WO2017150717A1 - ニッケル粉の製造方法 - Google Patents
ニッケル粉の製造方法 Download PDFInfo
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- WO2017150717A1 WO2017150717A1 PCT/JP2017/008562 JP2017008562W WO2017150717A1 WO 2017150717 A1 WO2017150717 A1 WO 2017150717A1 JP 2017008562 W JP2017008562 W JP 2017008562W WO 2017150717 A1 WO2017150717 A1 WO 2017150717A1
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- nickel
- nickel powder
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- ammine complex
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
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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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
- B22F2201/013—Hydrogen
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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
- B22F2203/00—Controlling
- B22F2203/11—Controlling temperature, temperature profile
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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
- B22F2203/00—Controlling
- B22F2203/13—Controlling pressure
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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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/15—Nickel or cobalt
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a method of obtaining nickel powder from a nickel sulfate ammine complex solution, and relates to a method of continuously adding a solution, hydrogen gas, etc. to a high-pressure vessel, and continuously discharging and collecting the nickel powder.
- Patent Document 1 As a method for industrially producing nickel powder using a hydrometallurgical process, as shown in Patent Document 1, after dissolving a nickel-containing raw material in a sulfuric acid solution, a purified solution for removing impurities contained in the solution Through the process, ammonia is added to the resulting nickel sulfate solution to form a nickel ammine complex, then this nickel sulfate ammine complex solution is placed in a high-temperature, high-pressure vessel, and hydrogen gas is supplied to the nickel sulfate ammine complex solution. There is known a method for producing nickel powder by reducing nickel contained therein.
- the nickel powder obtained by the batch method described above has a problem in terms of impurity quality as compared with a plate (sheet) -like electric nickel obtained by general electrolytic smelting. Specifically, sulfur quality is required to be 0.01% by weight or less in order to obtain high-purity grade certification in LME (London Metal Exchange), an international nickel market.
- LME London Metal Exchange
- the nickel powder obtained by using the batch method may have a higher sulfur quality than the specifications of the high-purity LME grade described above, and it was difficult to use it for an application that completely replaces electric nickel.
- the present invention continuously supplies solution, seed crystals and hydrogen gas to a reaction vessel maintained at high temperature and high pressure to produce nickel powder, and discharges and collects the continuously produced powder. It is intended to provide a production method capable of maintaining a high reaction operation rate while maintaining a quality with small variation in particle size of fine nickel powder while sufficiently growing in purity.
- a nickel sulfate ammine complex solution and a seed crystal are supplied to a reaction vessel, hydrogen gas is supplied to the reaction vessel, and the nickel sulfate ammine complex solution contains
- the reduction treatment is performed by continuously supplying the nickel sulfate ammine complex solution to the reaction vessel.
- the temperature is controlled in the range of 150 ° C. or more and 185 ° C. or less, and the supply amount of the hydrogen gas is controlled so that the internal pressure in the reaction vessel is maintained in the range of 2.5 to 3.5 MPa.
- the second invention of the present invention reduces the nickel complex ions in the nickel sulfate ammine complex solution by supplying hydrogen gas into the reaction vessel and supplying the nickel sulfate ammine complex solution and seed crystal into the reaction vessel.
- the reduction treatment stores a slurry containing ammonium sulfate and nickel powder to form a liquid phase part and a gas phase part in the reaction container, and the reaction container contains Control of the internal pressure of the gas phase by supplying hydrogen gas to the slurry, continuous supply of the slurry containing seed crystals and the nickel sulfate ammine complex solution to the liquid phase, and the reaction vessel internal temperature of 150 ° C. or higher and 185 ° C.
- a method for producing a nickel powder which comprises reducing the Le complex ions.
- the third invention of the present invention is characterized in that polyacrylic acid is added to the nickel sulfate ammine complex solution in the first or second invention so as to have a concentration of 0.5 to 1.0 g / liter. It is a manufacturing method of nickel powder.
- a fourth invention of the present invention is a nickel powder manufacturing method, wherein the seed crystal in the first and second inventions uses nickel powder having an average particle size in the range of 0.1 to 100 ⁇ m.
- a nickel powder manufacturing method characterized in that the seed crystal in the first to third aspects uses nickel powder having an average particle diameter in the range of 0.1 to 10 ⁇ m. is there.
- the sixth invention of the present invention is that the amount of seed crystals added in the first to fifth inventions is in the range of 1 to 100% by weight relative to the weight of nickel in the nickel sulfate ammine complex solution. It is the manufacturing method of the nickel powder characterized.
- the nickel sulfate ammine complex solution used for the reduction treatment in the first to sixth aspects is 0.5 to 5 based on the weight of the seed crystal in the nickel sulfate ammine complex solution.
- nickel ammine sulfate containing seed crystals so that the reduction treatment in the first to seventh aspects of the invention has a reduction treatment reaction time in the reaction vessel of not less than 5 minutes and not more than 120 minutes.
- a method for producing nickel powder characterized in that a complex solution is continuously supplied to a reaction vessel.
- nickel powder in which nickel precipitates are formed and grown on the seed crystal can be formed by reduction treatment with nickel precipitation and the repetition thereof, and nickel powder with little variation in size can be continuously formed.
- nickel powder can be extracted and recovered from the solution as a fine powdery precipitate with low sulfur grade due to the effect of the dispersant, and depending on the combination of the particle size of the nickel powder and the dispersant concentration, a spherical and smooth surface Coarse nickel powder having can also be obtained.
- the nickel powder produced in the present invention can be used as a nickel paste, which is an internal constituent material of a multilayer ceramic capacitor.
- the above-described reduction treatment with hydrogen is repeated to grow particles and produce high-purity nickel metal. This is a production method capable of maintaining a high reaction availability while maintaining a possible quality, and has a remarkable industrial effect.
- the present invention adds a seed crystal to a nickel sulfate ammine complex solution, produces nickel powder by reduction treatment with hydrogen gas blown into a reaction vessel that is a pressurized vessel while continuously supplying it, and pressurizes the nickel powder.
- a nickel powder production method characterized by continuously discharging from a container. Further, by using a dispersant, it is possible to obtain high purity, uniform and fine nickel powder with low sulfur quality.
- the manufacturing method of the nickel powder of this invention is demonstrated.
- the nickel sulfate ammine complex solution used in the present invention is not particularly limited, but one or a mixture selected from nickel and cobalt mixed sulfide, crude nickel sulfate, nickel oxide, nickel hydroxide, nickel carbonate, nickel powder and the like.
- nickel leaching solution solution containing nickel
- a solution obtained by adding ammonia to a solution obtained by removing impurity elements from the solution to form a nickel sulfate ammine complex solution is suitable.
- seed crystals are added to the nickel sulfate ammine complex solution to form a mixed slurry, which is subjected to a reduction treatment.
- the seed crystal added here is preferably a powder having an average particle size of 0.1 ⁇ m or more and 100 ⁇ m or less, more preferably 0.1 ⁇ m or more and 10 ⁇ m or less.
- nickel powder it is preferable to use nickel powder as a substance that does not contaminate the final nickel deposit.
- the nickel powder used as the seed crystal can be produced, for example, by adding a reducing agent such as hydrazine to the nickel sulfate ammine complex solution.
- the weight of the seed crystal to be added is preferably 1% by weight or more and 100% by weight or less based on the weight of nickel in the nickel sulfate ammine complex solution. If the amount is less than 1% by weight, the effect of suppressing non-uniform precipitation cannot be sufficiently obtained, and even if an amount exceeding 100% by weight is added, the effect is not affected and excessive addition is caused.
- a dispersing agent can be added in order to disperse the seed crystals in the mixed slurry.
- the dispersant used here is not particularly limited as long as it is a polyacrylate, but sodium polyacrylate is preferred as an industrially available product.
- the addition amount is preferably in the range of 0.5 to 5% by weight with respect to the weight of the seed crystal to be added. If it is less than 0.5%, the dispersion effect cannot be obtained, and even if added over 5%, the dispersion effect is not affected, and the addition is excessive.
- the polyacrylic acid to be added may be added so as to have a concentration of 0.5 to 1.0 g / liter relative to the amount of the nickel sulfate ammine complex solution.
- a seed crystal having a diameter of 0.1 ⁇ m or more and 10 ⁇ m or less is preferable.
- “ ⁇ ” in the above description of 0.5 to 5% by weight indicates 0.5 to 5% by weight.
- a mixed slurry formed by adding seed crystals or seed crystals and a dispersant to a nickel sulfate ammine complex solution is stored in a slurry containing ammonium sulfate and nickel powder, and high pressure resistance and high temperature are controlled by hydrogen gas.
- the container is continuously charged into a reaction tank, and a liquid phase part and a gas phase part occupied by the mixed slurry are formed in the reaction tank.
- a slurry containing a seed crystal or a slurry containing a seed crystal and a dispersant, and a nickel sulfate ammine complex solution are stored in a slurry containing ammonium sulfate and nickel powder, and an internal pressure controlled by hydrogen gas is controlled.
- the slurry is continuously charged into the reaction tank to form a mixed slurry, and a liquid phase part occupied by the mixed slurry and a gas phase part whose internal pressure is controlled by hydrogen gas are formed in the reaction tank.
- the nickel complex ions contained in the nickel sulfate ammine complex solution were reduced by hydrogen gas in the mixed slurry in the reaction vessel continuously charged, and the nickel was deposited on the added seed crystal to grow. While making it nickel powder, the nickel powder slurry which is the slurry containing the grown nickel powder is formed, and the grown nickel powder slurry is discharged
- the reaction temperature at this time is preferably in the range of 150 ° C. or higher and 185 ° C. or lower. If it is less than 150 degreeC, reduction efficiency will fall, and even if it exceeds 185 degreeC, there is no influence on reaction, rather, since loss, such as a heat energy, increases, it is unsuitable.
- the pressure in the gas phase portion of the reaction tank during the reaction is preferably maintained in the range of 2.5 to 3.5 MPa. If it is less than 2.5 MPa, the reaction efficiency decreases, and if it exceeds 3.5 MPa, there is no influence on the reaction, and the loss of hydrogen gas increases.
- nickel powder is formed and grown on the seed crystal, and nickel powder with little variation in size can be obtained continuously.
- nickel can be extracted and recovered from the solution as a fine powdery precipitate with a low sulfur grade due to the effect of the dispersant.
- coarse nickel powder having a spherical and smooth surface can be obtained by a combination of the particle diameter of nickel powder and the concentration of the dispersant.
- the nickel powder produced as described above can be used, for example, as a nickel paste, which is an internal constituent material of a multilayer ceramic capacitor.
- the particles are grown by repeating the hydrogen reduction described above, and high purity and suitable for handling.
- a uniform fine nickel metal of 20 ⁇ m or less can be produced.
- a pressure vessel (autoclave) with an internal volume of 190 liters was used as a reaction tank, and 90 liters of a solution slurry containing 269 g / L of ammonium sulfate and 100 g / L of nickel powder was put into this reaction tank, and the temperature was set with a lid. The temperature was maintained at 185 ° C., and then hydrogen gas was blown at a pressure of 3.5 MPa.
- an initial solution consisting of 150 g of ammonium sulfate per liter and a nickel sulfate ammine complex solution having a nickel concentration of 110 g / L is added to the pressurized container at a flow rate of 1 liter per minute and a nickel species having a slurry concentration of 300 g / L.
- the crystal slurry was added at a flow rate of 0.25 liters per minute to proceed with the reduction treatment.
- the nickel powder having an average particle diameter of 1 ⁇ m was used as the seed crystal constituting the nickel seed crystal slurry.
- hydrogen gas was blown in while controlling the internal pressure of the pressurized container to be 3.5 MPa.
- the reduction treatment reaction time in the reaction vessel was 75 minutes from the start of the initial solution and seed crystal slurry to the extraction of the nickel powder slurry.
- the nickel concentration in the extracted nickel powder slurry was 0.28 g / L, and the reduction rate (reaction rate), that is, the rate at which hydrogen gas was used for the nickel powder precipitation reaction, It was 99.6%.
- the proportion of 100 ⁇ m to 300 ⁇ m accounted for 99% or more, and sufficiently grown nickel powder was obtained.
- the overall particle size distribution is less than 0.1% over 300 ⁇ m, 91% over 150 ⁇ m and 300 ⁇ m or less, 8.3% over 100 ⁇ m and 150 ⁇ m or less, over 83 ⁇ m and over 100 ⁇ m.
- those having a diameter of more than 45 ⁇ m and 75 ⁇ m or less showed a distribution of less than 0.1% and those having a diameter of 45 ⁇ m or less were 0.7%.
- the sulfur grade was 0.062%.
- Example 2 Using the same reaction vessel as in Example 1, 90 liters of a solution slurry containing 205 g / L of ammonium sulfate, 1 g / L of polyacrylic acid, and 105 g / L of nickel powder was placed in this reaction vessel, and the lid was covered. The internal temperature was kept at 185 ° C.
- a starting solution comprising a nickel sulfate ammine complex solution having a nickel concentration of 83 g / L and ammonium sulfate having a concentration of 120 g / L is supplied to the reaction vessel at a flow rate of 1 liter per minute, and at the same time, the slurry concentration is 150 g / L.
- the nickel seed slurry of L was continuously supplied to the reaction vessel at a flow rate of 0.5 liters per minute to proceed the reduction treatment.
- the nickel powder which comprises a nickel seed crystal slurry used that whose average particle diameter is 1 micrometer.
- hydrogen gas was blown in while controlling the internal pressure of the reaction vessel to be 3.5 MPa.
- the reduced slurry was continuously extracted while controlling the amount of liquid stored in the reaction vessel to be in the range of 90 liters ⁇ 5 liters, and this operation was continued for 16 hours.
- the extracted reduced slurry was solid-liquid separated into a nickel powder and a filtrate using a Nutsche, and the obtained nickel powder was washed and vacuum dried.
- the reduction treatment reaction time in the reaction vessel was 60 minutes from the start of the initial solution and the seed crystal slurry to the extraction of the nickel powder slurry.
- the reduction rate (reaction rate) that is, the rate at which hydrogen gas was used for the nickel powder precipitation reaction, was 98.9%.
- the average particle diameter represented by D50 of the obtained nickel powder was 5.2 ⁇ m, which was finer than that of Example 1, but there was little variation (see FIG. 2). Furthermore, the sulfur quality was 0.003%, and a high purity nickel powder having a low sulfur quality that was below the LME grade specification of 0.01% was obtained.
- Example 2 In a reaction vessel having the same structure as in Example 1 and having a capacity of 90 liters, 205 g / L of ammonium sulfate, 105 g / L of nickel powder, and 90 liters of a solution of 1 g / L of polyacrylic acid were added, and the temperature was maintained at 185 ° C., and hydrogen gas was blown in. The pressure was 3.5 MPa.
- a starting solution composed of a nickel sulfate ammine complex solution having a nickel concentration of 83 g / L and ammonium sulfate contained at a concentration of 120 g / L is added to the pressure vessel at a rate of 1 liter / minute, and a slurry is also added.
- a nickel seed crystal slurry having a concentration of 150 g / L was added at a rate of 0.5 l / min.
- the starting nickel sulfate ammine complex solution was added at a concentration of 1 g / L of polyacrylic acid and supplied to the reaction vessel. Hydrogen gas was blown in so that the pressure in the pressurized container was 3.5 MPa.
- the average particle diameter of the nickel powder constituting the extracted nickel powder slurry was 5.9 ⁇ m.
- the nickel powder slurry was continuously extracted while controlling the amount of liquid in the pressurized container in the range of 90 liters ⁇ 5 liters, and this operation was continued for 12 hours.
- the reduction treatment reaction time in the reaction vessel was 60 minutes from the start of the initial solution and the seed crystal slurry to the extraction of the nickel powder slurry. At this time, the reduction rate, that is, the reaction rate was 96.8%.
- the sulfur grade was 0.003%, which was lower than the LME grade specification of 0.01%.
- the particle size was 6.4 ⁇ m at D50, and very fine powder could be stably obtained as seen in FIG.
- Example 2 Into the reaction vessel having the same capacity of 90 liters as in Example 1, 200 g / L of ammonium sulfate, 11 g / L of nickel powder, and 90 liters of a starting solution of 0.1 g / L of polyacrylic acid were put, and the temperature was maintained at 185 ° C., and hydrogen gas was supplied. The blowing pressure was 3.5 MPa.
- a nickel sulfate ammine complex solution having a nickel concentration of 83 g / L and a starting solution having a composition of ammonium sulfate concentration of 360 g / L were added to the reaction vessel at a flow rate of 1 liter / min, and a nickel seed crystal slurry having a concentration of 33 g / L was added. Added at a rate of 0.5 liters / minute. Moreover, hydrogen gas was blown so that the pressure of the pressurized container was maintained at 3.5 MPa, and the reduction treatment was advanced.
- the operation of continuously extracting the reduced nickel powder slurry from the reaction vessel was continued for 6 hours while controlling the amount of liquid stored in the reaction vessel to be in the range of 90 liters ⁇ 5 liters.
- the average particle diameter of the nickel powder constituting the 33 g / L nickel seed crystal slurry is 53 ⁇ m, and the reduction treatment reaction time in the reaction vessel is 60 minutes from the start and introduction of the seed crystal slurry to the extraction of the nickel powder slurry. Met.
- the reduction rate or reaction rate was 89.0%.
- the recovered nickel powder had a sulfur grade of 0.01%, which satisfied the LME grade specification of 0.01%. Further, the particle diameter was 78.0 ⁇ m at D50, and a sufficiently grown nickel powder was obtained. As shown in FIGS. 4 and 5, the surface of the nickel powder was very smooth and spherical.
- a pressure vessel autoclave with an inner volume of 190 liters and titanium lined on the inner wall of the vessel was used as a reaction vessel (reaction vessel).
- reaction vessel reaction vessel
- hydrogen gas was blown into the gas phase portion of the reaction vessel, and the pressure in the vessel was adjusted to 3.5 MPa.
- a nickel sulfate ammine complex solution having a nickel concentration of 83 g / liter and a solution having an ammonium sulfate concentration of 120 g / liter are supplied to the reaction vessel at a flow rate of 1 liter per minute, and at the same time, 150 g / liter of nickel powder is supplied.
- the slurry was continuously fed into the reaction vessel at a flow rate of 0.5 liters per minute.
- the nickel powder which comprises a nickel powder slurry used that whose average particle diameter is 1 micrometer.
- hydrogen gas was blown in while controlling the internal pressure of the reaction vessel to be 3.5 MPa.
- the nickel powder slurry was continuously extracted while controlling the liquid volume in the reaction vessel to be in the range of 90 liters ⁇ 5 liters, and this operation was continued for 16 hours.
- the extracted nickel powder slurry was solid-liquid separated into nickel powder and filtrate using a Nutsche, and the obtained nickel powder was washed and vacuum dried.
- the reduction rate that is, the rate at which hydrogen gas was used for the nickel powder precipitation reaction, was 98.9%.
- the obtained nickel powder was able to stably obtain a fine nickel powder of 5.2 ⁇ m with an average particle diameter represented by D50.
- Example 1 A solution of the same composition was continuously supplied at the same flow rate except that it did not contain polyacrylic acid in the same reaction vessel as in Example 1, and reduced with hydrogen gas under the same conditions to obtain a nickel powder slurry.
- the powder slurry was solid-liquid separated to obtain nickel powder.
- the reduction rate or reaction rate was 99.6%.
- the ratio of 100 ⁇ m to 300 ⁇ m occupies 99% or more, but the total particle size distribution is less than 0.1%, more than 300 ⁇ m and less than 300 ⁇ m. 91%, more than 100 ⁇ m and less than 150 ⁇ m 8.3%, more than 75 ⁇ m and less than 100 ⁇ m and less than 45 ⁇ m and less than 75 ⁇ m are both less than 0.1% and less than 45 ⁇ m Shows a distribution of 0.7%, and nickel powder as fine as the present invention could not be obtained. As described above, it was confirmed that fine nickel powder can be obtained continuously and efficiently by using the method of the present invention.
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Abstract
Description
また、本発明の第5の発明は、第1から第3の発明における種結晶が、0.1~10μmの範囲の平均粒径のニッケル粉を用いることを特徴とするニッケル粉の製造方法である。
また、分散剤の効果により低硫黄品位で微細な粉状の析出物としてニッケル粉を溶液から抽出、回収でき、さらに、ニッケル粉の粒径と分散剤濃度の組み合わせによっては、球状で平滑な表面を持つ粗大なニッケル粉をも得ることができる。
本発明で製造したニッケル粉は、積層セラミックコンデンサーの内部構成物質であるニッケルペースト用途として用いることができる他、水素による上記還元処理を繰り返すことにより粒子を成長させ、高純度のニッケルメタルを製造することが可能な品質を維持しつつ高い反応稼働率を維持できる製造方法であって、工業上顕著な効果を奏するものである。
以下、本発明のニッケル粉の製造方法を説明する。
ここで添加する種結晶は、平均粒径が0.1μm以上、100μm以下の粉末を用いることが好ましく、0.1μm以上、10μm以下であればより好ましい。
また、最終のニッケル析出物で不純物となって汚染することのない物質として、ニッケル粉を用いるのが好適である。この種結晶として使用するニッケル粉は、例えば上記硫酸ニッケルアンミン錯体溶液にヒドラジンなどの還元剤を添加することにより作製することができる。
ここで用いる分散剤としては、ポリアクリル酸塩であれば特に限定されないが、工業的に安価に入手できるものとしてポリアクリル酸ナトリウムが好適である。
分散剤を添加する場合、添加量は添加する種結晶の重量に対し0.5~5重量%となる範囲が好適である。0.5%未満では分散効果が得られず、また、5%を超えて添加しても分散効果に影響はなく、過剰な添加となる。
あるいは、添加するポリアクリル酸は硫酸ニッケルアンミン錯体溶液の液量に対して0.5~1.0g/リットルの濃度になるように添加してもよく、その時に添加する種結晶は、平均粒径が0.1μm以上、10μm以下の種結晶が良い。
なお、本発明において、例えば上記の0.5~5重量%の記述の「~」は0.5重量%以上5重量%以下である、ことを示す。
また、分散剤の効果により低硫黄品位で微細な粉状の析出物としてニッケルを、溶液から抽出、回収できる。また、ニッケル粉の粒径と分散剤濃度の組み合わせによって、球状で平滑な表面を持つ粗大なニッケル粉を得ることもできる。
なお、ニッケル種晶スラリーを構成する種結晶としたニッケル粉は、平均粒径が1μmのものを使用した。また、水素ガスは加圧容器の内圧力が3.5MPaを維持するように制御しながら吹き込んだ。
表1-1に示すように、その抜き出したニッケル粉スラリー中のニッケル濃度は0.28g/Lで、還元率(反応率)、すなわち水素ガスがニッケル粉の析出反応に用いられた割合は、99.6%であった。
全体の粒度分布は、300μmを超えた割合は0.1%未満で、150μmを超え300μm以下であるものが91%、100μmを超え150μm以下であるものが8.3%、75μmを超え100μm以下であるものと45μmを超え75μm以下であるものがいずれも0.1%未満、45μm以下であるものが0.7%という分布を示した。
図1に示すように、粒子の形状は一定でなく凝集が見られるものの、粒度分布のばらつきが少ないニッケル粉を連続して製造できることを確かめた。なお、硫黄品位は0.062%となった。
次に、この反応容器にニッケル濃度が83g/Lの濃度である硫酸ニッケルアンミン錯体溶液と濃度120g/Lの硫酸アンモニウムからなる始液を毎分1リットルの流量で供給し、同時にスラリー濃度が150g/Lのニッケル種晶スラリーを毎分0.5リットルの流量で反応容器に連続して供給して還元処理を進めた。
なお、ニッケル種晶スラリーを構成するニッケル粉は、平均粒径が1μmのものを使用した。また、水素ガスは反応容器の内圧力が3.5MPaを維持するように制御しながら吹き込んだ。
その還元率(反応率)、すなわち水素ガスがニッケル粉の析出反応に用いられた割合、は98.9%だった。
得たニッケル粉のD50であらわした平均粒径は5.2μmと上記実施例1よりは微細だったが、ばらつきは少なかった(図2参照)。さらに硫黄品位は0.003%となり、LMEグレードのスペックである0.01%を下回った低硫黄品位の高純度なニッケル粉が得られた。
このとき、還元率すなわち反応率は96.8%であった。
硫黄品位は0.003%となり、LMEグレードのスペックである0.01%を下回った。
粒径はD50で6.4μmであり、図3に見られるように非常に微細な粉を安定的に得ることができた。
回収したニッケル粉の硫黄品位は0.01%となり、LMEグレードのスペックである0.01%を満たした。
また粒径はD50で78.0μmであり、十分に成長したニッケル粉が得られた。図4、5に示すように、そのニッケル粉の表面は非常に平滑で真球状の粒子となった。
次いで水素ガスを反応容器の気相部に吹込み、容器内の圧力を3.5MPaにした。次に、この反応容器にニッケル濃度が83g/リットルの濃度である硫酸ニッケルアンミン錯体溶液と硫酸アンモニウム濃度が120g/リットルである溶液を毎分1リットルの流量で供給し、同時に150g/リットルのニッケル粉スラリーを毎分0.5リットルの流量で反応容器に連続して供給した。
なお、ニッケル粉スラリーを構成するニッケル粉は、平均粒径が1μmのものを使用した。また、水素ガスは反応容器の内圧力が3.5MPaを維持するように制御しながら吹き込んだ。
得たニッケル粉は、D50で表した平均粒径で、5.2μmと微細なニッケル粉を安定的に得ることができた。
上記実施例1と同じ反応容器に、ポリアクリル酸を含まない以外は、同じ組成の溶液を同じ流量で連続して供給し、同じ条件で水素ガスにより還元し、ニッケル粉スラリーを得、このニッケル粉スラリーを固液分離してニッケル粉を得た。還元率すなわち反応率は99.6%であった。
上記のように、本発明の方法を用いることで、微細なニッケル粉を連続して効率よく得ることができることが確認された。
Claims (8)
- 硫酸ニッケルアンミン錯体溶液と種結晶を反応容器に供給し、前記反応容器に水素ガスを供給して、前記硫酸ニッケルアンミン錯体溶液中のニッケル錯イオンを還元処理してニッケル粉を生成することを特徴とするニッケル粉の製造方法において、
前記還元処理が、硫酸ニッケルアンミン錯体溶液を反応容器に連続的に供給しつつ、
反応容器内の温度を150℃以上、185℃以下の範囲に制御し、
水素ガスの供給量を、反応容器内の内圧が2.5~3.5MPaの範囲に維持されるように制御することを特徴とするニッケル粉の製造方法。 - 反応容器内に水素ガスを供給すると共に、前記反応容器内に硫酸ニッケルアンミン錯体溶液と種結晶を供給して、前記硫酸ニッケルアンミン錯体溶液中のニッケル錯イオンを還元処理し、ニッケル粉を生成するニッケル粉の製造方法において、
前記還元処理が、
硫酸アンモニウムとニッケル粉を含むスラリーを貯留させて前記反応容器内に液相部と気相部を構成し、前記反応容器内への水素ガスの供給による前記気相部の内圧制御と、
前記液相部への種結晶を含むスラリーと硫酸ニッケルアンミン錯体溶液の連続的な供給と、
前記反応容器内の温度の150℃以上、185℃以下の範囲への制御と、
前記水素ガスの供給量を反応容器内の内圧が2.5~3.5MPaの範囲に維持する制御を行いながら、前記硫酸ニッケルアンミン錯体溶液中のニッケル錯イオンを還元することを特徴とするニッケル粉の製造方法。 - 前記硫酸ニッケルアンミン錯体溶液にはポリアクリル酸が、0.5~1.0g/リットルの濃度になるように添加されることを特徴とする請求項1又は2記載のニッケル粉の製造方法。
- 前記種結晶が、0.1~100μmの範囲の平均粒径のニッケル粉を用いることを特徴とする請求項1又は2に記載のニッケル粉の製造方法。
- 前記種結晶が、0.1~10μmの範囲の平均粒径のニッケル粉を用いることを特徴とする請求項1から3のいずれか1項に記載のニッケル粉の製造方法。
- 前記種結晶の添加量が、硫酸ニッケルアンミン錯体溶液中のニッケルの重量に対し、1~100重量%となる量の範囲であることを特徴とする請求項1から5のいずれか1項に記載のニッケル粉の製造方法。
- 前記還元処理に供される硫酸ニッケルアンミン錯体溶液が、前記硫酸ニッケルアンミン錯体溶液中の種結晶の重量に対し、0.5~5重量%となる量の範囲でポリアクリル酸を含むことを特徴とする請求項1から6のいずれか1項に記載のニッケル粉の製造方法。
- 前記還元処理が、前記反応容器内での還元処理反応時間を5分以上、120分以内になるように、前記種結晶を含む硫酸ニッケルアンミン錯体溶液を前記反応容器に連続的に供給することを特徴とする請求項1~7のいずれか1項に記載のニッケル粉の製造方法。
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JP2019218591A (ja) * | 2018-06-19 | 2019-12-26 | 住友金属鉱山株式会社 | ニッケル粉の回収方法 |
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