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EP0047076A1 - Procédé de production de poudre métallique de cobalt - Google Patents

Procédé de production de poudre métallique de cobalt Download PDF

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Publication number
EP0047076A1
EP0047076A1 EP81303653A EP81303653A EP0047076A1 EP 0047076 A1 EP0047076 A1 EP 0047076A1 EP 81303653 A EP81303653 A EP 81303653A EP 81303653 A EP81303653 A EP 81303653A EP 0047076 A1 EP0047076 A1 EP 0047076A1
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EP
European Patent Office
Prior art keywords
cobalt
reduction
powder
solution
cobalt powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP81303653A
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German (de)
English (en)
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EP0047076B1 (fr
Inventor
Eric August Devuyst
Victor Alexander Ettel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vale Canada Ltd
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Vale Canada Ltd
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Filing date
Publication date
Application filed by Vale Canada Ltd filed Critical Vale Canada Ltd
Publication of EP0047076A1 publication Critical patent/EP0047076A1/fr
Application granted granted Critical
Publication of EP0047076B1 publication Critical patent/EP0047076B1/fr
Expired legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
    • 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

Definitions

  • the present invention relates to the production of cobalt metal powder by hydrogen reduction from a cobalt containing.solution.
  • Hydrogen-reduced elemental cobalt powder is an article of commerce.
  • One presently available product of this type is known to be produced by hydrogen reduction of aqueous cobalt ammine ammonium sulphate solutions using a catalyst for example sodium sulphite- sodium cyanide.
  • the nucleation of cobalt powder in this .system is irregular, resulting in production of powder having an apparent density of 0.6 to 1 grams/cubic centimeter (g/cc).
  • repeated densification cycles are employed which deposit further cobalt upon the initially formed powder from fresh cobalt-containing solution.
  • the cobalt bite per reduction cycle is of the order of about 40 g/l.
  • About 30% of the cobalt metal produced is recycled and redissolved in a step in which cobaltic ions are reduced to cobaltous ions in a feed cobaltic ammine ammonium sulphate solution in order to obtain the starting solution for the hydrogen reduction stage.
  • the average hydrogen reduction cycle is reported to require about 30 minutes.
  • the final cobalt powder particles have an irregular shape with a rough pebbly surface. In many instances the powder is dark grey to black in colour.
  • the cobalt powder produced must be handled carefully and exposure to air should be avoided until the powder product is cool. Drying of the washed cobalt powder is usually conducted in an atmosphere of hydrogen or nitrogen.
  • a process of making dense cobalt powder of coarse, relatively uniform particle size which comprises subjecting a portion of a cobaltous sulphate solution to hydrogen reduction at a hydrogen partial pressure of at least one megapascal.and a temperature of at least 180°C in the presence.of a reaction initiator while introducing a solution of an alkali metal hydroxide or ammonium hydroxide at a rate not substantially exceeding the molar equivalent of the rate of sulphuric acid production due to hydrogen reduction, continuing the hydrogen reduction to reduce a substantial part of the cobalt content of said portion to produce an end reduction solution and cobalt powder, repeating said hydrogen reduction cyclically with fresh successive portions of cobaltous sulphate solution with each successive reduction being performed in the presence of co
  • the cobalt sulphate.solution will generally contain between about 50 and 100 grams per litre of cobalt and the hydrogen reduction is preferably stopped when about 80 to 95% of the cobalt has been reduced.
  • the pH of the solution is preferably not greater than 4 during any of the hydrogen reduction steps.
  • the number of densification steps, i.e. hydrogen reduction steps, employed is not important, the process being operated until the desired particle size and powder density is obtained.
  • ammonium hydroxide leads to problems in separating ammonium sulphate from the solution remaining after hydrogen reduction and it is therefore preferred to use sodium or potassium hydroxide in the neutralisation of the sulphuric acid generated.
  • the seed cobalt powder employed to initiate the precipitation of cobalt during hydrogen reduction may be finely divided cobalt powder produced by a reaction similar to the foregoing or produced from some other source.
  • extra fine cobalt powder having an average particle size in the range of 1 to 20 - microns known in the trade as "Afrimet" powder
  • cobalt powder produced by the thermal decomposition of cobalt oxalate as for example by heating cobalt oxalate at 500°C under nitrogen for 15 minutes may be employed.
  • Seed powder may be generated by nucleation using sodium cyanide and sodium sulphide as nucleating agents in the first hydrogen pressurized batch.
  • self-nucleated cobalt powder from the first reduction liquor may be employed.
  • the respective types of seed cobalt powders have different physical shapes and surface area per unit weight.
  • the very small needle shape particles and large surface area which characterize the Afrimet cobalt powder renders it a preferred starting material.
  • Thermally decomposed cobalt oxalate also produces fine needle-shaped particles but not as fine as the Afrimet product.
  • Powder produced by nucleation with sodium cyanide and sodium sulphide as catalysts is irregularly shaped and of large particle size.
  • Self-nucleated cobalt powder is in the form of large porous powders.
  • the finely divided needle-shaped initiating powders permit densification by growth of individual particles or aggregates of particles during reduction.
  • sulphuric acid is formed for each mole of cobalt sulphate that is reduced. It is important that the rate of addition of sodium hydroxide does not exceed that required to neutralize the sulphuric acid as it forms. Thus, for example, if sulphuric acid is produced at the rate of 200 grams per hour (2.04 moles per hour), sodium hydroxide should be added at a rate not substantially greater than 164 grams (4.1 moles) per hour. If the addition rate of sodium hydroxide exceeds that necessary to neutralize the sulphuric acid formed, cobaltous hydroxide can form which has a tendency to provide self-nucleated cobalt powder and which interferes with densification of the cobalt powder already present. A saturated solution of NaOH or KOH is preferably used to avoid dilution.
  • the source of the cobalt sulphate feed solution treated in accordance with the invention is immaterial.
  • the feed solution should be substantially free of impurities which co-reduce or coprecipitate with cobalt during hydrogen reduction.
  • the contents of nickel, copper, iron and lead should be as low as possible.
  • species such as chloride ion should be very low, e.g., less than 100 parts per million (ppm), since such ions tend to be corrosive toward the autoclave.
  • unsaturated sulphur species i.e., all sulphur compounds except sulphate which can lead to sulphur contamination of the cobalt product, e.g., dithionate ion, should be removed.
  • the invention advantageously is applied to the recovery of cobalt from cobaltic oxide hydrate obtained by oxidation-precipitation of cobalt from process leach solutions using sodium hypochlorite and a base.
  • Treatment of cobaltic hydrate to provide cobalt sulphate feed solution suitable for recovery of a cobalt as cobalt powder according to the invention may comprise the following steps:
  • the dechlorinated slurry was then subjected to a reductive leach by introducing a pure methanol solution into it at a rate of 600 ml/h for 15 minutes.
  • the progress of the leach was followed by monitoring the pH which increased from 0.1 to 1.5 in one hour.
  • pH 1.5 about 85% of the feed Co(OH) 3 had been dissolved and further dissolution of Co(OH)3 was very slow due to lack of H 2 SO 4 and methanol.
  • Complete reaction with methanol would require not only excess of methanol, but a large excess of H 2 SO 4 (pH of not greater than 1 in the end dissolution liquor) which must be neutralized with base. This operation would be costly.
  • H 2 0 2 which reacts with Co(OH) 3 as a reducing agent below pH 4.
  • a 30% H 2 0 2 solution was added into the leach slurry at a rate of 75 ml/h for 140 minutes. At this point completion of the leach was evidenced by a sharp change in colour from black to pink.
  • the pH was kept at 1.5 with H 2 SO 4 when required. This pH is preferred for the subsequent Pb removal operation.
  • Lead was removed from solution by the addition of 0.5 g of BaCO 3 per litre of solution. After 30 minutes at 60°C, the solution was neutralized to pH 5.5 using a 100 g/1 Co containing CoC0 3 slurry.
  • the final purified solution contained 96 g/1 Co and 0.038 g/l Ni, and in mg/1 Cu 1, Pb ⁇ 0.3, Fe 1, Zn 5 and C1 30.
  • Leach solution prepared in the aforedescribed manner and containing 92.2 g/l Co, 1.3 g/l Ni, 0.3 mg/l Cu, 0.3 mg/1 Pb and 0.6 mg/1 Fe was treated for cobalt recovery in the elemental powder form as follows: 0.8 litres of leach solution and 10 g of fine, discrete Co powder having an apparent density of 0.6 gm/cc were placed and sealed in a 2 litre capacity Parr all Ti autoclave provided with a twin propellor agitator which was rotated in all runs at 1000 revolutions per minute (rpm). The suspension was heated to 200°C and H 2 was admitted to the autoclave at a partial pressure of 1.3 MPa (a total pressure of 3 MPa).
  • a 9.4 N NaOH solution was then pumped into the autoclave at a rate of 150 ml/h for 90 minutes, representing an NaOH addition rate of 1.1 mole per mole of cobalt per hour.
  • the pH of the solution during NaOH addition was between 2.0 and 3.0.
  • the reduction was continued after NaOH addition for 20 minutes to ensure complete elimination of Co(OH) 2 .
  • the end reduction solution was cooled to 80°C and withdrawn from the autoclave through a carbon filter, leaving the Co powder inside 'the autoclave. About 100 ml of end reduction liquor was left in the autoclave.
  • Example II The H 2 reduction procedure used in Example I was repeated but using feed leach solution containing 85.5 g/1 Co, 0.13,g/l Ni, 0.2 mg/l Cu, 0.3 mg/l Pb and 0.9 mg/l Fe. After 8 reduction cycles the cobalt powder was washed and dried in air.. The cobalt powder product contained 99% by weight cobalt, 0.32% nickel and, in ppm, 7 copper, 20 iron, ⁇ .10 lead, ⁇ 5 zinc, 280 sulphur and 630 carbon. Table II illustrates the densification achieved during the 8 cycles.
  • Leach solution containing 96 g/1 Co, 0.038 g/l Ni, 0.3 mg/l Cu, 0.2 mg/l Pb, 1.3 mg/1 Fe and 5 mg/l Zn was treated for Co recovery in the elemental powder form as follows: 0.8 litres of leach solution and 40 g of fine, discrete cobalt powder (Afrimet) were placed in a 2 litre capacity Parr Ti autoclave. The suspension was heated with stirring to 200°C and H 2 was introduced into the vessel at a partial pressure of 1.2 MPa (total pressure of 3 MPa).
  • a 9.4 N NaOH solution was pumped into the autoclave at a rate of 780 ml/h (5.5 moles NaOH per mole of cobalt per hour) for 18 minutes and 20 seconds.
  • the pH of the solution during NaOH addition was between 2 and 3.
  • the reduction was continued thereafter for another 11 minutes and 40 seconds.(total time 30 minutes).
  • the end reduction liquor was cooled and withdrawn from the autoclave through a Ti inlet tube equipped with a carbon filter. About 100 ml of end reduction liquor and the reduced Co powder were left in the autoclave.
  • Feed CoSO 4 leach solution prepared by the method described in Example I and containing 92 g/1 Co, 0.035 g/l Ni, ⁇ 0.1 mg/l, Cu, 1.1 mg/l Fe, 0.25 mg/l Pb, and 2 mg/l Zn was treated for Co recovery by H 2 reduction in the following manner: 0.8 litres of CoSO 4 leach solution and 30 g of Co powder, made by decomposition of cobalt oxalate crystals at 500°C under N 2 atmosphere for 15 minutes, were placed in a 2 litre capacity Parr Ti autoclave.. The suspension was heated to about 200°C and H 2 was introduced into the autoclave at a partial pressure of 1.3 PMa (total pressure of 3 MPa).
  • a 9.95 N NaOH solution was then pumped into the autoclave at a rate of 150 ml/h for 90 minutes.
  • the pH of the solution during NaOH addition was between 2.5 and 3.5.
  • the reduction was carried out thereafter for another 30 minutes during which the pH of the solution decreased to 2.5.
  • the end reduction liquor was cooled to 80°C and withdrawn from the autoclave through a Ti inlet tube equipped with a carbon filter.
  • 0.8 litres of fresh C O SO 4 solution was fed to the autoclave and the H 2 reduction cycle was repeated as above 11 times.
  • the Co powder was washed and dried in air.
  • the cobalt powder contained, by weight, 99% cobalt and 0.089% nickel and, in ppm, 12 copper, 32 iron, 9 lead, 4 zinc and 518 sulphur.
  • Feed CoSO 4 leach solution containing 86 g/1 Co, 0.046 g/1 Ni, 0.3 mg/l Cu, 0.4 mg/l Pb and 2 mg/l Fe was treated for Co recovery by H 2 reduction in the following manner: 0.7 litres of CoSO 4 leach solution and 10 g of Afrimet Co powder were placed in a 2 litre capacity Parr Ti autoclave. The suspension was heated to 200°C and H 2 was introduced into the vessel at a partial pressure of 1.3 MPa (total pressure of 3 MPa).
  • a 10 N NaOH solution was then pumped into the autoclave at a rate of 1.44 litres per hour (12 moles NaOH per mole of cobalt per hour) for 7 minutes and 30 seconds.' The pH of the solution during NaOH addition increased from 2.0 to 7.0. The reduction was carried on thereafter until the pH in the solution was below about 3. This took about 110 minutes.
  • the end reduction liquor was cooled to 80°C and withdrawn from the autoclave through a Ti inlet tube equipped with a carbon filter. 0.7 litres of fresh CoSO 4 solution was fed into the autoclave and the H 2 reduction cycle was repeated as above 8 times. At the end of 8 cycles, the produced Co powder was washed and dried in air. The Co powder was light and porous.
  • the powder contained 99% cobalt and 0.05% nickel and, in ppm, 5 copper, 30 iron, ⁇ 5 lead, 6 zinc, 1,00 0 sulphur and 500 carbon.
  • Leach solution containing 96 g/1 Co, 0.038 g/1 Ni, ⁇ O. 3 mg/l Cu, ⁇ 0.3 mg/l Pb, 1.3 mg/l Fe and 5 mg/l Zn was treated for cobalt powder recovery as follows: 0.7 litres of leach solution was sealed in a 2 litre Ti autoclave and heated to 200°C. A 1.3 MPa partial pressure of H 2 was admitted to the autoclave and 0.1 litres of solution containing 20 g/1 NaCN and 2 g/l Na 2 S was pumped in. This was followed by the addition of a 9.4 N NaOH solution at a rate of 780 ml/h for 18 minutes and 36 seconds. The reduction was continued after NaOH addition for about 12 minutes. The autoclave contents were cooled to 80°C and the solution was withdrawn from the vessel through a Ti inlet tube equipped with a carbon filter.
  • a leach solution containing 92 g/l Co, 0.032 g/1 Ni, ⁇ 0.1 mg/l Cu, 1 mg/l Fe, ⁇ 0.25 mg/l and 2 mg/l Zn was treated for cobalt powder recovery as follows: 0.8 litres of CoSO 4 leach solution was heated in autoclave to 200 C and H 2 was admitted at 1.3 MPa partial pressure. A 9.4 N NaOH solution was pumped in at a rate of 1.2 litres per hour for 15 minutes (equivalent to 99% of the Co as C O (OH) 2 ) and the reduction was continued thereafter for another 35 minutes. After cooling the end reduction liquor was pumped out and 0.8 litres of fresh feed CoSO 4 solution was pumped in.
  • the structure of the seed powder at 200 diameters is shown in Figure 5. A large amount of void space is evident. The powder structure obtained after 6 densifications is shown in Figure 6. The powder is still porous and the tendency to deposit reduced cobalt in the void space of the seed particles is illustrated. The density of the product is notably low. We believe that the reason why the powder produced in Examples B and C is not particularly dense is that the seed particles are large and porous, cobalt is deposited in the voids in such particles and that results in a reduction in the surface area available for cobalt deposition in subsequent steps. This situation can be contrasted with the processes described earlier in which the surface area increases in each successive densification when small compact seed particles are used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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EP81303653A 1980-08-21 1981-08-11 Procédé de production de poudre métallique de cobalt Expired EP0047076B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA358741 1980-08-21
CA000358741A CA1151881A (fr) 1980-08-21 1980-08-21 Production de poudre metallique du cobalt par reduction a l'hydrogene

Publications (2)

Publication Number Publication Date
EP0047076A1 true EP0047076A1 (fr) 1982-03-10
EP0047076B1 EP0047076B1 (fr) 1985-05-02

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EP81303653A Expired EP0047076B1 (fr) 1980-08-21 1981-08-11 Procédé de production de poudre métallique de cobalt

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EP (1) EP0047076B1 (fr)
JP (1) JPH0351764B2 (fr)
AU (1) AU542235B2 (fr)
CA (1) CA1151881A (fr)
DE (1) DE3170282D1 (fr)
FI (1) FI71771C (fr)
NO (1) NO161130C (fr)
PH (1) PH18541A (fr)
ZA (1) ZA815530B (fr)
ZW (1) ZW19981A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770693A1 (fr) * 1995-10-27 1997-05-02 H.C. Starck GmbH & Co. KG Poudre ultrafine de cobalt, procédé d'obtention ainsi que l'utilisation de la poudre de cobalt métallique et du carbonate de cobalt
WO2003010345A1 (fr) * 2001-07-25 2003-02-06 Phelps Dodge Corporation Procede d'amelioration de la recuperation des metaux au moyen du lessivage par pression a haute temperature
WO2014009208A1 (fr) * 2012-07-10 2014-01-16 Basf Se Procédé de fabrication de solutions aqueuses de sulfate de cobalt
WO2014009173A1 (fr) * 2012-07-10 2014-01-16 Basf Se Procédé de fabrication de solutions aqueuses de sulfate de cobalt
CN107735199A (zh) * 2015-07-03 2018-02-23 住友金属矿山株式会社 钴粉的制造方法
CN110899719A (zh) * 2018-09-14 2020-03-24 上海铁路通信有限公司 一种片层结构钴颗粒材料的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1233047A (fr) * 1984-03-05 1988-02-23 Michael A. Tenhover Melange de poudres metalliques amorphe et objets frittes ainsi obtenus, ainsi que synthese par la technique des reactions de decomposition a l'etat solide
US4537625A (en) * 1984-03-09 1985-08-27 The Standard Oil Company (Ohio) Amorphous metal alloy powders and synthesis of same by solid state chemical reduction reactions
JPS63274706A (ja) * 1987-05-02 1988-11-11 Nippon Chem Ind Co Ltd:The 金属微粉末の製造法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734821A (en) * 1956-02-14 Table ix
US2749235A (en) * 1953-09-25 1956-06-05 Chemical Construction Corp Method of reducing cobaltic ammine salt
US2864692A (en) * 1956-09-24 1958-12-16 Bethlehem Steel Corp Recovery of copper and cobalt values from sulphate leach solutions
FR1223378A (fr) * 1957-12-18 1960-06-16 Metallurg De Hoboken Soc Gen Procédé d'élimination du nickel d'une solution cobaltifère de sulfate ou chlorure
US4151258A (en) * 1978-03-06 1979-04-24 Amax Inc. Dissolution of cobaltic hydroxide with organic reductant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2734821A (en) * 1956-02-14 Table ix
US2749235A (en) * 1953-09-25 1956-06-05 Chemical Construction Corp Method of reducing cobaltic ammine salt
US2864692A (en) * 1956-09-24 1958-12-16 Bethlehem Steel Corp Recovery of copper and cobalt values from sulphate leach solutions
FR1223378A (fr) * 1957-12-18 1960-06-16 Metallurg De Hoboken Soc Gen Procédé d'élimination du nickel d'une solution cobaltifère de sulfate ou chlorure
US4151258A (en) * 1978-03-06 1979-04-24 Amax Inc. Dissolution of cobaltic hydroxide with organic reductant

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770693A1 (fr) * 1995-10-27 1997-05-02 H.C. Starck GmbH & Co. KG Poudre ultrafine de cobalt, procédé d'obtention ainsi que l'utilisation de la poudre de cobalt métallique et du carbonate de cobalt
CN100352583C (zh) * 1995-10-27 2007-12-05 H·C·施塔克公司 超细钴金属粉末、其制备方法以及钴金属粉末和碳酸钴的用途
WO2003010345A1 (fr) * 2001-07-25 2003-02-06 Phelps Dodge Corporation Procede d'amelioration de la recuperation des metaux au moyen du lessivage par pression a haute temperature
US6626979B2 (en) 2001-07-25 2003-09-30 Phelps Dodge Corporation Method for improving metals recovery using high temperature pressure leaching
US6893482B2 (en) 2001-07-25 2005-05-17 Phelps Dodge Corporation Method for improving metals recovery using high temperature pressure leaching
AU2002332423B2 (en) * 2001-07-25 2005-12-15 Freeport-Mcmoran Corporation Method for improving metals recovery using high temperature pressure leaching
WO2014009208A1 (fr) * 2012-07-10 2014-01-16 Basf Se Procédé de fabrication de solutions aqueuses de sulfate de cobalt
WO2014009173A1 (fr) * 2012-07-10 2014-01-16 Basf Se Procédé de fabrication de solutions aqueuses de sulfate de cobalt
US9321656B2 (en) 2012-07-10 2016-04-26 Basf Se Process for preparing aqueous solutions of cobalt sulfate
US9416023B2 (en) 2012-07-10 2016-08-16 Basf Se Method for producing aqueous solutions of cobalt sulphate
CN107735199A (zh) * 2015-07-03 2018-02-23 住友金属矿山株式会社 钴粉的制造方法
EP3321015A4 (fr) * 2015-07-03 2019-03-20 Sumitomo Metal Mining Co., Ltd. Procédé de production de poudre de cobalt
CN110899719A (zh) * 2018-09-14 2020-03-24 上海铁路通信有限公司 一种片层结构钴颗粒材料的制备方法
CN110899719B (zh) * 2018-09-14 2022-11-15 上海铁路通信有限公司 一种片层结构钴颗粒材料的制备方法

Also Published As

Publication number Publication date
NO161130C (no) 1989-07-05
FI71771B (fi) 1986-10-31
FI812559L (fi) 1982-02-22
AU7421281A (en) 1982-02-25
NO812809L (no) 1982-02-22
JPS5754207A (fr) 1982-03-31
EP0047076B1 (fr) 1985-05-02
FI71771C (fi) 1987-02-09
DE3170282D1 (en) 1985-06-05
AU542235B2 (en) 1985-02-14
CA1151881A (fr) 1983-08-16
NO161130B (no) 1989-03-28
ZA815530B (en) 1982-08-25
PH18541A (en) 1985-08-09
JPH0351764B2 (fr) 1991-08-07
ZW19981A1 (en) 1982-01-06

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