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WO2020183728A1 - Procédé de production de poudre de nickel - Google Patents

Procédé de production de poudre de nickel Download PDF

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Publication number
WO2020183728A1
WO2020183728A1 PCT/JP2019/010678 JP2019010678W WO2020183728A1 WO 2020183728 A1 WO2020183728 A1 WO 2020183728A1 JP 2019010678 W JP2019010678 W JP 2019010678W WO 2020183728 A1 WO2020183728 A1 WO 2020183728A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
solution
nickel powder
reduction
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.)
Ceased
Application number
PCT/JP2019/010678
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English (en)
Japanese (ja)
Inventor
伸一 平郡
佳智 尾崎
龍馬 山隈
高石　和幸
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.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to PCT/JP2019/010678 priority Critical patent/WO2020183728A1/fr
Publication of WO2020183728A1 publication Critical patent/WO2020183728A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 for obtaining high-purity nickel powder and a briquette obtained by solidifying the nickel powder from a nickel sulfate ammine complex solution.
  • it can be applied to the treatment of intermediate solution in the process generated in the wet nickel smelting process.
  • Non-Patent Document 1 describes a process for producing nickel powder in which an iron compound is added as a seed crystal during a reduction reaction to precipitate nickel on the iron compound, but iron mixed from the seed crystal is mixed in the product. There is a problem.
  • Patent Document 1 states that it is inexpensive, has excellent weather resistance, has low electrical resistance when kneaded with a resin, reduces initial electrical resistance and electrical resistance during use, can be used stably for a long period of time, and is conductive.
  • nickel powders suitable as conductive particles for pastes and conductive resins and methods for providing methods for producing the same.
  • the nickel powder disclosed in Patent Document 1 is a nickel powder containing 1 to 20% by mass of cobalt, the balance of which is composed of nickel and unavoidable impurities, and is composed of secondary particles in which primary particles are aggregated, and contains oxygen. The amount is 0.8% by mass or less. It is said that it is preferable that cobalt is contained only in the surface layer portion of the secondary particles, and the cobalt content in the surface layer portion is 1 to 40% by mass.
  • cobalt coexists for example, nickel and cobalt coexist like nickel oxide ore, and these are separated and each is high. It is not suitable for pure and economically recoverable applications.
  • Patent Document 2 provides a method for producing a metal powder by a liquid phase reduction method, which is improved so as not to generate particle agglutinations.
  • This production method involves the first step of preparing an aqueous solution containing metal ions derived from a metal compound by dissolving a metal compound, a reducing agent, a complexing agent, and a dispersant, and adjusting the pH of the aqueous solution.
  • This is a method for producing a metal powder which comprises a second step of reducing metal ions with a reducing agent and precipitating the metal powder.
  • this production method is expensive using expensive chemicals, and is not economically advantageous for application to the process of large-scale operation as the nickel smelting.
  • various processes for producing nickel powder have been proposed, but a method for producing high-purity nickel powder using industrially inexpensive hydrogen gas has not been proposed.
  • Patent Document 3 describes a production method for producing coarse particles of high-purity nickel powder from a nickel sulfate ammine complex solution using industrially inexpensive hydrogen gas and fine nickel powder. Is disclosed. With this method, high-purity nickel powder can be obtained more efficiently than before, but on the other hand, there is a problem that the labor and cost for recovering ammonia from the post-reaction liquid after hydrogen reduction cannot be ignored. As described above, no cost-effective nickel recovery method has been found.
  • Addition process (4) Hydrogen gas is blown into the mixed slurry obtained in the seed crystal addition step of (3), and the nickel component in the mixed slurry is reduced and precipitated on the seed crystal to contain nickel powder. A reduction step of forming a slurry. (5) The reduction slurry obtained in the reduction step of (4) is solid-liquid separated, separated from the final reduction liquid using the nickel powder as a solid phase component, and recovered, and then nickel sulfate ammine complex is added to the recovered nickel powder. A growth step in which hydrogen gas is blown into a solution to which a solution has been added to grow the nickel powder to form high-purity nickel powder. (6) A reduction final solution utilization treatment in which the reduction final solution obtained in the reduction step of (4) is repeated as a sulfuric acid acidic solution used for dissolving nickel hydroxide in the complexing step of (2).
  • the second invention of the present invention comprises a leaching step in which the nickel-containing acidic solution of the first invention dissolves a nickel-containing substance containing cobalt as an impurity, and the nickel component and the cobalt component obtained in the leaching step. It is a method for producing nickel powder, which is obtained through a solvent extraction step in which the leachate containing the leachate is adjusted in pH and then separated into a nickel sulfate solution and a cobalt recovery solution by a solvent extraction method.
  • the pH of the leachate in the solvent extraction step of the second invention is adjusted by mixing a metal ion-extracted extractant and a metal ion-free extractant in a predetermined ratio. It is a method for producing nickel powder, which is characterized by being carried out.
  • nickel powder containing less impurities can be easily produced by using seed crystals that do not contaminate the produced product. It can be obtained in Japan and has a remarkable industrial effect.
  • high-purity nickel powder with less impurities is obtained from the nickel sulfate ammine complex solution by subjecting the step solution of the hydrometallurgy process to the following steps. It is characterized by manufacturing.
  • the method for producing the high-purity nickel powder of the present invention will be described with reference to the production flow chart of the high-purity nickel powder of the present invention shown in FIG.
  • the leaching step involves an industrial intermediate consisting of a mixture of nickel and cobalt mixed sulfide, crude nickel sulfate, nickel oxide, nickel hydroxide, nickel carbonate, nickel powder, etc., which is a starting material.
  • the step of dissolving the nickel-containing material of the above with sulfuric acid to leach nickel to produce a leachate (solution containing nickel) it is carried out by using a known method disclosed in JP-A-2005-350766. ..
  • impurity elements in the leachate are selectively extracted by using 2-ethylhexylphosphonic acid mono2-ethylhexyl ester or di- (2,4,4-trimethylpentyl) phosphinic acid in the organic phase.
  • a low nickel sulfate solution is obtained.
  • ammonia water used for pH adjustment in this step ammonia recovered from the step can be used.
  • the pH adjustment can also be performed by mixing an extractant from which metal ions such as nickel have been extracted in advance and an extractant containing no metal ions at a predetermined ratio. That is, in the case of an acidic extractant, the extraction behavior of cations such as nickel depends on the pH of the aqueous phase, so that the pH of the aqueous phase can be adjusted without adding a pH adjuster by using the above method. As a result, it becomes possible to arbitrarily control the distribution of the organic phase such as nickel and the aqueous phase.
  • a desired nickel powder can be obtained through the steps and treatments shown in (1) to (6) below.
  • a neutralizing agent such as slaked lime or sodium hydroxide is added to the nickel sulfate solution obtained in the solvent extraction step to adjust the pH of the solution to about 6 to 9 and nickel hydroxide.
  • a solid substance of the above is produced to form a slurry.
  • the slurry is solid-liquid separated into nickel hydroxide and a neutralized liquid using a known method such as a centrifuge, a nutche or a filter press.
  • an acidic sulfuric acid solution containing ammonia is added to the nickel hydroxide obtained in the neutralization step of (1) to obtain a nickel sulfate ammine complex solution.
  • a sulfuric acid solution may be added to nickel hydroxide to form a nickel sulfate solution, and ammonia may be added at the same time as or after dissolution to complex the nickel.
  • the reduction final solution described later is repeated. Is added, and the ammonia and sulfuric acid components contained in the final solution are dissolved and confused.
  • the nickel sulfate solution is once neutralized to obtain nickel hydroxide, which is then dissolved again to obtain a nickel sulfate ammine complex solution in which nickel is concentrated, and the subsequent process equipment is made compact and generated. It is characterized by efficient production such as reduction of wastewater.
  • the amount of ammonia When the amount of ammonia is insufficient, it may be adjusted by adding ammonia of ammonia gas or aqueous ammonia. Further, when the sulfuric acid concentration is insufficient, the sulfuric acid solution may be added in the same manner. In this way, a nickel sulfate ammine complex, which is an ammine complex of nickel, is produced, and a nickel sulfate ammine complex solution thereof is formed. At this time, ammonia is added so that the ammonium concentration is 1.9 or more in molar ratio with respect to the nickel concentration in the solution. If the ammonium concentration of the added ammonia is less than 1.9, nickel does not form an ammine complex and a nickel hydroxide precipitate is formed.
  • ammonium sulfate can be added in this step in order to adjust the concentration of ammonium sulfate.
  • the ammonium sulfate concentration at this time is preferably 100 to 500 g / L, and if it exceeds 500 g / L, the solubility is exceeded and crystals are precipitated, and it is difficult to achieve less than 100 g / L due to the metal balance of the process. is there.
  • the ammonia gas or ammonia water used in this step the ammonia gas or ammonia water recovered in the step can be used.
  • Nickel powder production process from nickel sulfate ammine complex solution The step of producing nickel powder from the nickel sulfate ammine complex solution shown in the treatment steps (3) to (5) surrounded by the broken line in FIG. 1 will be described below.
  • Nickel powder having an average particle size of 0.1 to 5 ⁇ m is added as seed crystals to the nickel sulfate ammine complex solution obtained in the complexing step of (2) above in the form of a nickel powder slurry.
  • the weight of the seed crystal added at this time is preferably 1 to 100% with respect to the weight of nickel in the nickel sulfate ammine complex solution. If it is less than 1%, the reaction efficiency at the time of reduction in the next step is significantly lowered. Further, if it exceeds 100%, the amount used is large, the seed crystal production is costly, and it is not economical.
  • the dispersant used here is not particularly limited as long as it has a sulfonate, but a lignin sulfonate is preferable as it can be obtained industrially at low cost.
  • the reaction temperature is preferably 150 to 200 ° C. If the temperature is lower than 150 ° C., the reduction efficiency is lowered, and if the temperature exceeds 200 ° C., there is no effect on the reaction and the loss of thermal energy and the like increases.
  • the pressure during the reaction is preferably 1.0 to 4.0 MPa. If it is less than 1.0 MPa, the reaction efficiency decreases, and if it exceeds 4.0 MPa, there is no effect on the reaction and the loss of hydrogen gas increases.
  • Magnesium ions, sodium ions, sulfate ions, and ammonium ions are mainly present as impurities in the liquid of the mixed slurry obtained in the seed crystal addition step of (3), but all of them remain in the solution and are therefore high. It is possible to produce nickel powder of purity.
  • the obtained nickel powder may be finished into a briquette shape that is coarser, less likely to be oxidized, and easy to handle through the following nickel powder complex ore step and briquette sintering step. Further, an ammonia recovery step may be provided.
  • the high-purity nickel powder produced by the present invention is molded by a mining machine or the like after drying to obtain a massive nickel briquette. Further, in order to improve the moldability into the briquette, in some cases, a substance such as water that does not contaminate the product quality is added to the nickel powder as a binder.
  • the nickel briquette produced in the complex ore step is roasted and sintered in a hydrogen atmosphere to produce a briquette sintered body.
  • the strength is increased and trace amounts of residual ammonia and sulfur components are removed, and the roasting / sintering temperature thereof is preferably 500 to 1200 ° C. If the temperature is lower than 500 ° C, sintering becomes insufficient, and even if the temperature exceeds 1200 ° C, the efficiency hardly changes and the energy loss becomes large.
  • the generated small particle size nickel powder was repeatedly applied (not shown), but in the first case where there was no repeating nickel powder, the nickel powder prepared by the following procedure was used. To 73 ml of 25% aqueous ammonia, 36 g of sodium hydroxide and 53 ml of a 60% hydrazine solution were added to adjust the total liquid volume to 269 ml.
  • nickel sulfate solution 100 g / L was added dropwise to the liquid in the beaker while maintaining and stirring so that the liquid temperature was 75 ° C., and the solution was held for 30 minutes. Then, solid-liquid separation was performed, and the produced nickel powder was recovered. The average particle size of the obtained nickel powder was 2 ⁇ m.
  • the nickel hydroxide obtained above was mixed with 1700 ml of the reduction final solution obtained in the reduction step (4) above to prepare a mixed slurry.
  • the nickel powder could be recovered by repeating this mixed slurry in the reduction step of (4) above and blowing hydrogen gas while pressurizing under the same conditions.
  • the nickel hydroxide obtained in the neutralization step of (1) above is subjected to sulfuric acid having a nickel concentration of 30 g / L because there is no final solution for reduction only in the first batch in which the present invention is repeated. It was added to 1700 ml of a mixed solution of a nickel solution and an ammonium sulfate solution having an ammonia concentration of 40 g / L and dissolved by stirring to obtain a nickel sulfate ammine complex solution.
  • a solution in which nickel hydroxide was dissolved was obtained by using it as a mixed solution into which the reduction final solution described later was added (reduction final solution utilization treatment).
  • the solution obtained in the complexing step of (2) contains 75 g of nickel, 330 g of ammonium sulfate, and 191 ml of 25% ammonia water, and the total amount of the solution. Was adjusted to 1000 ml.
  • the nickel powder obtained in the above seed crystal production step or the produced nickel powder was repeatedly added to this solution to form seed crystals, and 7.5 g was added to prepare a mixed slurry.
  • Diluting agent (naphthen-based cleaning agent, manufactured by JXTG Energy Co., Ltd.) so that the acidic extractant (2-ethylhexylphosphonic acid mono2-ethylhexyl ester, manufactured by No. 8 Chemical Industry Co., Ltd., trade name PC88A) is 20% by volume.
  • the extractant diluted with the trade name Teclean N20) and a nickel sulfate solution having a nickel concentration of 120 g / L are mixed, and then a sodium hydroxide solution is added to adjust the pH to 7.0, and the extractant (A). ) was extracted so that the concentration of nickel in the solution was 23 g / L. Further, an extractant (B) from which nickel was not extracted was separately prepared.
  • the extractant in which the mixing ratio of the organic phase of the extractant (A) extracting nickel and the organic phase of the extractant (B) not extracting nickel was changed.
  • the organic phase is brought into contact with a certain amount of the aqueous phase
  • the volume ratio O / A of the organic phase (O) and the aqueous phase (A) is large, that is, when the ratio of the organic phase in which nickel is not extracted is increased. It was confirmed that the pH of the aqueous phase decreased and the pH was adjusted.
  • the extraction behavior of cations such as nickel depends on the pH of the aqueous phase. Therefore, when the method of the present invention is used, the pH of the aqueous phase can be adjusted without adding a pH adjuster.
  • the distribution of the organic phase such as nickel and the aqueous phase can be arbitrarily controlled.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

L'invention concerne un procédé de production utilisant un gaz hydrogène peu coûteux au plan industriel et une poudre de nickel microscopique pour générer des particules grossières de poudre de nickel contenant une petite quantité d'impuretés à partir d'une solution complexe de sulfate de nickel ammine.　Le procédé de production de poudre de nickel est caractérisé en ce qu'une solution acide contenant du nickel est soumise à une étape de neutralisation (1), une étape de complexation (2), une étape d'addition de germe cristallin (3), une étape de réduction (4), une étape de croissance (5) et, en outre, un traitement d'utilisation de solution d'extrémité de réduction (6) consistant à utiliser les solutions d'extrémité de réduction obtenues dans l'étape de réduction (4) et l'étape de croissance (5) de façon répétée en tant que solution acide d'acide sulfurique dans l'étape de complexation.
PCT/JP2019/010678 2019-03-14 2019-03-14 Procédé de production de poudre de nickel Ceased WO2020183728A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2019/010678 WO2020183728A1 (fr) 2019-03-14 2019-03-14 Procédé de production de poudre de nickel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2019/010678 WO2020183728A1 (fr) 2019-03-14 2019-03-14 Procédé de production de poudre de nickel

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WO2020183728A1 true WO2020183728A1 (fr) 2020-09-17

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017082270A (ja) * 2015-10-26 2017-05-18 住友金属鉱山株式会社 コバルト粉の種結晶の製造方法
JP2017155253A (ja) * 2016-02-29 2017-09-07 住友金属鉱山株式会社 ニッケル粉の製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017082270A (ja) * 2015-10-26 2017-05-18 住友金属鉱山株式会社 コバルト粉の種結晶の製造方法
JP2017155253A (ja) * 2016-02-29 2017-09-07 住友金属鉱山株式会社 ニッケル粉の製造方法

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