.
• the ore was dried and crushed to a size of 100% below 1 mm before the tests.
• Dry laterite was ground with a ball mill to a grain size of 95% below 105 ⁇ m.
• the acid used was sulphuric acid. Sulphuric acid and laterite were mixed together in the mixing stage at a mass ratio of 1 :1. 348 g of the mixture was fed into the reaction stage rotary kiln, where the temperature in the central point of the kiln was 25O 0 C. The residence time of the mixture in the hot part of the kiln was about 30 min. The weight of the rotary kiln product was 296.3 g.
• the composition of the rotary kiln product is presented in Table 2. Table 2. Composition Ot the rotary kiln product.
• the importance of grinding for nickel yield in leaching is illustrated by the following example.
• the test was carried out with unground ore, which had been crushed to a grain size of 100% below 1 mm. Sulphuric acid and laterite were mixed together in the mixing stage at a mass ratio of 1 :1.
• the reaction stage took place in a rotary kiln, into which 400g of the mixture was fed.
• the temperature in the central point of the kiln was 25O 0 C.
• the residence time of the mixture in the hot part of the kiln was about 27 min.
• the weight of the rotary kiln product was 279.1 g.
• the composition of the rotary kiln product is presented in Table 5.

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• 2008
  • 2008-11-03 FI FI20080603A patent/FI121180B/fi not_active IP Right Cessation
• 2009
  • 2009-10-29 EA EA201100547A patent/EA018749B1/ru not_active IP Right Cessation
  • 2009-10-29 WO PCT/FI2009/050870 patent/WO2010061045A1/en active Application Filing
  • 2009-10-29 BR BRPI0921490A patent/BRPI0921490A2/pt not_active IP Right Cessation
  • 2009-10-29 EP EP09828687.5A patent/EP2350327A4/en not_active Withdrawn
  • 2009-10-29 CN CN200980143876.9A patent/CN102203307B/zh not_active Expired - Fee Related
  • 2009-10-29 AU AU2009321543A patent/AU2009321543B2/en not_active Ceased
• 2011
  • 2011-04-29 CU CU20110099A patent/CU23937B1/es active IP Right Grant

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