WO2002022898A1 - Separation de cobalt de manganese par extraction au moyen d'un solvant a base d'acide organophosphorique - Google Patents

Separation de cobalt de manganese par extraction au moyen d'un solvant a base d'acide organophosphorique Download PDF

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WO2002022898A1
WO2002022898A1 PCT/AU2001/001163 AU0101163W WO0222898A1 WO 2002022898 A1 WO2002022898 A1 WO 2002022898A1 AU 0101163 W AU0101163 W AU 0101163W WO 0222898 A1 WO0222898 A1 WO 0222898A1
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solution
aqueous
acid
cobalt
organic solution
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PCT/AU2001/001163
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English (en)
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Chu Yong Cheng
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Commonwealth Scientific And Industrial Research Organisation
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Priority claimed from AUPR0170A external-priority patent/AUPR017000A0/en
Priority claimed from AUPR0169A external-priority patent/AUPR016900A0/en
Application filed by Commonwealth Scientific And Industrial Research Organisation filed Critical Commonwealth Scientific And Industrial Research Organisation
Priority to AU2001293470A priority Critical patent/AU2001293470A1/en
Publication of WO2002022898A1 publication Critical patent/WO2002022898A1/fr

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    • 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
    • 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
    • C22B3/32—Carboxylic acids
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • 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
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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 present invention relates to a method of separating cobalt from other elements contained in an aqueous leach solution.
  • HPAL high pressure acid leach
  • SX-EW solvent extraction - electrowinning
  • the Bulong process uses a direct solvent extraction approach. Cobalt, copper, zinc and manganese are separated from nickel, calcium and magnesium by solvent extraction with Cyanex 272. The nickel in the raffinate is separated from calcium and magnesium by solvent extraction with Versatic 10 and then electrowon.
  • the solution containing cobalt, copper, zinc and manganese is subjected to sulphide precipitation, solids/liquid separation and acid pressure re-leach to separate cobalt, copper and zinc from manganese.
  • the copper is eliminated from the solution by ion exchange and zinc by solvent extraction with D2EHPA.
  • the cobalt is then recovered from the purified solution by electrowinning.
  • An object of the present invention is to provide a practical process for separating cobalt (and nickel if it is present) from impurities (particularly manganese) contained in leach solutions.
  • An object of a preferred embodiment of the invention is to provide process that also provides steps for the recovery of cobalt from such solutions .
  • the present invention provides a method of separating cobalt from impurity elements including manganese contained in an aqueous leach solution, the process including the steps of: (a) contacting the aqueous leach solution with an organic solution comprising an organophosphoric acid (and optionally a modifier) in an organic solvent to produce a loaded organic solution containing manganese and, to the extent that they are present, calcium, zinc and copper, and a some cobalt and, if present in the aqueous leach solution, some nickel and magnesium, and an aqueous raffinate solution containing most of the cobalt and, if they were present in the leach solution, nickel and magnesium; (b) scrubbing the loaded organic solution with an aqueous scrub solution containing (mainly) manganese and copper to produce a scrubbed organic solution containing less cobalt (and nickel if nickel was present in the aqueous leach solution) and a spent aqueous scrub solution containing some cobalt (and nickel if nickel was
  • step (d) selectively stripping the scrubbed organic solution to remove a portion of the manganese and copper to form the aqueous scrub solution for use in step (b) ;
  • step (e) recovering cobalt from the aqueous raffinate produced in step (a) .
  • the aqueous leach solution may be the leach solution obtained from acid digestion of an ore or ore concentrate, or may be a leach solution that has been subjected to other procedures to remove undesired elements therefrom.
  • the leach solution may be one that has been subjected to a preliminary iron precipitation step.
  • nickel is present in the aqueous leach solution, and in step (e) nickel could also recovered from the aqueous raffinate produced in step (a) .
  • the organophosphoric acid is di-2-ethylhexyl phosphoric acid (D2EHPA) , however it will be appreciated by persons skilled in the art that an organophosphoric acid having extraction characteristics similar to D2EHPA could be used.
  • Organophosphoric acids have the formula (RO) P0 2 H, in which R represents an organic group.
  • R represents an organic group.
  • the two organic groups R which may be the same or different, can be selected from optionally substituted branched, straight chained or cyclic alkyl, alkenyl or alkynyl groups.
  • the organic groups are fairly bulky, and have a minimum of 4 carbon atoms, more preferably from 6 to 18 carbon atoms.
  • the organic groups may suitably be n-octyl, cyclooctyl or 2-ethylhexyl .
  • the modifier can any suitable modifier that improves separation of the organic and aqueous phases.
  • Suitable modifiers include 2-ethylhexanol , isodecanol, isotridecanol and tri n-butyl phosphate (TBP) .
  • TBP is the preferred modifier.
  • the organic solvent may be any suitable organic solvent for the organophosphoric acid that achieves good phase separation from the aqueous phase with the modifier, and accordingly the organic solvent could be considered to be a diluent for the organophosphoric acid.
  • Kerosene is the most common solvent/diluent used for this purpose due to its low cost and availability.
  • the scrubbed organic solution may be selectively stripped of manganese and copper by contacting it with an acid. Sulphuric acid is preferred due to its low cost, however other acids such as HC1 and HN0 3 could be used.
  • the partially stripped scrubbed organic solution may be fully stripped of impurity elements by contacting the partially stripped scrubbed organic solution with a second (stronger) acid. Accordingly, when sulphuric acid is used as the first acid, a more concentrated sulphuric acid or hydrochloric acid may be used as the second acid to fully strip the partially stripped scrubbed organic solution of the impurity elements to avoid gypsum formation if the aqueous solution is saturated with calcium. The fully stripped organic solution may then be recycled to step (a) .
  • the range of the Mn and Cu in the aqueous scrub solution will depend on how much Co (and Ni) is to be scrubbed and the aqueous to organic (A/0) ratio.
  • the mole ratio of (Mn+Cu) / (Co+Ni) is at least 1.5 for complete scrubbing.
  • the amount of organophosphoric acid in the organic solution used in step (a) will depend on the concentration of the elements to be extracted and the A/0 ratio, however the amount would typically be in the range of from 3% to 35% v/v, with a preferred range of 5% to 25%. At levels above 35% the organic solution will be too viscous resulting in lower extraction kinetics.
  • the amount of modifier in the organic solution used in step (a) will also vary.
  • the range of modifier will typically be in the range of 3% to 15% v/v, with a preferred range of 5% to 10%.
  • the pH of the aqueous phase is maintained in a range from 3.0 to 4.5 and more preferably 3.5 to 4.0 in step (a) .
  • the temperature is preferably maintained in the range of from 10°C to 60°C, more preferably from 20 to 40°C. Whilst temperatures as low as 10°C are achievable, a temperature lower than 15°C results in high viscosity. At temperatures higher than 60°C there is a risk of evaporation and degradation of the organic phase .
  • the aqueous to organic ratio (A/0) in step (a) is most preferably 1:1, but may lie in the range from 10:1 to 1:10, and preferably 1:2 to 5:1.
  • the aqueous to organic ratio maintained in step (b) may lie within the range of from 1:5 to 1:200, but preferably it is in the range of 1:5 to 1:20.
  • the cobalt may be recovered from the solution by any suitable means.
  • cobalt could be recovered by electrowinning or precipitation.
  • the method may be combined with an organophosphinic acid solvent extraction step as described in further detail below, to effect separation of cobalt from nickel.
  • the present invention also provides a method of separating cobalt from other elements contained in an aqueous leach solution, the process including the steps of subjecting the aqueous leach solution to successive solvent extraction steps using an organophosphoric acid and an organophosphinic acid as extractants.
  • the leach solution is one containing manganese, zinc, copper, cobalt, nickel, calcium and magnesium (as would be the case for a lateritic or bio- leach solution)
  • the organophosphinic acid is used as the first organic extractant, it transfers manganese, zinc, copper and cobalt into an organic strip liquor leaving an aqueous raffinate containing nickel, calcium and magnesium.
  • Treatment of the organic strip liquor from the organophosphinic acid extraction stage with the organophosphoric acid results in a loaded organic solution containing manganese, zinc and copper and an aqueous raffinate containing cobalt.
  • the leach solution is one containing manganese, zinc, copper, cobalt, nickel, calcium and magnesium (as would be the case for a lateritic or bio- leach solution)
  • the organophosphoric acid is used as the first organic extractant
  • the loaded organic solution contains manganese, calcium, zinc and copper
  • the aqueous raffinate solution contains cobalt, nickel and magnesium.
  • Subsequent solvent extraction of the aqueous raffinate with organophosphinic acid results in an organic phase containing cobalt and an aqueous raffinate containing nickel and magnesium.
  • the organophosphinic acid is di-2,4,4- trimethylpentyl phosphinic acid (eg Cyanex 272).
  • organophosphinic acids have the formula R 2 PO 2 H, in which R represents an organic group.
  • the two organic groups R which may be the same or different, can be selected from optionally substituted branched, straight chained or cyclic alkyl, alkenyl or alkynyl groups .
  • the organic groups are fairly bulky, and have a minimum of 4 carbon atoms, more preferably from 6 to 18 carbon atoms.
  • the organic groups are preferably unsubstituted branched, straight chained or cyclic alkyl groups, and may suitably be n-octyl, cyclooctyl, 2-ethylhexyl or 2 , 4, 4-trimethylpentyl .
  • alkyl used either alone or in a compound word such as “optionally substituted alkyl” or
  • cycloalkyl denotes straight chain, branched or mono- or poly- cyclic alkyl, preferably Cl-30 alkyl or cycloalkyl .
  • straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isbutyl, sec-butyl, tert-butyl, amyl, isoamyl, sec- amyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, hexyl, 4- methylpentyl , 1-methylpentyl, 2-methylpentyl, 3- methylpentyl, 1, 1-dimethylbutyl, 2 , 2-dimethylbutyl, 3,3- dimethylbutyl , 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 1,2,2- trimethylpropyl , 1, 1, 2-trimethylpropyl, heptyl, 5- methylhexyl
  • cyclic alkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl and the like.
  • the alkyl may optionally be substituted by any non-deleterious substituent .
  • optionally substituted means that a group may or may not be further substituted with one or more groups selected from alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, benzylamino, dibenzylamino, acyl, alkenylacyl, alkynylacyl, arylacyl, acylamino, diacylamino,
  • Suitable optional substituents will be chosen on the basis that the organophosphinic or organophosphoric acid have the desired extraction characteristics, and the substituents do not react with any other component of the mixture under the given extraction conditions .
  • halogen denotes fluorine, chlorine, bromine or iodine.
  • organophosphinic acid in the organic solution used in the organophosphinic acid solvent extraction step will depend on the concentration of the elements to be extracted and the A/0 ratio, however the amount would typically be in the range of from 3% to 35% v/v, with a preferred range of 5% to 25%. At levels above 35% the organic solution will be too viscous resulting in lower extraction kinetics.
  • organophosphinic acid extraction stage it is also advantageous to use a modifier in the organophosphinic acid extraction stage as for the organophosphoric acid extraction stage. Again, TBP is preferred.
  • the pH of the aqueous phase is maintained in a range from 5.0 to 6.0 in the organophosphinic acid solvent extraction circuit .
  • the temperature is preferably maintained in the range of from 10°C to 60°C, more preferably from 20 to 40°C. Whilst temperatures as low as 10°C are achievable, a temperature lower than 15°C results in high viscosity. At temperatures higher than 60°C there is a risk of evaporation and degradation of the organic phase.
  • the aqueous to organic ratio (A/0) in the organophosphinic acid solvent extraction circuit is most preferably 1:1, but may lie in the range from 3:1 to 1:3.
  • the cobalt extracted into the loaded organic phase in the organophosphinic acid extraction circuit is stripped therefrom and either recovered (when following the organophosphoric acid extraction stage) or directed to the organophosphoric acid extraction stage.
  • the A/0 ratio may be from 1:2 up to 1:200, and the pH from 2.0 to 4.0.
  • Other details concerning the organophosphinic acid extraction stage are well within the knowledge and experience of persons in the art of the invention .
  • the steps outlined above can be conducted in combination with other solvent extraction steps and optionally one or more precipitation steps to separate certain elements from each other.
  • a preliminary iron precipitation step to be conducted to precipitate out iron to leave an aqueous leach solution containing the target elements.
  • precipitation steps involving precipitation out of the target elements such as cobalt and nickel
  • re-leaching of the precipitate can be avoided. Even when such a precipitation step is required, it is to be noted that no precipitation steps for the purpose of separating manganese from cobalt are required.
  • the process does not include a sulphide precipitation stage for separating cobalt from manganese.
  • the process does not include a precipitation step involving precipitation out of the target elements and re-leaching of the precipitate.
  • scrubbing stages of the type well known in the art may be used for recovering elements even if the scrubbing stages are not specifically mentioned.
  • the design of the optimum arrangement of scrubbing stages will depend on the specific aqueous leach solution and the elements desired to be recovered therefrom (and target percentage recovery levels) .
  • the present invention also provides a plant for conducting the methods and processes described above, the plant including: a solvent extraction contactor in which the aqueous leach solution is contacted with the organophosphoric acid-containing organic solution; a scrubbing contactor for scrubbing the loaded organic solution generated in solvent extraction contactor; a loaded organic solution conduit for conducting the loaded organic solution generated in the solvent extraction contactor to the scrubbing contactor; a stripping contactor in which the scrubbed organic solution generated in the scrubbing contactor is subjected to selective stripping to generate the aqueous scrub solution for use in the scrubbing contactor; a scrubbed organic solution conduit for conducting the scrubbed organic solution to the stripping contactor; - an aqueous scrub solution conduit for conducting the aqueous scrub solution to the scrubbing contactor; and a spent aqueous scrub solution conduit for conducting the spent aqueous scrub solution from the scrubbing contactor to the solvent extraction contactor.
  • the plant • further includes an organic solution recycle conduit for conducting the partially stripped scrubbed solution from the stripping contactor to the solvent extraction contactor. More preferably, a bulk stripping contactor is located in this recycle conduit, in which the partially stripped scrubbed solution is stripped of remaining impurities before being conducted to the solvent extraction contactor.
  • the solvent extraction contactor is preferably a countercurrent solvent extraction contactor. Similarly, further scrubbing stages and vessels may be included in the plant .
  • the plant will also include an organophosphinic acid solvent extraction contactorextraction circuit.
  • This circuit will include an organophosphinic acid solvent extraction contactor (preferably countercurrent), and one or more scrubbing contactors, together with the appropriate conduits for passing the various streams between the vessels in the plant.
  • the plant will also include a cobalt recovery stage, for instance a cobalt precipitation vessel or an electrolytic cell in which a cobalt electrowinning process can be conducted.
  • the arrangement of an appropriate plant including all of these elements is well within the skill of a person in the art of the invention now that the direction has been made to conduct the process for recovering cobalt as described above.
  • Figure 1 illustrates a flow chart for the di-2- ethylhexyl phosphoric acid solvent extraction step of the process of one preferred embodiment of the invention, and represents schematically a plant of one preferred embodiment of the invention
  • Figure 2 illustrates a schematic flow chart for one embodiment of the successive organophosphoric and organophosphinic acid solvent extraction process of the invention, and represents schematically a plant for this embodiment of the invention
  • Figure 3 illustrates a schematic flow chart for a second embodiment of the successive organophosphinic and organophosphoric acid solvent extraction process of the invention, and represents schematically a plant for this embodiment of the invention.
  • aqueous leach solution 1 (which may be the input aqueous leach solution - the "cobalt solution” in Figure 3 - or the strip liquor in Figure 2, or any other leach solution) is fed into a countercurrent solvent extraction contactor 2 in which the aqueous leach solution 1 is contacted with an organic extractant solution 3 comprising a solution of an organophosphoric acid (preferably D2EHPA) and a modifier (preferably TBP) in an organic solvent (preferably kerosene) .
  • an organophosphoric acid preferably D2EHPA
  • TBP modifier
  • the aqueous raffinate 4 from the solvent extraction contains most of the cobalt, nickel and a large proportion of the magnesium from which the cobalt and nickel may be recovered.
  • the aqueous raffinate 4 from the organophosphoric extraction stage contains cobalt.
  • the loaded organic liquor 5 from the solvent extraction contactor 2 is scrubbed in a scrubbing contactor 6 with a scrub solution 7 containing manganese and copper.
  • Scrubbed loaded organic solution 8 is selectively stripped with a first acid, a dilute sulphuric acid 9, in a stripping contactor 10 to form scrub solution 7, part of which is recycled to scrubbing contactor 6.
  • Partially stripped organic extractant 11 is then stripped of all impurities with a second acid, dilute hydrochloric acid 12, in a bulk stripping contactor 13.
  • Stripped organic solution 3 is recycled to extraction contactor 2.
  • Figure 2 shows the aqueous leach solution being subjected to a first solvent extraction with an organophosphinic acid, followed by a second solvent extraction step with di-2-ethylhexyl phosphoric acid.
  • Figure 3 shows the aqueous leach solution being subjected to a first solvent extraction using di-2-ethylhexyl phosphoric acid dissolved in kerosene, followed by solvent extraction of the aqueous raffinate with an organophosphinic acid.
  • the aqueous solution was a synthetic iron-free laterite leach solution containing 2.60 g/L Ni, 0.24 g/L Co, 0.27 g/L Zn, 0.52 g/L Ca, 0.09 g/L Cu, 1.87 g/L Mn and 2.89 g/L Mg.
  • the organic solution consisted of 12% di-2- ethylhexyl phosphoric acid (D2EHPA) , 2.5% tri-n-butyl phosphate (TBP) and 85.5% kerosene (Shellsol 2046), all by volume.
  • D2EHPA di-2- ethylhexyl phosphoric acid
  • TBP tri-n-butyl phosphate
  • Shellsol 2046 85.5% kerosene
  • the pH in the four mixers was controlled at 3.7 using three pH controllers with the addition of ammonia solution (Fig 1) .
  • the results are shown in Table 1. All the zinc, calcium, manganese and copper were extracted in four stages. Some 12.6% cobalt, 20% magnesium and no nickel were co-extracted. The raffinate contained only cobalt, nickel and magnesium.
  • One selective strip stage was used at an A/0 flowrate ratio of 1:5 with 14.9 g/L sulphuric acid.
  • the results are shown in Table 3.
  • the strip raffinate contained 7.3 g/L manganese and 0.54 g/L copper, which was just slightly higher than the scrubbing solution used in the previous stage (6.78 g/L manganese and 0.35 g/L copper) .
  • This could be easily corrected by using slightly more dilute sulphuric acid for stripping, say 12 g/L.
  • the chloride and magnesium concentration in the leach solution could be very high if saline water is used as process water in the plant.
  • the aqueous solution was a synthetic laterite leach solution containing 2.67 g/L Ni, 0.20 g/L Co, 0.29 g/L Zn, 0.50 g/L Ca, 0.08 g/L Cu, 1.80 g/L Mn, 13.3 g/L Mg and 17.7 g/L Cl .
  • the organic solution consisted of 12% di-2-ethylhexyl phosphoric acid (D2EHPA) , 2.5% tri-n-butyl phosphate (TBP) and 85.5% kerosene (Shellsol 2046), all by volume.
  • D2EHPA di-2-ethylhexyl phosphoric acid
  • TBP tri-n-butyl phosphate
  • Shellsol 2046 85.5% kerosene
  • the scrubbed organic solution would be selectively stripped with dilute sulphuric acid (part of which would be used as scrubbing solution) and then bulk-stripped with hydrochloric acid. The stripped organic would returned for extraction.
  • the aim of the extraction is to extract all the zinc, calcium, copper and manganese from the aqueous leach solution (PLS - "plant leach solution”) into the organic D2EHPA solution and to minimise the extraction of cobalt, nickel and magnesium.
  • the cobalt bio-leach solution contained 0.04 g/L Zn, 0.53 g/L Ca, 0.08 g/L Mn, 0.19 g/L Cu, 0.37 g/L Co, 0.01 g/L Ni and 0.32 g/L Mg.
  • the organic extraction solution consisted of 6% di-2-ethylhexyl phosphoric acid (D2EHPA) , 10% tri-n- butyl phosphate (TBP) and 84% kerosene (Shellsol 2046) , all by volume.
  • D2EHPA di-2-ethylhexyl phosphoric acid
  • TBP tri-n- butyl phosphate
  • Shellsol 2046 84% kerosene
  • the pH in the three mixers was controlled at 3.7 using three pH controllers with the addition of ammonia solution (Fig 1) .
  • the results are shown in Table 6. All the zinc, calcium, manganese and copper were extracted in three stages. Some 16% cobalt, 1% nickel and 62% magnesium were co-extracted. The raffinate contained only cobalt, nickel and magnesium.
  • the above raffinate containing Co, Ni and Mg is subjected to a subsequent solvent extraction step where cobalt is extracted from the aqueous solution by di-2, 4, 4-trimethylpentyl phosphinic acid (Cyanex 272), using a well proven commercial process.
  • the cobalt is then recovered by electrowinning (as illustrated in the process of Figure 3 - this is the preferred method of recovery according to this embodiment of the invention) or hydroxide precipitation.
  • the aim of scrubbing is to scrub all of the co- extracted cobalt (and nickel, to the extent that it is in the organic extraction solution, and likewise magnesium) from the organic D2EHPA extraction solution to the aqueous scrub raffinate and to minimise the scrubbing of manganese, copper, calcium and zinc.
  • Two scrubbing stages were used with a combined solution of sulphuric acid (4.4 g/L) manganese (0.01 g/L) and copper (0.02 g/L) at A/O flowrate ratio of 1:4. Scrubbing results are listed in Table 7.
  • the cobalt and nickel scrubbing efficiencies were 100% with no cobalt and nickel being left in the organic solution.
  • This scrub raffinate containing 0.30 g/L cobalt would be recycled back to the feed (PLS) . By doing this, the cobalt and nickel recovery would approach 100%.
  • the aim of selective stripping is to generate a solution containing mainly manganese and copper for using as scrubbing solution in the previous stage.
  • One selective strip stage was used at an A/O flowrate ratio of 1:5 using 5 g/L sulphuric acid.
  • the results are shown in Table 8.
  • the strip raffinate generated by this procedure was too strong (too much Zn, Ca, Mn and Cu present) to use as a scrubbing solution. However this would be corrected by using a more dilute acid for stripping, say 2 g/L sulphuric acid.
  • the ' aim of bulk stripping is to re-generate the D2EHPA organic solution by stripping all elements from the organic extractant.
  • Two bulk strip stages were used at an A/O flowrate ratio of 1:5 with 10 g/L hydrochloric acid.
  • the results are also shown in Table 8. Some zinc and calcium were left in the organic solution. However this could be corrected by using a slightly stronger hydrochloric acid, say 15 g/L. If no calcium is present in the feed, sulphuric acid can be used for bulk stripping.
  • the aqueous solution was a bio-leach solution containing 0.010 g/L Ni, 0.387 g/L Co, 0.041 g/L Zn, 0.565 g/L Ca, 0.352 g/L Cu, 0.072 g/L Mn and 0.300 g/L Mg.
  • the organic solution consisted of 4% di-2 , 4, 4-trimethylpentyl phosphinic acid (eg Cyanex 272), 5% tri-n-butyl phosphate (TBP) and 91% kerosene (Shellsol 2046), all by volume.
  • Three counter-current extraction stages were used at an A/O flowrate ratio of 1.5:1.
  • the pH in the three mixers was controlled at 5.5 using three pH controllers with the addition of ammonia solution.
  • the results are shown in Table 9. All zinc, and almost all cobalt, manganese and copper were extracted. Small amounts of calcium, nickel and magnesium was co-extracted. Since the concentration of calcium, nickel and magnesium in the organic solution was low, scrubbing was not necessary.
  • a synthetic aqueous solution mimicking the strip liquor from the previous circuit (Cyanex 272 circuit) containing 0.093 g/L Zn, 0.330 g/L Mn, 1.518 g/L Cu and 1.041 g/L Co was used as the feed for the D2EHPA circuit.
  • the organic solution consisted of 5% di-2-ethylhexyl phosphoric acid (D2EHPA) , 5% tri-n-butyl phosphate (TBP) and 90% kerosene (Shellsol 2046), all by volume.
  • Three counter-current extraction stages were used at an A/O flowrate ratio of 1.1:1.
  • the pH in the three mixers was controlled at 3.70 using three pH controllers with the addition of sodium hydroxide solution. The results are shown in Table 11. Almost all the zinc, manganese and copper were extracted. Some 8% of cobalt was co-extracted, which would be scrubbed in the next stage .
  • the scrubbed organic solution was bulk-stripped with sulphuric acid.
  • the stripped organic would be returned for extraction.

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Abstract

Cette invention a trait à un procédé de séparation de cobalt présent dans des impuretés renfermant du manganèse dans une solution aqueuse de lixiviation. Ce procédé comporte une étape d'extraction faisant intervenir un solvant à base d'acide organophosphorique consistant, (a), à mettre en contact la solution aqueuse de lixiviation avec une solution organique contenant un acide organophosphorique dans un solvant organique afin d'obtenir une solution organique chargée contenant du manganèse et, le cas échéant, du calcium, du zinc et du cuivre ainsi qu'une certaine quantité de cobalt et une solution aqueuse de raffinat contenant la majeure partie du cobalt, (b), à laver la solution organique chargée avec une solution aqueuse de lavage contenant du manganèse et du cuivre afin de produire une solution organique lavée contenant moins de cobalt ainsi qu'une solution aqueuse de lavage épuisée contenant une certaine quantité de cobalt ainsi que du manganèse, (c), à recycler la solution aqueuse de lavage épuisée en vue d'une utilisation en phase (a), (d), à procéder à un tri sélectif de la solution organique aqueuse lavée afin d'enlever une partie du manganèse et du cuivre pour former la solution aqueuse de lavage à utiliser dans la phase (b) et, (e), à récupérer le cobalt dans le raffinat aqueux produit lors de la phase (a).
PCT/AU2001/001163 2000-09-15 2001-09-14 Separation de cobalt de manganese par extraction au moyen d'un solvant a base d'acide organophosphorique WO2002022898A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001293470A AU2001293470A1 (en) 2000-09-15 2001-09-14 Separation of cobalt from manganese using organophosphoric acid solvent extraction

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPR0170 2000-09-15
AUPR0169 2000-09-15
AUPR0170A AUPR017000A0 (en) 2000-09-15 2000-09-15 A novel process to recover cobalt from aqueous solutions using solvent extraction
AUPR0169A AUPR016900A0 (en) 2000-09-15 2000-09-15 Separqtion of manganese from cobalt and nickel by solvent extraction

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WO2002022898A1 true WO2002022898A1 (fr) 2002-03-21

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087308A1 (fr) 2003-03-31 2004-10-14 Medical Research Council Methode de synthese et d'essai de bibliotheques combinatoires au moyen de microcapsules
CN102464372A (zh) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 一种含锰废水的处理方法
CN106544505A (zh) * 2015-09-16 2017-03-29 金发科技股份有限公司 一种萃取剂组合物及其制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3411885A1 (de) * 1984-03-30 1985-10-10 Hermann C. Starck Berlin, 1000 Berlin Verwendung eines synergistischen extraktionsmittelgemisches fuer die co/ni-trennung
KR940007372B1 (ko) * 1992-09-22 1994-08-16 김병남 코발트를 주성분으로 하는 공구 스크랲으로부터 코발트를 분리, 정제하는 방법
AU4089096A (en) * 1995-01-09 1996-07-18 Lionore Australia (Avalon) Pty Ltd The recovery of nickel and cobalt from lateritic ores

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3411885A1 (de) * 1984-03-30 1985-10-10 Hermann C. Starck Berlin, 1000 Berlin Verwendung eines synergistischen extraktionsmittelgemisches fuer die co/ni-trennung
KR940007372B1 (ko) * 1992-09-22 1994-08-16 김병남 코발트를 주성분으로 하는 공구 스크랲으로부터 코발트를 분리, 정제하는 방법
AU4089096A (en) * 1995-01-09 1996-07-18 Lionore Australia (Avalon) Pty Ltd The recovery of nickel and cobalt from lateritic ores

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; Class J01, AN 1996-219924/22 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087308A1 (fr) 2003-03-31 2004-10-14 Medical Research Council Methode de synthese et d'essai de bibliotheques combinatoires au moyen de microcapsules
CN102464372A (zh) * 2011-10-20 2012-05-23 常州亚环环保科技有限公司 一种含锰废水的处理方法
CN106544505A (zh) * 2015-09-16 2017-03-29 金发科技股份有限公司 一种萃取剂组合物及其制备方法与应用

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