JP2017082270A5 - - Google Patents
Download PDFInfo
- Publication number
- JP2017082270A5 JP2017082270A5 JP2015210258A JP2015210258A JP2017082270A5 JP 2017082270 A5 JP2017082270 A5 JP 2017082270A5 JP 2015210258 A JP2015210258 A JP 2015210258A JP 2015210258 A JP2015210258 A JP 2015210258A JP 2017082270 A5 JP2017082270 A5 JP 2017082270A5
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- powder
- solid
- solution
- ammine complex
- 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
Links
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 93
- 229910052803 cobalt Inorganic materials 0.000 claims description 93
- 239000010941 cobalt Substances 0.000 claims description 93
- 239000000843 powder Substances 0.000 claims description 64
- 239000007787 solid Substances 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- KTVIXTQDYHMGHF-UHFFFAOYSA-L Cobalt(II) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 27
- 229940044175 cobalt sulfate Drugs 0.000 claims description 27
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006722 reduction reaction Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000011268 mixed slurry Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- -1 ammonia compound Chemical class 0.000 claims description 7
- 230000000536 complexating Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 210000004940 Nucleus Anatomy 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000003638 reducing agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L Cobalt(II) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- PJQDFOMVKDFESH-UHFFFAOYSA-N cobalt(2+);N-(9H-fluoren-2-yl)-N-oxidoacetamide Chemical class [Co+2].C1=CC=C2C3=CC=C(N([O-])C(=O)C)C=C3CC2=C1.C1=CC=C2C3=CC=C(N([O-])C(=O)C)C=C3CC2=C1 PJQDFOMVKDFESH-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000037250 Clearance Effects 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N Cobalt(II,III) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000035512 clearance Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001888 polyacrylic acid Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、硫酸コバルトアンミン錯体を含有する溶液から、コバルト粉末を製造する方法に関する。特に結晶成長に用いる種結晶を得る方法に関する。 The present invention relates to a method for producing cobalt powder from a solution containing a cobalt sulfate ammine complex. In particular, the present invention relates to a method for obtaining a seed crystal used for crystal growth.
電子材料や耐熱合金として用いられるコバルトを得る様々な方法が知られている。近年は、電池材料などの原料になるコバルト塩類の需要が高まっている。
これらのコバルト塩類は、コバルトメタルを酸に溶解して製造することが一般であるが、従来から一般的な電気コバルトなどシートや塊状の形態は取扱いしやすいものの酸への溶解が極端に遅く、一方で微粉末の形状は、酸には溶解しやすいものの飛散しやすいなど取扱いに難があり、両者の長所を生かすためにブリケットと呼ばれる粒ないし粉末を圧密あるいは焼結して得たものが好まれている。
Various methods for obtaining cobalt used as electronic materials and heat-resistant alloys are known. In recent years, the demand for cobalt salts as raw materials for battery materials and the like has increased.
These cobalt salts are generally produced by dissolving cobalt metal in an acid, but the conventional sheet and block form such as general electric cobalt are easy to handle, but dissolution in acid is extremely slow, On the other hand, the shape of the fine powder is difficult to handle because it is easy to dissolve in acid, but it is difficult to handle, and in order to take advantage of both, it is preferable to obtain a powder or powder obtained by compacting or sintering briquettes. It is rare.
このような小サイズのコバルト粒や粉末を得る方法として、溶融させたコバルトをガスまたは水中に分散させ微細粉を得るアトマイズ法や、特許文献1に示されるような、コバルトを揮発させ、気相中で還元することでコバルト粉を得るCVD法などの乾式法が知られている。 As a method for obtaining such small-sized cobalt particles and powder, an atomizing method in which molten cobalt is dispersed in gas or water to obtain a fine powder, or cobalt is volatilized as disclosed in Patent Document 1, and a gas phase is obtained. A dry method such as a CVD method is known in which cobalt powder is obtained by reduction in the inside.
また、湿式プロセスによりコバルト粉を製造する方法として特許文献2に示されるような、還元剤を用いて生成する方法や、特許文献3に示されるような高温で還元雰囲気中にコバルト溶液を噴霧することにより、熱分解反応によりコバルト粉を得る噴霧熱分解法などがある。
しかし、これらの方法は高価な試薬類や多量のエネルギーを必要とするため、上記の電池材料など大量の物量を工業的に得る方法としては経済的ではない。
Further, as a method for producing cobalt powder by a wet process, a method using a reducing agent as shown in Patent Document 2 or a cobalt solution sprayed in a reducing atmosphere at a high temperature as shown in Patent Document 3 Thus, there is a spray pyrolysis method for obtaining cobalt powder by a thermal decomposition reaction.
However, since these methods require expensive reagents and a large amount of energy, they are not economical as methods for industrially obtaining a large amount of materials such as the battery materials described above.
また、特許文献4に示されるような、種結晶としてコバルト粉末を使用し成長させる方法では、pHが4以下の酸性溶液中で反応させるために、種結晶や成長したコバルト粉が再溶解して実収率が下がってしまう課題があった。 Further, in the method of growing by using cobalt powder as a seed crystal as shown in Patent Document 4, the seed crystal and the grown cobalt powder are re-dissolved in order to react in an acidic solution having a pH of 4 or less. There was a problem that the actual yield was lowered.
さらに、原料の硫酸コバルト溶液に水酸化ナトリウム水溶液を添加し、水素還元を行う方法では、pH4を維持できずにpHが上昇してしまうと、コバルトの水酸化物が発生して還元反応が進まなくなり、その結果、還元反応での効率が低下する課題があった。 Furthermore, in the method in which a sodium hydroxide aqueous solution is added to the raw material cobalt sulfate solution and hydrogen reduction is performed, if the pH rises without being able to maintain pH 4, cobalt hydroxide is generated and the reduction reaction proceeds. As a result, there was a problem that the efficiency in the reduction reaction was reduced.
一方で、非特許文献1に示されるような、コバルトをアンモニア錯体の形態とした硫酸コバルトアンミン錯体溶液に、水素ガスを供給して錯体溶液中のコバルトイオンを還元してコバルト粉を得る方法は、工業的に安価であり有用である。
けれども、この方法でも、湿式反応により水溶液中から粒子を発生させ成長させようとすることから、上記の各先行技術と同じように不均一に多数の結晶核が発生し、成長が阻害される課題がある。つまり派生する結晶の核の数を適正な範囲に制御し、効率よく成長させることが欠かせない。
そこで前述したように種結晶と呼ばれる微細な結晶を少量共存させたスラリーに還元剤を供給し、種結晶の表面に目的物を成長させ所定の粒径の粉末を得る方法が一般に用いられている。
On the other hand, as shown in Non-Patent Document 1, a method of obtaining cobalt powder by supplying hydrogen gas to a cobalt sulfate ammine complex solution in which cobalt is in the form of an ammonia complex to reduce cobalt ions in the complex solution. Industrially inexpensive and useful.
However, even in this method, since particles are generated and grown from an aqueous solution by a wet reaction, a large number of crystal nuclei are generated non-uniformly and the growth is hindered in the same manner as each of the prior arts described above. There is. In other words, it is indispensable to control the number of derived crystal nuclei within an appropriate range for efficient growth.
Therefore, as described above, a method is generally used in which a reducing agent is supplied to a slurry in which a small amount of fine crystals called seed crystals coexist and a target product is grown on the surface of the seed crystals to obtain a powder having a predetermined particle size. .
上記において添加する種結晶は、製品の一部を繰り返して粉砕するなどの処理を行って使用することが多い。しかし、加工には手間も要し、また繰り返す分だけ収率が減少するので、コスト増加につながる課題があった。さらに、単純に粉砕によってだけでは必ずしも最適な粒径や性状の種結晶を安定して得ることができるとは限らないなどの課題もあった。
すなわち結晶成長に用いる種結晶を安定して得る方法が求められていた。
The seed crystals added in the above are often used after being subjected to a treatment such as pulverizing a part of the product repeatedly. However, it takes time and effort for processing, and the yield decreases as much as it is repeated. Furthermore, there has been a problem that the optimum grain size and properties of the seed crystal cannot always be obtained simply by pulverization.
That is, a method for stably obtaining a seed crystal used for crystal growth has been demanded.
このような状況の中で、本発明は、硫酸コバルトアンミン錯体を含有する溶液からコバルト粉を製造する上で還元反応効率を上げる方法により効率良くコバルト粉を得る製造方法を提供する。 Under such circumstances, the present invention provides a production method for efficiently obtaining cobalt powder by a method for increasing the reduction reaction efficiency in producing cobalt powder from a solution containing a cobalt ammine sulfate complex.
このような課題を解決する本発明の第1の発明は、硫酸コバルト溶液に、アンモニア、アンモニア化合物の溶液、或いは前記アンモニア及びアンモニア化合物の溶液の両者を添加して硫酸コバルトアンミン錯体を含有する溶液を得る錯化工程と、前記錯化工程で得た硫酸コバルトアンミン錯体を含有する溶液に、前記硫酸コバルトアンミン錯体を含有する溶液に不溶又は難溶性の固形物としてニッケル粉を加えて混合スラリーとする混合工程と、前記混合工程で得た混合スラリーを反応槽内に装入し、反応槽に水素ガスを吹き込んで混合スラリーに含まれるコバルトを還元してコバルト成分がコバルト粉として固形物表面に析出したコバルト析出物を含有するコバルト粉スラリーを得る還元・析出工程と、次いで得られたコバルト粉スラリーからコバルト析出物と還元後液を分離する固液分離処理と、得られたコバルト析出物を、加えた固形物のニッケル粉と前記固形物のニッケル粉表面に析出したコバルト粉とに分離する固形物分離処理を有し、前記還元後液と固形物のニッケル粉とコバルト粉を形成する固液分離工程を順に経ることを特徴とするコバルト粉の種結晶の製造方法である。 A first invention of the present invention that solves such problems is a solution containing a cobalt sulfate ammine complex by adding ammonia, an ammonia compound solution, or both of the ammonia and ammonia compound solution to a cobalt sulfate solution. To the solution containing the cobalt ammine complex obtained in the complexing step, and adding the nickel powder as a solid insoluble or sparingly soluble in the solution containing the cobalt ammine complex, And mixing the slurry obtained in the mixing step into the reaction vessel, blowing hydrogen gas into the reaction vessel to reduce the cobalt contained in the mixed slurry, and the cobalt component as cobalt powder on the solid surface a step reduction-precipitation to obtain a cobalt powder slurry containing precipitated cobalt precipitate, then the resulting cobalt powder slurry Solid separating Luo cobalt precipitate and a solid-liquid separation process for separating the reduced solution after the resulting cobalt precipitates in the added cobalt was deposited on the nickel powder surface of the nickel powder and the solid solid powder It is a manufacturing method of the seed crystal of cobalt powder which has a substance separation process, and goes through the solid-liquid separation process which forms the nickel after said reduction liquid, solid nickel powder, and cobalt powder in order.
本発明の第2の発明は、第1の発明における固形物のニッケル粉の平均粒径が、0.1μm以上、5μm以下であることを特徴とするコバルト粉の種結晶の製造方法である。 A second invention of the present invention is a method for producing a seed crystal of cobalt powder, characterized in that the average particle size of the solid nickel powder in the first invention is 0.1 μm or more and 5 μm or less.
本発明の第3の発明は、第1及び第2の発明における硫酸コバルトアンミン錯体を含有する溶液中のコバルト濃度が、75g/L以下であることを特徴とするコバルト粉の種結晶の製造方法である。 According to a third aspect of the present invention, there is provided a method for producing a seed crystal of cobalt powder, wherein the cobalt concentration in the solution containing the cobalt ammine sulfate complex in the first and second aspects is 75 g / L or less. It is.
本発明によれば、硫酸コバルトアンミン錯体溶液を水素ガスで還元してコバルト粉を製造する際に、硫酸コバルトアンミン錯体溶液に種結晶として添加してコバルト粉を形成するのに適切なサイズの種結晶を効率よく得ることができる。 According to the present invention, when producing a cobalt powder by reducing a cobalt sulfate ammine complex solution with hydrogen gas, a seed of an appropriate size is added to the cobalt sulfate ammine complex solution as a seed crystal to form the cobalt powder. Crystals can be obtained efficiently.
本発明は、硫酸コバルトアンミン錯体溶液に、水素ガスを吹き込んでコバルト粉を製造する際に添加する種結晶を効率よく製造する方法である。 The present invention is a method for efficiently producing a seed crystal to be added when a cobalt powder is produced by blowing hydrogen gas into a cobalt sulfate ammine complex solution.
以下、本発明のコバルト粉の製造方法を、図1に示す製造フロー図を参照して説明する。本発明では、元液となる硫酸コバルト溶液を錯化工程、混合工程、還元・析出工程、固液分離工程を経ることで、コバルト粉を得る。
なお、本発明でいう還元率は、得たコバルト粉の重量(g)を、供給した硫酸コバルト溶液(L)中に含有されるコバルト物量(g/L)で除した割合で定義した。
Hereinafter, the manufacturing method of the cobalt powder of this invention is demonstrated with reference to the manufacturing flowchart shown in FIG. In this invention, cobalt powder is obtained by passing the cobalt sulfate solution used as an original liquid through a complexing process, a mixing process, a reduction / precipitation process, and a solid-liquid separation process.
In addition, the reduction rate as used in the field of this invention was defined by the ratio which remove | divided the weight (g) of the obtained cobalt powder by the cobalt substance amount (g / L) contained in the supplied cobalt sulfate solution (L).
[錯化工程]
本発明で用いることのできる硫酸コバルト溶液は、特に限定はされないが、コバルトおよびコバルトを含有する混合硫化物、粗硫酸コバルト、酸化コバルト、水酸化コバルト、炭酸コバルト、コバルト粉などから選ばれる一種、または複数の混合物から成る工業中間物などのコバルト含有物を、硫酸あるいはアンモニアにより浸出・溶解して得たコバルト浸出液を用いることができる。なお、工業的には上記のコバルト浸出液には様々な不純物も含有されるのが普通であり、上述の浸出液は溶媒抽出法、イオン交換法、中和などの浄液工程を施すことにより浸出液中の不純物元素を除去して用いることが一般である。
[Complexing process]
The cobalt sulfate solution that can be used in the present invention is not particularly limited, but is a kind selected from cobalt and cobalt-containing mixed sulfide, crude cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt powder, and the like, Alternatively, a cobalt leaching solution obtained by leaching and dissolving a cobalt-containing material such as an industrial intermediate composed of a plurality of mixtures with sulfuric acid or ammonia can be used. In addition, industrially, the cobalt leachate generally contains various impurities, and the leachate described above is contained in the leachate by performing a liquid purification process such as solvent extraction, ion exchange, and neutralization. In general, it is used after removing the impurity element.
次に上記のコバルト浸出液に、アンモニア水や硫酸アンモニウムを添加し、硫酸コバルトアンミン錯体溶液を得る。
なお、溶液中の硫酸アンモニウム濃度は10〜500g/Lの範囲とすることが好ましい。500g/L以上の濃度にすると、溶解度を超えてしまい結晶が析出する場合があり操業上のトラブルを生じるので好ましくない。また、10g/L未満の濃度は反応により硫酸アンモニウムが新たに生成するため、工業的に10g/L未満は困難である。
また、硫酸コバルトアンミン錯体溶液でのコバルト濃度は75g/L以下の濃度とする。これは、後工程で固形物を添加して反応させる際に、硫酸コバルトアンミン錯体溶液中のコバルト濃度が高すぎると反応場が不足して還元率が低下するためである。
Next, aqueous ammonia or ammonium sulfate is added to the cobalt leaching solution to obtain a cobalt sulfate ammine complex solution.
The ammonium sulfate concentration in the solution is preferably in the range of 10 to 500 g / L. If the concentration is 500 g / L or more, the solubility may be exceeded and crystals may be deposited, which may cause operational troubles. Moreover, since ammonium sulfate newly produces | generates by reaction by the density | concentration of less than 10 g / L, industrially less than 10 g / L is difficult.
The cobalt concentration in the cobalt sulfate ammine complex solution is 75 g / L or less. This is because, when adding and reacting a solid in the subsequent step, if the cobalt concentration in the cobalt sulfate ammine complex solution is too high, the reaction field is insufficient and the reduction rate is lowered.
[混合工程]
この工程では、上記で作製された硫酸コバルトアンミン錯体溶液に、析出の母体となる固形物を添加する。
添加する固形物は、硫酸コバルトアンミン錯体溶液、硫酸アンモニウム水溶液或いはアルカリ溶液に対して不溶、若しくは溶解度が小さい難溶なものであれば、特に限定はない。
[Mixing process]
In this step, a solid substance that serves as a base material for precipitation is added to the cobalt sulfate ammine complex solution prepared above.
The solid substance to be added is not particularly limited as long as it is insoluble in the cobalt sulfate ammine complex solution, the ammonium sulfate aqueous solution, or the alkali solution, or is hardly soluble and has low solubility.
具体的にはニッケル粉を用いる事が好ましい。
コバルト粉を固形物に用いると、コバルト析出物と同一なので、後工程でこれらを引き剥がす必要がなく、種晶として用いるには最適であるが、工業的に微細なコバルト粉を低価格かつ安定して入手することは困難である。
Specifically, it is preferable to use nickel powder.
When cobalt powder is used as a solid substance, it is the same as cobalt precipitate, so it is not necessary to peel them off in the subsequent process and is optimal for use as a seed crystal, but industrially fine cobalt powder is inexpensive and stable. It is difficult to obtain.
なお、鉄粉は安価・容易に入手できる利点があるが、酸性溶液に容易に溶解し、結晶核となり難い欠点がある。また、溶解した鉄イオンが新たなコンタミの原因となるなど適さない。
また本発明のように難溶ないし不溶性の固形物を用いて、その上にコバルトを析出させる方法では、従来一般に使われてきた種結晶を用いてコバルトを析出させ、種結晶ごと製品とする方法と異なり、再溶解の影響を無視できるほど避けられ、製品の一部を繰り返す必要もないので、プロセスの物量バランス上ではアンミン錯体溶液中に含有されるコバルト錯イオンをほぼ完全に還元する事が出来る特徴がある。
Iron powder has the advantage of being inexpensive and easily available, but has the disadvantage of being easily dissolved in an acidic solution and difficult to form crystal nuclei. Also, the dissolved iron ion is not suitable because it causes new contamination.
Also, in the method of depositing cobalt on a hardly soluble or insoluble solid as in the present invention, a method of depositing cobalt using a seed crystal that has been conventionally used to produce a product together with the seed crystal. Unlike the process, the effect of redissolving is negligibly avoided and there is no need to repeat a part of the product, so that the cobalt complex ions contained in the ammine complex solution can be reduced almost completely in terms of the process quantity balance. There are features that can be done.
なお、固形物は、析出したコバルト粉が効果的に分離できるように表面がなだらかな形状であるものが好ましく、添加量は前述したように、溶液中に存在するコバルト量と当量以上となる量が必要で、具体的には固形物にニッケル粉を用いる場合には、75g/L以上の添加が必要となる。 In addition, it is preferable that the solid has a gentle shape so that the precipitated cobalt powder can be effectively separated, and the amount added is an amount that is equal to or more than the amount of cobalt present in the solution, as described above. More specifically, when nickel powder is used as a solid material, 75 g / L or more must be added.
[還元・析出工程]
次に、混合工程でニッケル粉を添加して形成したスラリーを、圧力容器の反応槽内に装入し、その反応槽内に水素ガスなどの還元剤を吹き込み、そのスラリー中のコバルト錯イオンを還元し、前記の固形物の表面にコバルトを析出させる。
[Reduction / precipitation process]
Next, the slurry formed by adding nickel powder in the mixing step is charged into a reaction vessel of a pressure vessel, a reducing agent such as hydrogen gas is blown into the reaction vessel, and cobalt complex ions in the slurry are injected. Reduce to deposit cobalt on the surface of the solid.
このときの混合スラリーの温度、即ち反応温度は、150〜200℃の範囲が好ましい。150℃未満では還元効率が低下し、200℃以上にしても反応への影響はなく、むしろ熱エネルギー等のロスが増加する。 The temperature of the mixed slurry at this time, that is, the reaction temperature is preferably in the range of 150 to 200 ° C. If it is less than 150 degreeC, reduction | restoration efficiency will fall, and even if it is 200 degreeC or more, there will be no influence on reaction, rather, loss, such as a heat energy, will increase.
また、反応槽内の溶液との隙間である気相部の圧力は、水素ガスの供給により1.0〜4.0MPaの範囲に維持することが好ましい。1.0MPa未満の圧力では気相部から溶液へのガスの混入量が少ないので反応効率が低下する。一方、4.0MPaを超えた圧力でも反応が促進されるなどの影響はなく、むしろ水素ガスのロスが増加するだけで有利にはならない。
なお、水素ガスは反応槽内の気相部に吹き込んでもスラリー中に直接吹き込んでもいずれでも構わない。
Moreover, it is preferable to maintain the pressure of the gaseous-phase part which is a clearance gap with the solution in a reaction tank in the range of 1.0-4.0 MPa by supply of hydrogen gas. When the pressure is less than 1.0 MPa, the reaction efficiency is lowered because the amount of gas mixed into the solution from the gas phase is small. On the other hand, even if the pressure exceeds 4.0 MPa, there is no influence such as that the reaction is promoted. Rather, the loss of hydrogen gas only increases, which is not advantageous.
The hydrogen gas may be blown into the gas phase portion in the reaction tank or directly into the slurry.
[固液分離工程]
還元・析出工程で得た表面にコバルト析出物を有する固形物を、圧力容器内の還元後液と共に圧力容器から取り出し、還元後液と固液分離する。
この固液分離は、例えばヌッチェと濾瓶を使う方法や、遠心分離機を用いる方法、フィルタープレスを用いる方法などいずれでも構わない。
[Solid-liquid separation process]
The solid matter having cobalt precipitates on the surface obtained in the reduction / precipitation step is taken out from the pressure vessel together with the post-reduction liquid in the pressure vessel, and solid-liquid separated from the post-reduction solution.
This solid-liquid separation may be any method such as a method using Nutsche and a filter bottle, a method using a centrifuge, or a method using a filter press.
次に固形物にコバルト以外の物質を使用する場合は、固形物と表面のコバルト析出物を分離する操作を行ってもよい。
具体的に分離する方法は、固形物とコバルト析出物に衝撃を与えるなど適宜おこなうことができる。
Next, when using a substance other than cobalt as the solid, an operation of separating the solid and the cobalt deposit on the surface may be performed.
The method of specifically separating can be appropriately performed by giving an impact to the solid and the cobalt precipitate.
なお、固形物を含んだままのコバルト析出物や固形物と分離したあとのコバルト析出物の大きさが、種晶として用いる用途に対して小さすぎる場合は、再度上記混合工程に繰り返してコバルト析出物の大きさを増加させることができる。
また、ここで回収した固形物は再度上記混合工程に繰り返して使用することができる。
還元後液は、そのままあるいは加熱・蒸留等の処理によってアンモニアに再生し、前記錯化工程の錯化剤として繰り返し使用することができる。
In addition, if the size of the cobalt precipitate containing the solid matter and the cobalt precipitate after being separated from the solid matter is too small for the use to be used as a seed crystal, repeat the above mixing step again to precipitate cobalt. The size of the object can be increased.
Moreover, the solid substance collect | recovered here can be repeatedly used for the said mixing process again.
The solution after reduction can be regenerated to ammonia as it is or by treatment such as heating / distillation and repeatedly used as a complexing agent in the complexing step.
以下に本発明のコバルト粉を得るための種結晶を生成する実施例を説明する。
なお、平均粒径は市販のレーザ回折・散乱式粒子径分布測定装置(マイクロトラック)を用いて測定した。
The Example which produces | generates the seed crystal for obtaining the cobalt powder of this invention below is demonstrated.
The average particle size was measured using a commercially available laser diffraction / scattering particle size distribution measuring device (Microtrack).
コバルト75gに相当する硫酸コバルトと硫酸アンモニウム330gに25%アンモニア水を191ml加えて溶解し、さらに合計の液量が1000mlになるように調整して、硫酸コバルトアンミン錯体を含有する溶液を得た。
この溶液に、析出母体となる粒径1μmのニッケル粉75gを添加して混合スラリーを得た。
A solution containing a cobalt sulfate ammine complex was obtained by adding 191 ml of 25% aqueous ammonia to 330 g of cobalt sulfate and 75 g of cobalt corresponding to 75 g of cobalt and dissolving the solution, and adjusting the total liquid volume to 1000 ml.
To this solution, 75 g of nickel powder having a particle size of 1 μm serving as a precipitation matrix was added to obtain a mixed slurry.
次いで、上記の混合スラリーを容量3リットルのオートクレーブの内筒缶内に装入後、撹拌しながら185℃に昇温、保持した状態で、混合スラリー中に水素ガスを吹き込み、オートクレーブの内筒缶内の圧力を3.5MPaに維持するように水素ガスを供給した。水素ガスの供給から60分が経過した後に水素ガスの供給を停止し、内筒缶を冷却した。 Next, after charging the above mixed slurry into an inner can of an autoclave having a capacity of 3 liters, with stirring and raising the temperature to 185 ° C., hydrogen gas was blown into the mixed slurry, and the inner can of the autoclave Hydrogen gas was supplied so as to maintain the internal pressure at 3.5 MPa. After 60 minutes had passed since the supply of hydrogen gas, the supply of hydrogen gas was stopped and the inner cylinder can was cooled.
室温まで冷却後、内筒缶内の混合スラリーを濾過して表面にコバルトの析出物を生成した不溶体固体を取り出し、次いで濾ビンとヌッチェを使用し、吸引濾過によって固液分離した。
このときのコバルトの還元反応率は99%であった。
After cooling to room temperature, the mixed slurry in the inner cylinder can was filtered to take out an insoluble solid having a cobalt precipitate formed on the surface, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche.
The reduction reaction rate of cobalt at this time was 99%.
(比較例1)
コバルト75gと硫酸アンモニウム330gと25%アンモニア水を191ml含む溶液を得、これに本発明の種結晶の固形物の代わりに、濃度40wt%のポリアクリル酸3.73gを分散剤として添加し、合計の液量が1000mlになるように調整して、硫酸コバルトアンミン錯体を含有する溶液を作製した。
この溶液に、析出母体となるコバルト粉75gを添加して混合スラリーを作製した。
(Comparative Example 1)
A solution containing 75 g of cobalt, 330 g of ammonium sulfate, and 191 ml of 25% aqueous ammonia was obtained. To this, 3.73 g of polyacrylic acid having a concentration of 40 wt% was added as a dispersant in place of the solid of the seed crystal of the present invention. The liquid volume was adjusted to 1000 ml to prepare a solution containing a cobalt sulfate ammine complex.
To this solution, 75 g of cobalt powder as a precipitation matrix was added to prepare a mixed slurry.
その作製した混合スラリーを実施例1と同じオートクレーブの内筒缶内に装入後、撹拌しながら185℃に昇温、保持した状態で、水素ガスを吹き込み、オートクレーブの内筒缶内の圧力を3.5MPaに維持するように水素ガスを供給した。
水素ガスの供給から60分が経過した後に水素ガスの供給を停止し、内筒缶を冷却した。
After the prepared mixed slurry was charged into the inner cylinder can of the same autoclave as in Example 1, the hydrogen gas was blown in a state where the temperature was raised and maintained at 185 ° C. while stirring, and the pressure in the inner cylinder can of the autoclave was changed. Hydrogen gas was supplied so as to maintain the pressure at 3.5 MPa.
After 60 minutes had passed since the supply of hydrogen gas, the supply of hydrogen gas was stopped and the inner cylinder can was cooled.
室温まで冷却後、内筒缶内の混合スラリーを濾過して表面にコバルトの析出物が生成した不溶体固体を取り出し、次いで濾ビンとヌッチェを使用し、吸引濾過による固液分離を行なった。このときのコバルト還元反応率は72%と本発明の実施例ほどの効率は得られなかった。 After cooling to room temperature, the mixed slurry in the inner cylinder can was filtered to take out an insoluble solid having a cobalt precipitate formed on the surface, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche. At this time, the cobalt reduction reaction rate was 72%, which was not as efficient as the examples of the present invention.
(比較例2)
コバルト75gの硫酸コバルト溶液に、硫酸アンモニウム330gを含む溶液に25%アンモニア水を191ml、合計の液量が1000mlになるように調整して、硫酸コバルトアンミン錯体を含有する溶液を作製した。
この溶液に、この溶液に溶解する固形物として市販の平均粒径1μmの鉄粉75gを添加して混合スラリーを作製した。
(Comparative Example 2)
A solution containing cobalt sulfate ammine complex was prepared by adjusting 191 ml of 25% aqueous ammonia to a solution containing 330 g of ammonium sulfate in a cobalt sulfate solution of 75 g of cobalt to a total liquid volume of 1000 ml.
To this solution, 75 g of commercially available iron powder having an average particle diameter of 1 μm was added as a solid substance dissolved in this solution to prepare a mixed slurry.
作製した混合スラリーを実施例1で用いたオートクレーブの内筒缶内に装入後、撹拌しながら185℃に昇温、保持した状態で、水素ガスを吹き込み、オートクレーブの内筒缶内の圧力を3.5MPaに維持するように水素ガスを供給した。水素ガスの供給から60分が経過した後に水素ガスの供給を停止し、内筒缶を冷却した。 After the prepared mixed slurry was charged into the inner can of the autoclave used in Example 1, the temperature was raised to 185 ° C. while being stirred, and hydrogen gas was blown into the autoclave so that the pressure inside the inner can of the autoclave was increased. Hydrogen gas was supplied so as to maintain the pressure at 3.5 MPa. After 60 minutes had passed since the supply of hydrogen gas, the supply of hydrogen gas was stopped and the inner cylinder can was cooled.
室温まで冷却後、内筒缶内の混合スラリーを濾過して表面にコバルトの析出物を生成した鉄粉を取り出し、次いで濾ビンとヌッチェを使用し吸引濾過による固液分離を行なった。 After cooling to room temperature, the mixed slurry in the inner cylinder can was filtered to take out iron powder on which cobalt precipitates were formed, and then solid-liquid separation was performed by suction filtration using a filter bottle and Nutsche.
この比較例2に係るコバルト還元反応率は、76%と従来の分散剤を用いた場合よりは高いものの、溶解しやすい固形物を添加しても本発明の実施例ほどの効果は得られないことがわかった。 Although the cobalt reduction reaction rate according to Comparative Example 2 is 76%, which is higher than in the case of using a conventional dispersant, the effect as in the examples of the present invention cannot be obtained even when a solid substance that is easily dissolved is added. I understood it.
Claims (3)
前記錯化工程で得た硫酸コバルトアンミン錯体を含有する溶液に、前記硫酸コバルトアンミン錯体を含有する溶液に不溶又は難溶性の固形物としてニッケル粉を加えて混合スラリーとする混合工程と、
前記混合工程で得た混合スラリーを反応槽内に装入し、反応槽に水素ガスを吹き込んで混合スラリーに含まれるコバルトを還元してコバルト成分がコバルト粉として固形物表面に析出したコバルト析出物を含有するコバルト粉スラリーを得る還元・析出工程と、
次いで得られたコバルト粉スラリーからコバルト析出物と還元後液を分離する固液分離処理と、得られたコバルト析出物を、加えた固形物のニッケル粉と前記固形物のニッケル粉表面に析出したコバルト粉とに分離する固形物分離処理を有し、前記還元後液と固形物のニッケル粉とコバルト粉を形成する固液分離工程を順に経ることを特徴とするコバルト粉の種結晶の製造方法。 A complexing step of adding ammonia, an ammonia compound solution, or both of the ammonia and ammonia compound solution to a cobalt sulfate solution to obtain a solution containing a cobalt sulfate ammine complex;
A mixing step in which nickel powder is added to the solution containing the cobalt sulfate ammine complex obtained in the complexing step as a solid that is insoluble or hardly soluble in the solution containing the cobalt sulfate ammine complex ;
The mixed slurry obtained in the mixing step is charged into a reaction vessel, and hydrogen gas is blown into the reaction vessel to reduce cobalt contained in the mixed slurry, whereby a cobalt precipitate is deposited on the solid surface as cobalt powder. Reduction / precipitation step to obtain a cobalt powder slurry containing
Next, a solid-liquid separation process for separating the cobalt deposit and the post-reduction liquid from the obtained cobalt powder slurry, and the obtained cobalt deposit were deposited on the solid nickel powder and the solid nickel powder surface. A method for producing a seed crystal of cobalt powder , comprising: a solid matter separation process for separating the powder into cobalt powder, wherein the post-reduction liquid, the solid nickel powder, and a solid-liquid separation step for forming cobalt powder are sequentially performed. .
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015210258A JP6350830B2 (en) | 2015-10-26 | 2015-10-26 | Method for producing seed crystal of cobalt powder |
US15/770,546 US20190061006A1 (en) | 2015-10-26 | 2016-10-17 | Method for producing seed crystal of cobalt powder |
CN201680062357.XA CN108349011A (en) | 2015-10-26 | 2016-10-17 | The manufacturing method of the crystal seed of cobalt powder |
PCT/JP2016/080690 WO2017073392A1 (en) | 2015-10-26 | 2016-10-17 | Method for producing seed crystal of cobalt powder |
EP16859622.9A EP3369499A4 (en) | 2015-10-26 | 2016-10-17 | Method for producing seed crystal of cobalt powder |
AU2016345951A AU2016345951B2 (en) | 2015-10-26 | 2016-10-17 | Method for producing seed crystal of cobalt powder |
CA3003239A CA3003239C (en) | 2015-10-26 | 2016-10-17 | Method for producing seed crystal of cobalt powder |
PH12018500896A PH12018500896A1 (en) | 2015-10-26 | 2018-04-26 | Method for producing seed crystal of cobalt powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015210258A JP6350830B2 (en) | 2015-10-26 | 2015-10-26 | Method for producing seed crystal of cobalt powder |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2017082270A JP2017082270A (en) | 2017-05-18 |
JP2017082270A5 true JP2017082270A5 (en) | 2018-01-25 |
JP6350830B2 JP6350830B2 (en) | 2018-07-04 |
Family
ID=58630124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015210258A Active JP6350830B2 (en) | 2015-10-26 | 2015-10-26 | Method for producing seed crystal of cobalt powder |
Country Status (8)
Country | Link |
---|---|
US (1) | US20190061006A1 (en) |
EP (1) | EP3369499A4 (en) |
JP (1) | JP6350830B2 (en) |
CN (1) | CN108349011A (en) |
AU (1) | AU2016345951B2 (en) |
CA (1) | CA3003239C (en) |
PH (1) | PH12018500896A1 (en) |
WO (1) | WO2017073392A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020183728A1 (en) * | 2019-03-14 | 2020-09-17 | 住友金属鉱山株式会社 | Nickel powder production method |
CN116199270B (en) * | 2022-12-20 | 2023-08-11 | 科立鑫(珠海)新能源有限公司 | Treatment process for reducing wastewater in cobalt oxide production process |
CN116177614B (en) * | 2023-03-23 | 2023-11-21 | 科立鑫(珠海)新能源有限公司 | Technological method for reducing waste rate in cobalt oxide preparation process |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3730756A (en) * | 1971-04-28 | 1973-05-01 | Sherritt Gordon Mines Ltd | Method of producing cobalt-coated composite powder |
US3775098A (en) * | 1971-12-27 | 1973-11-27 | Sherritt Gordon Mines Ltd | Cobalt precipitation from aqueous solutions |
US4545814A (en) * | 1984-05-23 | 1985-10-08 | Amax Inc. | Production of cobalt and nickel powder |
US4761177A (en) * | 1987-06-26 | 1988-08-02 | Amax Inc. | Production of cobalt and nickel powder |
US5246481A (en) * | 1992-10-26 | 1993-09-21 | Sherritt Gordon Limited | Production of metallic powder |
CN1060703C (en) * | 1996-05-30 | 2001-01-17 | 北京有色金属研究总院 | Method for preparing nanometre metal powder |
CN100374231C (en) * | 2006-04-06 | 2008-03-12 | 北京工业大学 | Preparation method of nano-cobalt powder |
CN101298102B (en) * | 2008-06-13 | 2011-03-23 | 上海师范大学 | Preparation of nano cobalt granule |
CN101428349B (en) * | 2008-07-29 | 2011-06-22 | 张建玲 | Method for producing nickel-cobalt metal powder |
JP6099601B2 (en) * | 2014-02-17 | 2017-03-22 | 国立大学法人高知大学 | Method for producing nickel powder |
CN104439280A (en) * | 2014-12-09 | 2015-03-25 | 英德佳纳金属科技有限公司 | Simultaneous preparing method of cobalt hydroxide and cobalt powder |
-
2015
- 2015-10-26 JP JP2015210258A patent/JP6350830B2/en active Active
-
2016
- 2016-10-17 CA CA3003239A patent/CA3003239C/en not_active Expired - Fee Related
- 2016-10-17 CN CN201680062357.XA patent/CN108349011A/en active Pending
- 2016-10-17 EP EP16859622.9A patent/EP3369499A4/en not_active Withdrawn
- 2016-10-17 US US15/770,546 patent/US20190061006A1/en not_active Abandoned
- 2016-10-17 WO PCT/JP2016/080690 patent/WO2017073392A1/en active Application Filing
- 2016-10-17 AU AU2016345951A patent/AU2016345951B2/en not_active Ceased
-
2018
- 2018-04-26 PH PH12018500896A patent/PH12018500896A1/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5828923B2 (en) | Method for producing nickel powder | |
JP6610425B2 (en) | Method for producing nickel powder | |
JP5936783B2 (en) | Method for producing nickel powder | |
JP6099601B2 (en) | Method for producing nickel powder | |
JP2015166488A5 (en) | ||
WO2016117138A1 (en) | Method for producing nickel powder | |
JP6350830B2 (en) | Method for producing seed crystal of cobalt powder | |
JP6489315B2 (en) | Method for producing cobalt powder | |
JP2017082270A5 (en) | ||
JP5796696B1 (en) | Method for producing nickel powder | |
JP6726396B2 (en) | Nickel powder manufacturing method | |
JP6641632B2 (en) | Nickel powder manufacturing method | |
JP6531913B2 (en) | Method of producing nickel powder | |
JP6241617B2 (en) | Method for producing cobalt powder | |
JP5881091B2 (en) | Method for producing nickel powder | |
JP2017155319A5 (en) | ||
JP7194349B2 (en) | Nickel powder manufacturing method | |
WO2017150105A1 (en) | Nickel powder production method | |
JP2017155265A5 (en) | ||
JP7007650B2 (en) | Nickel powder manufacturing method | |
JP2020015971A (en) | Manufacturing method of nickel powder | |
JP2018178232A (en) | Method for manufacturing nickel powder | |
JP2018141203A (en) | Method of producing nickel powder for seed crystals |