AU2012300185A1 - Method for the treatment of acidic leach liquors - Google Patents
Method for the treatment of acidic leach liquors Download PDFInfo
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- AU2012300185A1 AU2012300185A1 AU2012300185A AU2012300185A AU2012300185A1 AU 2012300185 A1 AU2012300185 A1 AU 2012300185A1 AU 2012300185 A AU2012300185 A AU 2012300185A AU 2012300185 A AU2012300185 A AU 2012300185A AU 2012300185 A1 AU2012300185 A1 AU 2012300185A1
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- sulphuric acid
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- nickel
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- 238000000034 method Methods 0.000 title claims abstract description 100
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 174
- 238000000926 separation method Methods 0.000 claims abstract description 84
- 239000012465 retentate Substances 0.000 claims abstract description 41
- 239000012466 permeate Substances 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims description 96
- 239000002184 metal Substances 0.000 claims description 96
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 95
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 87
- 239000001117 sulphuric acid Substances 0.000 claims description 87
- 235000011149 sulphuric acid Nutrition 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 81
- 239000002253 acid Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000001728 nano-filtration Methods 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 150000002739 metals Chemical class 0.000 claims description 36
- 238000011084 recovery Methods 0.000 claims description 32
- 238000001223 reverse osmosis Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000502 dialysis Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 14
- 238000009792 diffusion process Methods 0.000 claims description 13
- 238000002203 pretreatment Methods 0.000 claims description 9
- 230000000717 retained effect Effects 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000010908 decantation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000005569 Iron sulphate Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000001164 aluminium sulphate Substances 0.000 claims description 3
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 3
- 230000008719 thickening Effects 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims 3
- 230000004907 flux Effects 0.000 description 7
- 238000002386 leaching Methods 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
- B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/243—Dialysis
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Urology & Nephrology (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method (10) for the separation of multivalent species from monovalent species in an acidic leach solution (14). The method (14) comprises the steps of passing the acidic leach solution (14) through a membrane in a membrane treatment step (16) to separate a membrane permeate (20) and a membrane retentate (22). The method also comprises recovering the membrane permeate (20) containing the monovalent species; and collecting the membrane retentate containing the multivalent species.
Description
WO 2013/026093 PCT/AU2012/000982 1 "METHOD FOR THE TREATMENT OF ACIDIC LEACH LIQUORS" Field of the Invention The present invention relates to a method for the treatment of acidic leach 5 liquors obtained from a metal recovery process, such as in a leaching process for the recovery of nickel from lateritic ores. The method preferably also involves steps for the recovery of sulphuric acid from leach liquors. 10 Background to the Invention The most commonly used hydrometallurgical process route for the production of nickel involves the leaching of nickel bearing lateritic ore in sulphuric acid (H 2
SO
4 ) at either atmospheric or elevated pressure. The solid residue is separated from the leach liquor by counter current washing for 15 disposal. The leach liquor contains substantial residual free acid, which is most commonly consumed by introducing limestone (CaCO 3 ) slurry to decrease solution acidity to approximately pH 4. The neutralisation reaction produces solid gypsum waste (CaSO 4 *2H 2 0) 20 and liberates carbon dioxide gas (C0 2 ). For every ton of H 2
SO
4 neutralised, over a ton of CaCO 3 is consumed, producing 1.8 ton of solid CaSO 4 *2H 2 0 waste and releasing 450 kg of C02 to the atmosphere. The costs associated with this include: * The additional tailings storage costs 25 e the CaCO 3 reagent cost * the cost of wasted H 2
SO
4 not being reacted during leaching * the environmental cost of releasing C02 to the atmosphere.
WO 2013/026093 PCT/AU2012/000982 2 Therefore the disposal of the excess acidic solution is costly due to the techniques required for disposal and is of course wasteful since the excess acid is thrown away. The disposal of such solutions is also not ideal for the environment and can leave toxic residues. Therefore there is a need to 5 employ this excess acid in a positive way, both by trying to recover any remaining nickel and/or other valuable metals such as cobalt in the excess acid solution, as well as by reusing the excess acid such as for the leaching stage. 10 There have been many studies carried out investigating the behaviour of acidic aqueous solutions in methods using nano-filtration (NF) membranes and diffusion dialysis technology. Most of the work in this area has centred around the specific details of the membrane process rather than being focussed on any useful commercial application of these techniques. In the 15 commercial field there has been some work carried out in relation to the use of membrane technology to treat effluent streams, but no commercially useful application of this technology to a metal recovery process and liquors derived from such a process. 20 References to prior art in this specification are provided for illustrative purposes only and are not to be taken as an admission that such prior art is part of the common general knowledge in Australia or elsewhere. Summary of the Invention 25 According to one aspect of the present invention there is provided a method for the separation of multivalent species from monovalent species in an acidic leach solution, the method comprising the steps of: i) passing the acidic leach solution through a membrane in a 30 membrane treatment step to separate a membrane permeate and a membranetentate; WO 2013/026093 PCT/AU2012/000982 3 ii) recovering the membrane permeate containing the monovalent species; and iii) collecting the membrane retentate containing the multivalent species. 5 Typically the acidic leach solution is a leach solution from a metal recovery process. , Preferably the metal recovery process is a process for the recovery of nickel and/or cobalt from lateritic ore or concentrate. Preferably the acidic solution is a sulphuric acid solution. 10 According to another aspect of the present invention there is provided a method for the separation of nickel and other valuable metals leached from lateritic ore using sulphuric acid, the method comprising the steps of: i) passing an acidic leach solution containing the nickel and other 15 valuable metals through a membrane in a membrane treatment step to separate a membrane permeate and a membrane retentate; ii) recovering the membrane permeate containing the sulphuric acid; and, iii) collecting the membrane retentate containing the nickel and other 20 valuable, metals for further processing. The membrane treatment step may comprise nano-filtration. Preferably the membrane is a nano-filtration (NF) membrane. Preferably the NF membrane has high acid resistance and a Dalton cut off of around 200 to. 25 300. Examples of NF membranes commercially available and that may be suitable are: Koch MPF-30 and GE Osmonics Desal DK. The membrane treatment step may comprise reverse osmosis. The membrane treatment step may comprise nano-filtration combined with 30 reverse osmosis. The membrane treatment step may comprise diffusion dialysis.
WO 2013/026093 PCT/AU2012/000982 4 Preferably the method also comprises a pre-treatment step prior to the membrane treatment step, the pre-treatment step comprising the removal of residual tailings solids from the acidic leach solution. Preferably the pre treatment step comprises clarification and/or filtration of the acid leach 5 solution to form a treated acidic leach solution which is then passed to the membrane treatment step. Preferably subsequent to the membrane treatment step the collected membrane retentate is treated to remove iron and aluminium using a 10 pressurised autoclave, and the solids precipitated in the autoclave are separated from the solution by means of a solid/liquid separation step. Advantageously the resulting solution from the solid/liquid separation step is again treated by a membrane in a second membrane treatment step to recover some of the sulphuric acid. Preferably the membrane in the second 15 membrane treatment step is a nano-filtration (NF) membrane. Preferably the NF membrane has high acid resistance and a Dalton cut off of around 200 to 300, and the membrane permeate consists predominantly of water and sulphuric acid, which pass through the membrane as 20 monovalent H* and HS0 4 ions. Preferably the membrane retentate contains the remaining water, plus the majority of the metal sulphate salute species in a more concentrated stream. The membrane permeate may be further treated in a separation step to 25 separate the sulphuric acid from water. Preferably the separation step- is carried out using a reverse osmosis (RO) membrane. Typically RO membranes that may be suitable for use in this step are Hydranautics ESPA1 4040 and Dow Filmtec TW-30. 30 The majority of the water typically passes through the RO membrane while the sulphuric acid is retained. In this way the sulphuric acid becomes more con-centratediidrnday be fed1o an acid stream. The acid stream may be WO 2013/026093 PCT/AU2012/000982 5 returned to the leach circuit, reducing overall acid consumption. The water which passes through the RO membrane may be used as a slightly acidic water source elsewhere in the nickel process flowsheet, possibly as wash water in the counter current decantation (CCD) circuit. 5 The membrane retentate containing the various metal species may be further treated to recover the metals using usual metal recovery processing steps. The benefit of treating the membrane retentate obtained in this way is that the retentate contains less free acid than the original liquor so that 10 less calcium carbonate is required in a subsequent neutralisation step, thereby producing less CaSO 4 *2H 2 0 waste and emitting less C02 to the atmosphere. According to a still further aspect of the present invention there is provided a 15 method for the separation of multivalent metal species from sulphuric acid in a sulphuric acid leach solution, the method comprising the steps of: i) passing the sulphuric acid leach solution through a membrane in a membrane treatment step to separate a permeate and a retentate, 20 the permeate comprising sulphuric acid and the retentate comprising a multivalent metal sulphate solution; ii) recovering the permeate comprising sulphuric acid; and iii) treating the retentate to remove iron and aluminium. 25 Typically the sulphuric acid leach solution is a leach solution from a metal recovery process. Preferably the metal recovery process is a process for the recovery of nickel and/or cobalt from lateritic ore or concentrate. The membrane in the membrane treatment step is preferably a diffusion 30 dialysis membrane. The membrane in the membrane treatment step may be an NF membrane. The membrane treatment step may comprise reverse osmosis.
WO 2013/026093 PCT/AU2012/000982 6 Preferably the iron and aluminium removal step is carried out using a pressurised autoclave to remove iron and aluminium sulphate from the retentate solution to form an autoclave treated solution. Preferably the iron 5 and aluminium removal step is carried out at a temperature in the range of about 150-250 0 C, and more preferably at about 2000C. The discharge autoclave treated solution or slurry may be subjected to a solid liquid separation step. Preferably the solid liquid separation step 10 involves thickening and/or filtration. Preferably the resulting solids free solution from the solid liquid separation step passes to a further membrane treatment step such as by using an NF membrane. 15 Preferably further sulphuric acid is generated by passing the autoclave treated solution or slurry through the NF membrane in the further membrane treatment step. The resulting NF permeate comprises the monovalent species such as sulphuric acid, and the resulting NF retentate comprises 20 the multivalent species. The NF permeate comprises water and solute species which pass through the pores in.the membrane, -and the NF retentate comprises water and solute species which do not pass through the membrane. The majority of 25 the solute species produced during the leaching of lateritic ore are divalent and trivalent cations (including one or more of Ni 2 +, Co 2 +, Mg 2 +, Al'*, Mn2+ Cr 3 *) charge balanced by sulphate'(S042-) and bisulphate (HS0 4 ) anions. NF membranes reject the majority of divalent and trivalent solute species while allowing monovalent species to pass through relatively unhindered. 30 Thus the NF permeate consists predominantly of water, and sulphuric acid, which pass through the membrane as monovalent H* and-HSO 4 ihos. The WO 2013/026093 PCT/AU2012/000982 7 NF retentate contains the remaining water, plus the majority of the metal sulphate solute species. The NF permeate may be further treated in a separation step to separate 5 the sulphuric acid from water. Preferably the separation step is carried out using a reverse osmosis (RO) membrane. Typically RO membranes that may be suitable for use in this step are Hydranautics ESPA1 4040 and Dow Filmtec TW-30. 10 The majority of the water typically passes through the RO membrane while the sulphuric acid is retained. In this way the sulphuric acid becomes more concentrated and may be fed to an acid stream. The acid stream may. be returned to the leach circuit, reducing overall acid consumption. The water which passes through the RO membrane may be used as a slightly acidic 15 water source elsewhere in the nickel process flowsheet, possibly as wash water in the counter current decantation (CCD) circuit. The NF retentate containing the various metal species may be further treated to recover the metals using usual metal recovery processing steps. 20 The benefit of treating the retentate obtained in this way is that the retentate contains less free acid than the original liquor so that less calcium carbonate is required in a subsequent neutralisation step, thereby producing less CaSO 4 *2H 2 0 waste and emitting less CO 2 to the atmosphere. 25 Throughout the specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. Likewise the word "preferably" or variations such as "preferred", will be understood to 30 imply that a stated integer or group of integers is desirable but not essential to the working of the invention.
WO 2013/026093 PCT/AU2012/000982 8 Brief Description of the Drawings The nature of the invention will be better understood from the following detailed description of an embodiment of a method for the separation of multivalent species from monovalent species in an acidic leach solution, 5 given by way of example only, with reference to the, accompanying drawings, in which: Figure 1 is a flow diagram of an embodiment of a method for the separation of multivalent species from monovalent species in an acidic 10 leach solution. Detailed Description of Preferred Embodiments A preferred embodiment of a method 10 for the separation of multivalent species from monovalent species (sulphuric acid) in an acidic leach solution 15 in accordance with the invention, is illustrated in Figure 1. The method includes the recovery of sulphuric acid which may then be recycled for use in the metal recovery process. The method 10 for the separation of multivalent species from monovalent 20 species in an acidic leach solution 14 comprises the steps of passing the acidic leach solution 14 through a membrane in a membrane treatment step 16 to separate the permeate (water and solute species which pass through the pores in the membrane), namely, a sulphuric acid solution 20, and retentate (water and solute species which do not pass through the 25 membrane) namely a less concentrated sulphuric acid solution containing metal sulphate species 22. The method then comprises recovering the sulphuric acid solution 20 and collecting the solution 22 containing mainly the multivalent species for further processing. 30 The acidic leach solution 14 is typically-a-sulphuric-acid-solution-containirg divalent and trivalent metal sulphates leached from lateritic nickel ore 24 in WO 2013/026093 PCT/AU2012/000982 9 a sulphuric acid leach step 12. The acidic leach solution 14 is produced by first leaching lateritic nickel ore 24 in a sulphuric acid leach step 12 followed by separating it from solid tailings residue 42 in a counter current decantation (CCD) 18 circuit. 5 The membrane treatment step 16 typically comprises the use of diffusion dialysis equipment such as that marketed by Mech-Chem Associates, Inc. The membrane treatment step 16 may comprise NF, but the NF permeate is 10 preferably diluted with water to reduce the sulphuric acid concentration before introducing the solution to the iron and aluminium removal autoclave 44. Diffusion dialysis is preferable in the membrane treatment step because: 15 * The concentration of sulphuric acid in the metal sulphate solution which does not pass through the membrane is lower than would be achieved by using a NF membrane. This increases the effectiveness of the pressurised autoclave 44 as used in the later precipitation of 20 iron and aluminium. * Diffusion dialysis does not require elevated pressure to operate. The membrane treatment step 16 may comprise reverse osmosis 26. 25 Preferably the method 10 also comprises a pre-treatment step 28 prior to the membrane treatment step 16. The pre-treatment step 28 comprises the removal of residual solids from the acidic leach solution. Typically the pre treatment step 28 comprises clarification and/or filtration of the acid leach solution 12 to form a treated solids free acidic leach solution which is then 30 passed to the membrane treatment step 16.
WO 2013/026093 PCT/AU2012/000982 10 The sulphuric acid solution (permeate) 20 comprises chiefly water and solute species which pass through the pores in the membrane during the membrane treatment step, and the retained stream (retentate) 22 comprises mainly water and solute species which do not pass through the membrane. 5 The majority of the solute species produced during the leaching of lateritic ore are divalent and trivalent cations charge balanced by sulphate (S0 4 2 ) and bisulphate (HS0 4 ) anions. Membranes such as NF membranes reject the majority of divalent and trivalent solute species while allowing monovalent species to pass through relatively unhindered. 10 Thus. the sulphuric acid solution 20 consists predominantly of water and sulphuric acid, which pass through the membrane as monovalent H* and HS0 4 ions. The retained stream 22 contains water, plus the majority of the metal sulphate solute species. 15 The sulphuric acid solution 20 may be further treated using a reverse osmosis (Rd) membrane 26 to separate the sulphuric acid 30 from water 32. Typically RO membranes that may be suitable for use in this step are commercially available products sold under the brand names of 20 Hydranautics ESPA1 4040 and Dow Filmtec TW-30. A large fraction of the water 32 typically passes through the RO membrane 26 while almost all of the sulphuric acid is retained in a more concentrated stream 30 than the feed 20 to the RO membrane 26. In this way the 25 sulphuric acid may be recycled to an ore feed preparation step 36 or to the sulphuric acid leach step 34. By recycling the acid stream 30, overall acid consumption is reduced. The water 32 which passes through the RO membrane may be used as slightly acidic water source elsewhere in the nickel process flowsheet, possibly as supplementary wash water to the CCD 30 circuit 18.
WO 2013/026093 PCT/AU2012/000982 11 The retained solution 22 from diffusion dialysis (retentate), containing the various metal species may be treated to remove iron and aluminium using a pressurised autoclave 44 at elevated temperature in the range of about 150 250 0 C, preferably 200 0 C. Increasing the temperature in the autoclave 5 reduces the solubility of both iron and aluminium, causing hematite and alunite solids to precipitate. This increases the amount of sulphuric acid in solution. The solids 40 precipitated in the autoclave 44 are separated from the 10 solution 46 by means of a solid/liquid separation step 45. Preferably the solid/liquid separation step 45 involves a thickener and filter. The liquid stream 46 from the solid/liquid separation step 45 is now low in both iron and aluminium content but contains a higher concentration of sulphuric acid than the autoclave feed solution 22. The resulting solution 46 can again be 15 treated by a membrane in a second membrane treatment step 48 to recover some of the sulphuric acid. Preferably the membrane employed in the second membrane treatment step 48 is an NF membrane. Examples of NF membranes commercially 20 available and that may be suitable are: Koch MPF-30 and GE Osmonics Desal DK. Preferred NF membranes have high acid resistance and a Dalton cut off of around 200 to 300. The membrane permeate 50 is predominantly a sulphuric acid solution 50. The membrane retentate 52 is of similar concentration sulphuric acid to the membrane permeate 50, but 25 contains most of the metal sulphate species in a more concentrated stream. The membrane retentate 52 is further treated to recover the metals in usual metal recovery processing steps, such as a neutralisation step 38 using limestone, a mixed hydroxide precipitation (MHP) step 54 and manganese 30 removal step 56.
WO 2013/026093 PCT/AU2012/000982 12 The membrane permeate 50 (sulphuric acid solution) may be further treated in a separation step to separate the sulphuric acid from water. Advantageously the separation step is carried out using the reverse osmosis (RO) membrane 26. 5 The benefit of treating the leach solution 14 in this way is that the retentate 52 contains less free acid and dissolved iron and aluminium than the original liquor. Therefore less calcium carbonate is required in the subsequent neutralisation step 38, thereby producing less gypsum waste 41 10 and emitting less CO 2 to the atmosphere. Clearly by concentrating the process solutions according to the various steps in the method of the invention (for example in the membrane treatment steps 16, 26 and 48) the volumes of leach liquor to be processed 15 are reduced thereby decreasing the required equipment size, the energy requirements, net water consumption and so on. Test Results Two stages of laboratory test work were completed to evaluate the 20 performance of diffusion dialysis. A sample of leach solution was supplied by an industry partner. The leach solution is a water based solution containing nickel and cobalt (of about 4g/L nickel). The monovalent ions include sodium and potassium. The main divalent ions are nickel, cobalt, copper, zinc, iron(ll), manganese. The main trivalent ions are aluminium, 25 iron(llI) and chrome(ll). Total membrane operating time to date is three months. The lab unit has a total active membrane area of 0.0929 m 2 and a linear flow path of 1.22 m. The unit has two feed solution reservoirs, for water and for the leach liquor. It is equipped with two diaphragm metering pumps to 30 control the flow through the membrane stack for the water/recovered acid and the leach liquor/acid depleted liquor. The-performance-of-the-diffusion- WO 2013/026093 PCT/AU2012/000982 13 dialysis unit was evaluated for the leach liquor supplied. The effect of the following process variables were to be assessed: * total flux * relative flux 5 * feed liquor acid concentration * magnesium sulphate concentration in the PLS and acid recovery stream. A summary of the diffusion dialysis test results is shown in Table 1. PLS feed Reclaim Acid Monovalent Divalent Trivalent Data point flux to reject recovery metal retal metal (PLS)_fluxrejection rejection rejection L/(m 2 .h)- v/v % % % % Program I A 1.0 0.6 75 92.3 98.0 98.0 B 1.0 1.1 92 96.0 98.6 97.9 C 1.3 1.0 78 93.3 98.2 98.4 D - 2.3 1.0 59 96.7 98.8 99.0 E 2.4 0.7 54 97.4 99.4 99.2 Program 2 IA 0.7 1.1 77 - 1B 1.3 0.6 49 - -- - IC 2.3 0.4 37 - 2A 0.7 10 76 - - 2B 1.5 0.5 50 - - 2C 2.4 0.3 3O - -- 3A 0.8 1.0 82 3B 1.5 0.5 46 - 3C 2.4 0.4 28 Table 1: Summary of diffusion dialysis test work results 10 The diffusion dialysis test rig was first operated continuously for a month on real plant PLS (Program 1), with no appreciable decrease in performance over the period of tests. The test rig was then operated for a second month of continuous operation on synthetic solutions (Program 2), again without decrease in performance over the period of the tests. The acid recovery 15 performance was excellent, with over 90% of sulphuric acid recovery achievable, with only 1 - 4 % of metals permeating through the membranes when operating on real plant PLS.
WO 2013/026093 PCT/AU2012/000982 14 The second month of operation demonstrated that recycling magnesium sulphate solution to the water (acid recovery) side did not impact acid recovery significantly. This enables higher water recycle rates within the overall process flow sheet. 5 The lower acid recovery in the synthetic tests compared to the plant PLS tests at a given total flux rate demonstrates the inherent benefit of diffusion dialysis compared to other membrane systems. The synthetic tests were completed with lower total sulphate concentration in solution than the actual plant PLS samples. This demonstrates the benefit of high metal sulphates in 10 solution providing increased driving force for sulphate through the membrane. The selection of flux rate is a tradeoff between acid recovery and capital cost. The highest possible reject flux rate decreases the number of membrane cells required to process the PLS, but reduces the acid recovery. 15 It is also desirable to operate at the lowest reclaim to reject flux ratio, as this minimises the amount of water addition to the process and increases the concentration of the recovered acid. Now that preferred embodiments of a method for the separation of 20 multivalent species from monovalent species (such sulphuric acid) in an acidic leach solution have been described in detail, as well as the further steps to recover sulphuric acid, it will be apparent that the described embodiments provide a number of advantages over the prior art, including the following: 25 (i) Neutralisation of excess acid by limestone generates vast quantities of carbon dioxide and gypsum waste. The preferred method reduces the environmental impact, both by reducing greenhouse gas emissions and the required tailings storage footprint. 30 WO 2013/026093 PCT/AU2012/000982 15 (ii) Any neutralised excess acid increases the net acid requirements for the nickel leach circuit. By returning the recovered acid to the leach circuit, the costs associated with the production of sulphuric acid are reduced. 5 (iii) Iron and aluminium sulphate can be partially precipitated prior to neutralisation and the acid generated by the precipitation reactions can be partially recovered. The recovered acid can be returned to the leach circuit, reducing the costs associated with 10 the sulphuric acid production. (iv) The net raw water requirements for the process plant are reduced. Depending on the plant location, decreasing water consumption may significantly reduce costs. 15 (v) Membrane technology has advanced to the point where it can be considered for large-scale industrial processes. 20 It will be readily apparent to persons skilled in the relevant arts that various modifications and improvements may be made to the foregoing embodiments, in addition to those already described, without departing from the basic inventive concepts of the present invention. Therefore, it will be appreciated that the scope of the invention is not limited to the specific 25 embodiments described.
Claims (52)
1. A method for the separation of multivalent species from monovalent 5 species in an acidic leach solution, the method comprising the steps of: i) passing the acidic leach solution through a membrane in a membrane treatment step to separate a membrane permeate and a membrane retentate; 10 ii) recovering the membrane permeate containing the monovalent species; and iii) collecting the membrane retentate containing the multivalent species.
2. A method for the separation of multivalent species from monovalent 15 species as defined in claim 1, wherein the acidic leach solution is a leach solution from a metal recovery process.
3. A method for the separation of multivalent species from monovalent species as defined in claim 2, wherein the metal recovery process is a 20 process for the recovery of nickel and/or cobalt from lateritic ore or concentrate.
4. A method for the separation of multivalent species from monovalent species as defined in claim 3, wherein the acidic solution is a sulphuric acid 25 solution.
5. A method for the separation of nickel and other valuable metals leached from lateritic ore using sulphuric acid, the method comprising the steps of: 30 i) passing an acidic leach solution containing the nickel and other valuable metals through a membrane in a membrane treatment step to separate a membrane permeate and a membrane retentate; WO 2013/026093 PCT/AU2012/000982 17 ii) recovering the membrane permeate containing the sulphuric acid; and, iii) collecting the membrane retentate containing the nickel and other valuable metals for further processing. 5
6. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 5, wherein the membrane treatment step comprises nano-filtration. 10
7. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 6, wherein the membrane is a nano filtration (NF) membrane.
8. A method for the separation of nickel and other valuable metals leached 15 from lateritic ore as defined in claim 7, wherein the NF membrane has high acid resistance and a Dalton cut off of around 200 to 300.
9. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 8, wherein the NF membranes is a 20 Koch MPF-30 or GE Osmonics Desal DK membrane.
10. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 5, wherein the membrane treatment step may comprise reverse osmosis. 25
11. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 5, wherein the membrane treatment step comprises nano-filtration combined with reverse osmosis. 30
12. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 5, wherein the membrane treatment step comprises diffusion-dialysis. WO 2013/026093 PCT/AU2012/000982 18
13. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 5, wherein the method also comprises a pre-treatment step prior to the membrane treatment step, the pre-treatment 5 step comprising the removal of residual tailings solids from the acidic leach solution.
14. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 13, wherein the pre-treatment step 10 comprises clarification and/or filtration of the acid leach solution to form a treated acidic leach solution which is then passed to the membrane treatment step.
15. A method for the separation of nickel and other valuable metals leached 15 from lateritic ore as defined in claim 12, wherein subsequent to the membrane treatment step the collected membrane retentate is treated to remove iron and aluminium using a pressurised autoclave, and the solids precipitated in the autoclave are separated from the solution by means of a solid/liquid separation step. 20
16. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 15, wherein the resulting solution from the solid/liquid separation step is again treated by a membrane in a second membrane treatment step to recover some of the sulphuric acid. 25
17. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 16, wherein the membrane in the second membrane treatment step is a nano-filtration (NF) membrane. 30
18. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 17, wherein the NF membrane has high acid-resistance-and-a-Dalton-cut-off-of-arotnd200--to30, and the WO 2013/026093 PCT/AU2012/000982 19 membrane permeate consists predominantly of water and sulphuric acid, which pass through the membrane as monovalent H* and HS0 4 ions.
19. A method for the separation of nickel and other valuable metals leached 5 from lateritic ore as defined in claim 18, wherein the membrane retentate contains the remaining water, plus the majority of the metal sulphate solute species in a more concentrated stream.
20. A method for the separation of nickel and other valuable metals leached 10 from lateritic ore as defined in claim 12 or claim 18, wherein the membrane permeate is further treated in a separation step to separate the sulphuric acid from water.
21. A method for the separation of nickel and other valuable metals leached 15 from lateritic ore as defined in claim 20, wherein the separation step is carried out using a reverse osmosis (RO) membrane.
22. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 21, wherein RO membranes are 20 Hydranautics ESPA1 4040 and Dow Filmtec TW-30 membranes.
23. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 22, wherein the majority of the water typically passes through the RO membrane while the sulphuric acid is 25 retained forming a more concentrated sulphuric acid.
24. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 23, wherein the more concentrated sulphuric acid is fed to an acid stream. 30 WO 2013/026093 PCT/AU2012/000982 20
25. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 24, wherein the acid stream is returned to the leach circuit, reducing overall acid consumption. 5
26. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 23, wherein the water which passes through the RO membrane is used as a slightly acidic water source elsewhere in the nickel process flowsheet. 10
27. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 26, wherein the slightly acidic water source is used as wash water in the counter current decantation, (CCD) circuit. 15
28. A method for the separation of nickel and other valuable metals leached from lateritic ore as defined in claim 15, wherein the membrane retentate containing the various metal species is further treated to recover the metals using usual metal recovery processing steps. 20
29. A method for the separation of multivalent metal species from sulphuric acid in a sulphuric acid leach solution, the method comprising: i) passing the sulphuric acid leach solution through a membrane in a 25 membrane filtration step to separate a permeate and a retentate, the permeate comprising sulphuric acid and the retentate comprising a multivalent metal sulphate solution; ii) recovering the permeate comprising sulphuric acid; and iii) treating the retentate to remove iron and aluminium. 30 WO 2013/026093 PCT/AU2012/000982 21
30. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 29, wherein the sulphuric acid leach solution is a leach solution from a metal recovery process. 5
31. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 30, wherein the metal recovery process is a process for the recovery of nickel and/or cobalt from lateritic ore or concentrate.
32. A method for the separation of multivalent metal species from sulphuric 10 acid as defined in claim 29, wherein the membrane in the membrane filtration step is a diffusion dialysis membrane.
33. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 29, wherein the membrane in the membrane 15 filtration step is an NF membrane.
34. A method for the separation of multivalent metal species from sUlphuric acid as defined in claim 29, wherein the membrane filtration step comprises reverse osmosis. 20
35. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 29, wherein the iron and aluminium removal step is carried out using a pressurised autoclave to remove iron and aluminium sulphate from the retentate solution to form an autoclave treated solution. 25
36. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 29, wherein the iron and aluminium removal step is carried out at a temperature in the range of about 150-250*C. 30
37. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 36, wherein the iron and aluminium removal step is carried-out-at-a-temperature of about-200*C. WO 2013/026093 PCT/AU2012/000982 22
38. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 35, wherein the autoclave treated solution may be subjected to a solid liquid separation step. 5
39. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 38, wherein the solid liquid separation step involves thickening and/or filtration. 10
40. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 39, wherein the resulting solids free solution from the solid liquid separation step passes to a further membrane treatment step. 15
41. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 40, wherein the further membrane treatment step is effected by using an NF membrane.
42. A method for the separation of multivalent metal species from sulphuric 20 acid as defined in claim 41, wherein further sulphuric acid is generated by passing the autoclave treated solution through the NF membrane in the further membrane treatment step.
43. A method for the separation of multivalent metal species from sulphuric 25 acid as defined in claim 36, wherein the resulting NF permeate comprises the monovalent species such as sulphuric acid, and the resulting NF retentate comprises the multivalent species.
44. A method for the separation of multivalent metal species from sulphuric 30 acid as defined in claim 43, wherein the NF permeate comprises water and solute species which pass through the pores in the membrane, and the NF WO 2013/026093 PCT/AU2012/000982 23 retentate comprises water and solute species which do not pass through the membrane.
45. A method for the separation of multivalent metal species from sulphuric 5 acid as defined in claim 44, wherein the NF membrane rejects the majority of divalent and trivalent solute species while allowing monovalent species to pass through relatively unhindered.
46. A method for the separation of multivalent metal species from sulphuric 10 acid as defined in claim 45, wherein the NF permeate consists predominantly of water, and sulphuric acid, which pass .through the membrane as monovalent H* and HS0 4 ions.
47. A method for the separation of multivalent metal species from sulphuric 15 acid as defined in claim 45, wherein the NF retentate contains the remaining water, plus the majority of the metal sulphate solute species.
48. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 46, wherein the NF permeate is further treated in a 20 separation step to separate the sulphuric acid from water..
49. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 48, wherein the separation step is carried out using a reverse osmosis (RO) membrane. 25
50. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 49, wherein the RO membrane is a Hydranautics ESPA1 4040 or a Dow Filmtec TW-30 membrane. 30
51. A method for the separation of multivalent metal species from sulphuric acid as defined in claim 49, wherein the majority of the water typically WO 2013/026093 PCT/AU2012/000982 24 passes through the RO membrane while the sulphuric acid is retained forming a more concentrated sulphuric acid solution.
52. A method for the separation of multivalent metal species from sulphuric 5 acid as defined in claim 47, wherein the NF retentate containing the various metal species is further treated to recover the metals using usual metal recovery processing steps.
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| AU2011903354A AU2011903354A0 (en) | 2011-08-22 | Method for the Treatment of Acidic Leach Liquors | |
| AU2012300185A AU2012300185B2 (en) | 2011-08-22 | 2012-08-22 | Method for the treatment of acidic leach liquors |
| PCT/AU2012/000982 WO2013026093A1 (en) | 2011-08-22 | 2012-08-22 | Method for the treatment of acidic leach liquors |
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| CA3185166A1 (en) * | 2020-05-29 | 2021-12-02 | Toray Industries, Inc. | Method for separating and recovering cobalt salt and nickel salt |
| CN114262804B (en) * | 2021-12-24 | 2023-07-04 | 四川顺应动力电池材料有限公司 | Method for high-value comprehensive utilization of laterite nickel ore resources |
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| WO1998056494A1 (en) * | 1997-06-09 | 1998-12-17 | Hw Process Technologies, Inc. | Method for separating and isolating precious metals from non precious metals dissolved in solutions |
| WO2008034189A1 (en) * | 2006-09-21 | 2008-03-27 | Metallica Minerals Ltd | Improved process and plant for producing nickel |
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|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) | ||
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |