JP7415276B2 - Method for producing metal cadmium - Google Patents
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- JP7415276B2 JP7415276B2 JP2020070336A JP2020070336A JP7415276B2 JP 7415276 B2 JP7415276 B2 JP 7415276B2 JP 2020070336 A JP2020070336 A JP 2020070336A JP 2020070336 A JP2020070336 A JP 2020070336A JP 7415276 B2 JP7415276 B2 JP 7415276B2
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims description 182
- 229910052793 cadmium Inorganic materials 0.000 title claims description 181
- 239000002184 metal Substances 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 202
- 229910052759 nickel Inorganic materials 0.000 claims description 101
- 229910052725 zinc Inorganic materials 0.000 claims description 50
- 239000011701 zinc Substances 0.000 claims description 50
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 49
- 239000007858 starting material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- -1 cadmium Chemical compound 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Description
本発明は、カドミウム溶液から、金属カドミウムを製造する方法に関する。 The present invention relates to a method for producing metallic cadmium from a cadmium solution.
亜鉛製錬所における亜鉛地金の原料として、粗酸化亜鉛等から不純物を分離回収して得た酸化亜鉛鉱が広く用いられている。この粗酸化亜鉛は、例えば、鉄鋼業における高炉や電気炉等の製鋼炉から発生する鉄鋼ダストから還元焙焼処理を経て得ることができ、資源リサイクルの促進の観点からは、鉄鋼ダストの亜鉛原料としての再利用は望ましいものである。 Zinc oxide ore obtained by separating and recovering impurities from crude zinc oxide and the like is widely used as a raw material for zinc ingots in zinc smelters. This crude zinc oxide can be obtained, for example, from steel dust generated from steelmaking furnaces such as blast furnaces and electric furnaces in the steel industry through reduction roasting treatment. Reuse as a resource is desirable.
このような鉄鋼ダスト由来の粗酸化亜鉛には、その主成分である酸化亜鉛以外に、塩素やフッ素等のハロゲン成分及びカドミウム等の不純物が高い割合で含有されている。これらの不純物のうち、特にカドミウムについては有害金属としての性質を持っており、酸化亜鉛の製造プラントにおいては、カドミウムを分離回収する処理が必須となっている。
一方、カドミウムはニッケルカドミウム電池の負極材として使用されるなど、電子エレクトロニクス材料として重要な有用金属のひとつとなっている。
Such crude zinc oxide derived from steel dust contains high proportions of halogen components such as chlorine and fluorine, and impurities such as cadmium, in addition to its main component, zinc oxide. Among these impurities, cadmium in particular has properties as a toxic metal, and in zinc oxide manufacturing plants, it is essential to separate and recover cadmium.
On the other hand, cadmium is used as a negative electrode material in nickel-cadmium batteries, making it an important useful metal as an electronic material.
ところで、カドミウムを分離回収する方法としては、例えば、湿式処理で不純物を粗分離後、乾式処理によって精分離する方法が一般的に行われている。
しかしながら、乾式処理は化石燃料や、電力の使用において環境やエネルギー負荷が高いという問題があった。よって、不純物の分離を一層高度に行い、湿式工程に続く乾式工程での化石燃料や電力の使用を抑制する、湿式処理技術の開発が望まれている。
By the way, as a method for separating and recovering cadmium, for example, a method is generally used in which impurities are roughly separated by wet treatment and then purified by dry treatment.
However, dry processing has the problem of high environmental and energy burden due to the use of fossil fuels and electricity. Therefore, there is a need for the development of a wet processing technology that can further improve the separation of impurities and suppress the use of fossil fuels and electricity in the dry process that follows the wet process.
不純物の分離を湿式処理において行う既存の技術としては、具体的に、特許文献１の技術を挙げることができる。特許文献１に開示される技術は、通常乾式処理で分離される不純物としてのニッケルを、予め析出母液となるカドミウム溶液からジメチルグリオキシム処理で分離を行う湿式処理技術であるが、このような予備処理を行うことは非効率であり、ジメチルグリオキシムは高価な薬剤であるため、コストが掛かるという課題があった。 As an existing technique for separating impurities in a wet process, the technique disclosed in Patent Document 1 can be specifically mentioned. The technology disclosed in Patent Document 1 is a wet processing technology in which nickel, which is an impurity that is usually separated in dry processing, is separated in advance from a cadmium solution, which is a precipitation mother liquor, by dimethylglyoxime treatment. There were problems in that the treatment was inefficient, and dimethylglyoxime was an expensive drug, so it was expensive.
このような背景から、ニッケルを含有するカドミウム溶液から、ニッケルの析出を抑えつつ、効率的に金属カドミウムを析出する湿式処理技術の開発が期待されていた。 Against this background, there have been expectations for the development of a wet processing technology that efficiently precipitates metallic cadmium from a nickel-containing cadmium solution while suppressing the precipitation of nickel.
本発明は、このような実情に鑑みてなされたものであり、ニッケルを含有するカドミウム溶液から、ニッケルの析出が抑制された空孔を有する金属カドミウムを析出する、金属カドミウムの製造方法を提供するものである。 The present invention has been made in view of the above circumstances, and provides a method for producing metallic cadmium, which precipitates metallic cadmium having pores in which nickel precipitation is suppressed from a nickel-containing cadmium solution. It is something.
本発明者らは、上述の目的を達成するために鋭意研究を重ねた結果、カドミウム溶液に対する亜鉛セメンテーションにおいて、亜鉛セメンテーション終了時のカドミウム濃度を調整することによって、上述の課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive research to achieve the above object, the present inventors have found that the above problems can be solved by adjusting the cadmium concentration at the end of zinc cementation in zinc cementation for cadmium solution. This discovery led to the completion of the present invention.
本発明の第１の発明は、始液のニッケルを含むカドミウム溶液から亜鉛セメンテーションを用いて空孔を有する金属カドミウムを析出させる、金属カドミウムの製造方法であって、「前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液（以下、亜鉛セメンテーション終点のカドミウム溶液）」のカドミウム濃度を、出発物質となる始液のニッケルを含むカドミウム溶液のニッケル含有量とカドミウム含有量に応じて、前記始液のニッケルを含むカドミウム溶液からのニッケルの析出が抑制される濃度範囲に調整することを特徴とする、金属カドミウムの製造方法である。 A first aspect of the present invention is a method for producing metal cadmium, which comprises precipitating metal cadmium having pores from a cadmium solution containing nickel as an initial solution by using zinc cementation, which comprises: The cadmium concentration of the nickel-containing cadmium solution (hereinafter referred to as the nickel-containing cadmium solution at the end point of zinc cementation) is adjusted according to the nickel content and cadmium content of the nickel-containing cadmium solution as the starting material . This is a method for producing metallic cadmium, which is characterized by adjusting the concentration of nickel from a liquid nickel-containing cadmium solution to a range in which precipitation of nickel is suppressed.
本発明の第２の発明は、第１の発明において、前記出発物質となる始液のニッケルを含むカドミウム溶液が、カドミウム含有量が２．０質量％以上、ニッケル含有量が０．００２質量％以下のニッケルを含むカドミウム溶液であり、前記始液のニッケルを含むカドミウム溶液に対する前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液のカドミウム濃度を、１．０～１０．０ｇ／Ｌの範囲となるように調整することを特徴とする、金属カドミウムの製造方法である。 A second aspect of the present invention is that in the first aspect, the cadmium solution containing nickel as the starting material has a cadmium content of 2.0% by mass or more and a nickel content of 0.002% by mass. The cadmium solution containing nickel is as follows, and the cadmium concentration of the cadmium solution containing nickel at the end of the zinc cementation is in the range of 1.0 to 10.0 g/L with respect to the cadmium solution containing nickel as the starting solution. This is a method for producing metal cadmium, which is characterized by adjusting the metal cadmium so that
本発明の第３の発明は、第１の発明において、前記出発物質となる始液のニッケルを含むカドミウム溶液が、カドミウム含有量が７．０質量％以上、ニッケル含有量が０．００５質量％以下の始液のニッケルを含むカドミウム溶液であり、前記始液のニッケルを含むカドミウム溶液に対する前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液のカドミウム濃度を、１．４～１０．０ｇ／Ｌの範囲となるように調整することを特徴とする、金属カドミウムの製造方法である。 The third invention of the present invention is the first invention, wherein the cadmium solution containing nickel as the starting material has a cadmium content of 7.0% by mass or more and a nickel content of 0.005% by mass. The following starting solution is a cadmium solution containing nickel , and the cadmium concentration of the nickel -containing cadmium solution at the end of the zinc cementation with respect to the starting solution containing nickel is 1.4 to 10.0 g/L. This is a method for producing metal cadmium, which is characterized by adjusting the cadmium so as to fall within the range of .
本発明によれば、ニッケルを含有するカドミウム溶液から、その溶液からのニッケルの析出が抑制された空孔を有する金属カドミウムを製造することが可能である。 According to the present invention, it is possible to produce metallic cadmium having pores in which precipitation of nickel from the solution is suppressed from a nickel-containing cadmium solution.
以下、本発明の具体的な実施形態について詳細に説明する。なお、本発明は以下の実施形態に限定されるものではなく、本発明の範囲から逸脱しない内容において、種々の変更が可能である。
本発明の金属カドミウムの製造方法の一実施形態は、カドミウム溶液の亜鉛セメンテーションにおいて、その亜鉛セメンテーション終了時（以下、「亜鉛セメンテーション終点」または単に「終点」と略す場合もある。）のカドミウム溶液中のカドミウム濃度を、出発物質となるカドミウム溶液のニッケル含有量とカドミウム含有量に応じて、調整することによって、ニッケルの大半を、その溶液中に残留させ、その溶液からのニッケルの析出が抑制された空孔を有する金属カドミウム（以下、スポンジカドミウムとも称す。）を得るものである。
Hereinafter, specific embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and various changes can be made without departing from the scope of the present invention.
One embodiment of the method for producing metal cadmium of the present invention is a method for zinc cementation of a cadmium solution at the end of the zinc cementation (hereinafter sometimes abbreviated as "zinc cementation end point" or simply "end point"). By adjusting the cadmium concentration in the cadmium solution according to the nickel content and cadmium content of the cadmium solution as a starting material, most of the nickel remains in the solution, and nickel is precipitated from the solution. Metal cadmium (hereinafter also referred to as sponge cadmium) having pores with suppressed pores is obtained.
ここで、前記カドミウム溶液に対する亜鉛セメンテーションは、主に下記（１）の化学反応式で表される反応に基づいて進行する。 Here, the zinc cementation of the cadmium solution proceeds mainly based on the reaction represented by the following chemical reaction formula (1).
また、本実施形態では、始液となるカドミウム溶液のニッケル含有量とカドミウム含有量に応じて、前記亜鉛セメンテーションの終了時のカドミウム濃度を調整することによって、得られる空孔を有する金属カドミウム（スポンジカドミウム）のニッケル品位を抑制することが可能である。この場合、出発物質となるカドミウム溶液のニッケル含有量とカドミウム含有量は特に限定されない。
さらに、後述のニッケル含有量とカドミウム含有量を有するカドミウム溶液に対して亜鉛セメンテーションを行い、且つ、この亜鉛セメンテーションの終了時のカドミウム濃度を、後述の濃度範囲に調整することによって、ニッケル品位が電池材料として好適に利用できる品位に抑制された、金属カドミウムを効率的に得ることが可能である。
In addition, in this embodiment, the cadmium concentration at the end of the zinc cementation is adjusted according to the nickel content and cadmium content of the starting cadmium solution. It is possible to suppress the nickel quality of sponge cadmium. In this case, the nickel content and cadmium content of the cadmium solution serving as the starting material are not particularly limited.
Furthermore, by performing zinc cementation on a cadmium solution having the nickel content and cadmium content described below, and adjusting the cadmium concentration at the end of this zinc cementation to the concentration range described below, the nickel grade can be improved. It is possible to efficiently obtain metallic cadmium whose quality is suppressed to such a level that it can be suitably used as a battery material.
ここで、カドミウム２２ｇ／Ｌ（２．２質量％）、ニッケル０．０１９ｇ／Ｌ（０．００１９質量％）を含有する硫酸イオンを含んだ溶液（以下、浸出液という）２００ｍＬずつを、５００ｍｌビーカーに分取し、その分取した浸出液を２５℃の常温で撹拌しながら、その浸出液に純度９９．４質量％、表面積４０ｃｍ２の亜鉛板を浸漬し、亜鉛セメンテーションを行うことにより得られた、空孔を有する金属カドミウムであるスポンジカドミウムのニッケル品位を分析した結果を表１に示す。
前記の亜鉛セメンテーションは、この亜鉛セメンテーションの間、適時間隔で浸出液を５ｍｌずつ分取し、その浸出液中のカドミウム濃度を直ちに分析し、分析のカドミウム濃度が所定のカドミウム濃度に到達した時点を終点として、直ちに亜鉛板をビーカーから取り出して亜鉛セメンテーションを停止し、その時点で生成されているスポンジカドミウムを分析する手順を繰り返すことにより実施した。
Here, 200 mL each of a solution containing sulfate ions (hereinafter referred to as leachate) containing 22 g/L (2.2 mass %) of cadmium and 0.019 g/L (0.0019 mass %) of nickel was placed in a 500 ml beaker. A zinc plate with a purity of 99.4% by mass and a surface area of 40 cm 2 was immersed in the leachate while stirring the leachate at room temperature of 25 ° C., and zinc cementation was performed. Table 1 shows the results of analyzing the nickel quality of sponge cadmium, which is metal cadmium having pores.
In the above-mentioned zinc cementation, 5 ml of the leachate is taken at appropriate intervals during the zinc cementation, the cadmium concentration in the leachate is immediately analyzed, and the time point when the analyzed cadmium concentration reaches the predetermined cadmium concentration is determined. At the end point, the zinc cementation was stopped by immediately removing the zinc plate from the beaker, and the procedure was repeated to analyze the sponge cadmium that had been formed at that point.
表１を参照すると、亜鉛セメンテーション終点のカドミウム濃度が７．２ｇ／Ｌ（０．７２質量％）を下回る付近から徐々に析出するニッケルの量が増加し始め、さらに１．０ｇ／Ｌ（０．１質量％）を下回る付近から析出するニッケルの増加割合が増加する様子が窺える。
これは、亜鉛セメンテーション終点のカドミウム濃度を、浸出液からのニッケルの析出が抑制される濃度範囲に調整することによって、所望のニッケル品位を有するスポンジカドミウムを析出させることが可能であることを示すものである。
Referring to Table 1, when the cadmium concentration at the end point of zinc cementation falls below 7.2 g/L (0.72 mass%), the amount of nickel precipitated gradually begins to increase, and further increases to 1.0 g/L (0.72 mass%). It can be seen that the rate of increase in the amount of nickel precipitated increases from below .1% by mass).
This shows that it is possible to precipitate sponge cadmium with the desired nickel grade by adjusting the cadmium concentration at the end point of zinc cementation to a concentration range that suppresses the precipitation of nickel from the leachate. It is.
例えば、ニッケル品位が１５０ｐｐｍ以下に抑制されたスポンジカドミウムを析出させる場合には、亜鉛セメンテーション終点のカドミウム濃度を１．０ｇ／Ｌ（０．１質量％）以上の濃度範囲に調整すればよく、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムを析出させる場合には、亜鉛セメンテーション終点のカドミウム濃度を０．０９１ｇ／Ｌ（０．００１９質量％）以上の濃度範囲に調整すればよい。 For example, when depositing sponge cadmium whose nickel grade is suppressed to 150 ppm or less, the cadmium concentration at the end of zinc cementation may be adjusted to a concentration range of 1.0 g/L (0.1% by mass) or more. When depositing sponge cadmium whose nickel grade is suppressed to 200 ppm or less, the cadmium concentration at the end of zinc cementation may be adjusted to a concentration range of 0.091 g/L (0.0019 mass %) or more.
ところで、析出によって得られるスポンジカドミウムのニッケル品位は、亜鉛セメンテーション終点のカドミウム濃度だけでなく、出発物質となるカドミウム溶液のニッケル含有量や、カドミウム含有量にも影響される。
このため、あるニッケル含有量とカドミウム含有量とを有するカドミウム溶液を出発物質として、ニッケル品位が抑制されたスポンジカドミウムを得るためには、予め、その組成を有するカドミウム溶液に対応する、スポンジカドミウム中のニッケル品位と、亜鉛セメンテーション終点のカドミウム濃度との対応関係を、上記と同様な試験によって求めておくことが好ましい。そのうえで、求めたこの対応関係に基づいて、亜鉛セメンテーション終点のカドミウム濃度を、ニッケル品位を抑制する濃度範囲内になるように調整する。
By the way, the nickel quality of the sponge cadmium obtained by precipitation is affected not only by the cadmium concentration at the end of zinc cementation, but also by the nickel content and cadmium content of the cadmium solution that is the starting material.
Therefore, in order to obtain sponge cadmium with suppressed nickel quality using a cadmium solution having a certain nickel content and cadmium content as a starting material, it is necessary to prepare a sponge cadmium solution corresponding to the cadmium solution having the composition in advance. It is preferable to determine the correspondence between the nickel grade of the zinc cementation and the cadmium concentration at the end point of the zinc cementation by a test similar to the above. Then, based on this determined correspondence, the cadmium concentration at the end point of zinc cementation is adjusted so that it falls within a concentration range that suppresses the nickel quality.
なお、電池材料として好適に利用することのできるスポンジカドミウムは、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムであるが、こうしたスポンジカドミウムを得るための亜鉛セメンテーション終点のカドミウム濃度範囲も、上記と同様な試験によって求めることができる。 Note that sponge cadmium that can be suitably used as a battery material is sponge cadmium with a nickel content suppressed to 200 ppm or less, but the cadmium concentration range at the end of zinc cementation to obtain such sponge cadmium is also the same as above. It can be determined by a similar test.
例えば、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムを得るための亜鉛セメンテーション終点のカドミウム濃度範囲は、ニッケル含有量が０．００２質量％以下であり、カドミウム含有量が２．０質量％以上であるカドミウム溶液を出発物質とする場合には、１．０ｇ／Ｌ（０．１質量％）以上の濃度範囲として求めることができ、そして、ニッケル含有量が０．００５質量％以下であり、カドミウム含有量が７．０質量％以上であるカドミウム溶液を出発物質とする場合には、１．４ｇ／Ｌ（０．１４質量％）以上の濃度範囲として求めることができる。上記については、後述の実施例において説明する。 For example, the cadmium concentration range at the end of zinc cementation to obtain sponge cadmium with a nickel quality suppressed to 200 ppm or less is such that the nickel content is 0.002% by mass or less and the cadmium content is 2.0% by mass or more. When using a cadmium solution as a starting material, it can be determined as a concentration range of 1.0 g / L (0.1% by mass) or more, and the nickel content is 0.005% by mass or less, When a cadmium solution having a cadmium content of 7.0% by mass or more is used as a starting material, the concentration range can be determined to be 1.4 g/L (0.14% by mass) or more. The above will be explained in Examples below.
この場合、さらに亜鉛セメンテーションの終了時のカドミウム濃度を１０．０ｇ／Ｌ（１．０質量％）以下の濃度範囲となるように調整することによって、液中に残存するカドミウムを抑制できて、効率的なスポンジカドミウムの析出が可能である。 In this case, by further adjusting the cadmium concentration at the end of zinc cementation to a concentration range of 10.0 g/L (1.0% by mass) or less, the amount of cadmium remaining in the liquid can be suppressed. Efficient sponge cadmium precipitation is possible.
以下、本発明の実施例を示してさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in further detail by showing examples, but the present invention is not limited to these examples in any way.
カドミウム２０ｇ／Ｌ（２．０質量％）、ニッケル０．０２ｇ／Ｌ（０．００２質量％）、を含有する硫酸イオンを含んだ溶液（以下、浸出液という）２００ｍＬずつ、５００ｍｌビーカーに分取した。 200 mL each of a solution containing sulfate ions (hereinafter referred to as leachate) containing 20 g/L (2.0 mass %) of cadmium and 0.02 g/L (0.002 mass %) of nickel was dispensed into a 500 ml beaker. .
浸出液を２５℃の常温で撹拌しながら純度９９．４質量％、表面積４０ｃｍ２の亜鉛板を浸漬し、亜鉛セメンテーションを行った。 Zinc cementation was performed by immersing a zinc plate with a purity of 99.4% by mass and a surface area of 40 cm 2 in the leachate while stirring at room temperature of 25°C.
上記亜鉛セメンテーションの間、適時浸出液を５ｍｌずつ分取し、浸出液中のカドミウム濃度を直ちに分析し、カドミウム濃度が１０．０ｇ／Ｌ（１．０質量％）となった時点を終点として直ちに亜鉛板をビーカーから取り出して亜鉛セメンテーションを停止した。
その後、得られたセメンテーション済浸出液を濾過した後、得られた空孔を有する金属カドミウムであるスポンジカドミウムのニッケル品位を分析した。
During the above zinc cementation, 5 ml of the leachate was taken at appropriate times, and the cadmium concentration in the leachate was immediately analyzed. The zinc cementation was stopped by removing the board from the beaker.
Thereafter, the obtained cemented leachate was filtered, and the nickel quality of the obtained sponge cadmium, which is metal cadmium having pores, was analyzed.
終点を、１．０ｇ／Ｌ（０．１質量％）とする以外は、実施例１と同じ条件で亜鉛セメンテーションを実施し、空孔を有する金属カドミウムであるスポンジカドミウムのニッケル品位を分析した。 Zinc cementation was carried out under the same conditions as in Example 1, except that the end point was set to 1.0 g / L (0.1 mass %), and the nickel quality of sponge cadmium, which is metal cadmium with pores, was analyzed. .
カドミウム７０ｇ／Ｌ（７．０質量％）、ニッケル０．０５ｇ／Ｌ（０．００５質量％）、を含有する硫酸イオンを含んだ溶液を使用し、終点を、９．７ｇ／Ｌ（０．９７質量％）とする以外は、実施例１と同じ条件で亜鉛セメンテーションを実施し、空孔を有する金属カドミウムであるスポンジカドミウムのニッケル品位を分析した。 A solution containing sulfate ions containing 70 g/L (7.0% by mass) of cadmium and 0.05 g/L (0.005% by mass) of nickel was used, and the end point was set at 9.7 g/L (0.0% by mass). Zinc cementation was carried out under the same conditions as in Example 1, except that the cadmium content was 97% by mass), and the nickel quality of sponge cadmium, which is metal cadmium having pores, was analyzed.
カドミウム７０ｇ／Ｌ（７．０質量％）、ニッケル０．０５ｇ／Ｌ（０．００５質量％）、を含有する硫酸イオンを含んだ溶液を使用し、終点を、１．４ｇ／Ｌ（０．１４質量％）とする以外は、実施例１と同じ条件で亜鉛セメンテーションを実施し、空孔を有する金属カドミウムであるスポンジカドミウムのニッケル品位を分析した。 A solution containing sulfate ions containing 70 g/L (7.0% by mass) of cadmium and 0.05 g/L (0.005% by mass) of nickel was used, and the end point was set to 1.4 g/L (0.0% by mass). Zinc cementation was carried out under the same conditions as in Example 1, except that the zinc cementation rate was 14% by mass), and the nickel quality of sponge cadmium, which is metal cadmium having pores, was analyzed.
次に、上記実施例を基に、「亜鉛セメンテーション前の浸出液（始液）のカドミウム濃度」「亜鉛セメンテーション前の浸出液（始液）のニッケル濃度」と「亜鉛セメンテーション終点における浸出液のカドミウム濃度」と、「その終点で取り出したスポンジカドミウム中のニッケル品位」との関係を表２に示す。 Next, based on the above example, "Cadmium concentration in the leachate (starting solution) before zinc cementation," "Nickel concentration in the leachate (starting solution) before zinc cementation," and "Cadmium concentration in the leachate at the end point of zinc cementation." Table 2 shows the relationship between the "concentration" and the "nickel grade in the sponge cadmium taken out at the end point."
はじめに、実施例１から実施例２を参照すると、浸出液の始液のニッケル濃度が０．０２ｇ／Ｌ（０．００２質量％）、浸出液の始液のカドミウム濃度が２０ｇ／Ｌ（２．０質量％）である場合に、浸出液の終点のカドミウム濃度を１０．０ｇ／Ｌ（１．０質量％）に調整することによって、ニッケル品位が１１９ｐｐｍであるスポンジカドミウムが得られ、また、浸出液の終点のカドミウム濃度を１．０ｇ／Ｌ（０．１質量％）に調整することによって、ニッケル品位が１５１ｐｐｍであるスポンジカドミウムが得られることが窺える。
これは、浸出液の終点のカドミウム濃度を１．０ｇ／Ｌ（０．１質量％）以上の濃度範囲に調整することによって、スポンジカドミウム中のニッケル品位が１５１ｐｐｍ以下のスポンジカドミウムが得られることを意味する。そして、このスポンジカドミウムは、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムでもある。
First, referring to Examples 1 to 2, the nickel concentration in the starting solution of the leachate was 0.02 g/L (0.002% by mass), and the cadmium concentration in the starting solution of the leachate was 20 g/L (2.0% by mass). %), by adjusting the cadmium concentration at the end point of the leachate to 10.0 g/L (1.0 mass%), sponge cadmium with a nickel content of 119 ppm can be obtained. It can be seen that by adjusting the cadmium concentration to 1.0 g/L (0.1% by mass), sponge cadmium with a nickel grade of 151 ppm can be obtained.
This means that by adjusting the cadmium concentration at the end point of the leachate to a concentration range of 1.0 g/L (0.1% by mass) or more, sponge cadmium with a nickel content of 151 ppm or less can be obtained. do. This sponge cadmium is also sponge cadmium in which the nickel content is suppressed to 200 ppm or less.
ここで、浸出液の始液のニッケル濃度は低ければ低い程、スポンジカドミウムのニッケル品位を抑制するうえで有利であるが、浸出液の始液のニッケル濃度が高い場合であっても、カドミウム濃度の高い始液を採用することによって、スポンジカドミウムのニッケル品位を抑制することが可能である。これは、浸出液の始液のカドミウム濃度が高ければ、析出するカドミウム量が析出するニッケル量に対して、相対的に増加するためであり、例えば、実施例３はこのことを示すものとなっている。実施例３の浸出液の始液のニッケル濃度が実施例１よりも高い０．０５ｇ／Ｌ（０．００５質量％）であるにも拘らず、始液のカドミウム濃度が７０ｇ／Ｌ（７．０質量％）と高いため、スポンジカドミウム中のニッケル品位が実施例１よりも低くなっている。 Here, the lower the nickel concentration in the starting solution of leachate, the more advantageous it is in suppressing the nickel quality of sponge cadmium, but even if the nickel concentration in the starting solution of leachate is high, By employing the starting liquid, it is possible to suppress the nickel quality of the sponge cadmium. This is because if the cadmium concentration in the starting solution of the leachate is high, the amount of cadmium precipitated increases relative to the amount of nickel precipitated. For example, Example 3 shows this. There is. Although the nickel concentration of the starting solution of the leachate of Example 3 is 0.05 g/L (0.005% by mass), which is higher than that of Example 1, the cadmium concentration of the starting solution is 70 g/L (7.0 % by mass), the nickel quality in the sponge cadmium is lower than in Example 1.
ところで、前述の通り、実施例２を参照すると、浸出液の始液のニッケル濃度が０．０２ｇ／Ｌ（０．００２質量％）、カドミウム濃度が２０ｇ／Ｌ（２．０質量％）である場合に、浸出液の終点のカドミウム濃度を１．０ｇ／Ｌ（０．１質量％）に調整することによって、ニッケル品位が１５１ｐｐｍであるスポンジカドミウムを得ることができるが、この場合にも上記があてはまる。
つまり、浸出液の始液のニッケル濃度が０．０２ｇ／Ｌ（０．００２質量％）以下である場合に、その始液が２０ｇ／Ｌ（２．０質量％）以上のカドミウムを含むものであれば、析出するカドミウム量が析出するニッケル量に対して相対的に増加するため、この始液に対して終点のカドミウム濃度が１．０ｇ／Ｌ（０．１質量％）以上の濃度範囲となるように調整すれば、少なくとも、スポンジカドミウム中のニッケル品位が１５１ｐｐｍを超えることはない。すなわち、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムを得ることが可能である。
By the way, as mentioned above, referring to Example 2, when the nickel concentration of the starting solution of the leachate is 0.02 g / L (0.002 mass %) and the cadmium concentration is 20 g / L (2.0 mass %) Furthermore, by adjusting the cadmium concentration at the end point of the leachate to 1.0 g/L (0.1% by mass), sponge cadmium with a nickel grade of 151 ppm can be obtained, and the above also applies in this case.
In other words, if the nickel concentration of the starting solution of the leachate is 0.02 g/L (0.002% by mass) or less, even if the starting solution contains 20g/L (2.0% by mass) or more of cadmium. For example, since the amount of cadmium that precipitates increases relative to the amount of nickel that precipitates, the cadmium concentration at the end point is in a concentration range of 1.0 g/L (0.1% by mass) or more with respect to this starting liquid. If adjusted in this manner, at least the nickel content in the sponge cadmium will not exceed 151 ppm. That is, it is possible to obtain sponge cadmium in which the nickel quality is suppressed to 200 ppm or less.
さらに、亜鉛セメンテーションの終了時のカドミウム濃度を１０．０ｇ／Ｌ（１．０質量％）以下の濃度範囲となるように調整することによって、液中に残存するカドミウムを抑制できて、効率的なスポンジカドミウムの析出が可能である。 Furthermore, by adjusting the cadmium concentration at the end of zinc cementation to a concentration range of 10.0 g/L (1.0% by mass) or less, it is possible to suppress the cadmium remaining in the liquid, resulting in efficient It is possible to deposit a large amount of sponge cadmium.
次に、実施例３から実施例４を参照すると、浸出液の始液のニッケル濃度が０．０５ｇ／Ｌ（０．００５質量％）、浸出液の始液のカドミウム濃度が７０ｇ／Ｌ（７．０質量％）である場合に、浸出液の終点のカドミウム濃度を１．４ｇ／Ｌ（０．１４質量％）に調整することによって、ニッケル品位が１７０ｐｐｍであるスポンジカドミウムが得られ、また、浸出液の終点のカドミウム濃度を９．７ｇ／Ｌ（０．９７質量％）に調整することによって、ニッケル品位が７３ｐｐｍであるスポンジカドミウムが得られることが窺える。 Next, referring to Examples 3 to 4, the nickel concentration of the starting solution of the leachate was 0.05 g/L (0.005% by mass), and the cadmium concentration of the starting solution of the leachate was 70 g/L (7.0 g/L). By adjusting the cadmium concentration at the end point of the leachate to 1.4 g/L (0.14 mass%), sponge cadmium with a nickel content of 170 ppm can be obtained. It can be seen that by adjusting the cadmium concentration to 9.7 g/L (0.97% by mass), sponge cadmium with a nickel grade of 73 ppm can be obtained.
これは、浸出液の終点のカドミウム濃度を１．４ｇ／Ｌ以上（０．１４質量％）の濃度範囲に調整することによって、スポンジカドミウム中のニッケル品位が１７０ｐｐｍ以下のスポンジカドミウムが得られることを意味する。そして、このスポンジカドミウムは、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムでもある。 This means that by adjusting the cadmium concentration at the end point of the leachate to a concentration range of 1.4 g/L or more (0.14% by mass), sponge cadmium with a nickel content of 170 ppm or less can be obtained. do. This sponge cadmium is also sponge cadmium in which the nickel grade is suppressed to 200 ppm or less.
したがって、浸出液の始液のニッケル濃度が０．０５ｇ／Ｌ（０．００５質量％）以下である場合に、その始液が７０ｇ／Ｌ（７．０質量％）以上のカドミウムを含むものであれば、浸出液の終点のカドミウム濃度を１．４ｇ／Ｌ（０．１４質量％）以上の濃度範囲に調整することによって、少なくとも、スポンジカドミウム中のニッケル品位が１７０ｐｐｍを超えることはなく、ニッケル品位が２００ｐｐｍ以下に抑制されたスポンジカドミウムを得ることが可能である。 Therefore, if the nickel concentration of the starting solution of the leachate is 0.05 g/L (0.005% by mass) or less, even if the starting solution contains 70 g/L (7.0% by mass) or more of cadmium; For example, by adjusting the cadmium concentration at the end point of the leachate to a concentration range of 1.4 g/L (0.14% by mass) or more, at least the nickel content in the sponge cadmium will not exceed 170 ppm, and the nickel content will be reduced. It is possible to obtain sponge cadmium suppressed to 200 ppm or less.
さらに、この場合もまた、亜鉛セメンテーションの終了時のカドミウム濃度を１０．０ｇ／Ｌ（１．０質量％）以下の濃度範囲となるように調整することによって、液中に残存するカドミウムを抑制できて、効率的なスポンジカドミウムの析出が可能である。 Furthermore, in this case as well, the cadmium remaining in the liquid is suppressed by adjusting the cadmium concentration at the end of zinc cementation to a concentration range of 10.0 g/L (1.0 mass%) or less. This method enables efficient sponge cadmium precipitation.
Claims (3)
「前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液（以下、亜鉛セメンテーション終点のカドミウム溶液）」のカドミウム濃度を、
出発物質となる前記始液のニッケルを含むカドミウム溶液のニッケル含有量とカドミウム含有量に応じて、
前記始液のニッケルを含むカドミウム溶液からのニッケルの析出が抑制される濃度範囲に調整することを特徴とする、
金属カドミウムの製造方法。 A method for producing metallic cadmium, comprising precipitating metallic cadmium having pores using zinc cementation from a cadmium solution containing nickel as an initial solution, the method comprising:
The cadmium concentration of " the cadmium solution containing nickel at the end of the zinc cementation (hereinafter referred to as the cadmium solution at the end of the zinc cementation)" is
Depending on the nickel content and cadmium content of the nickel- containing cadmium solution as the starting material ,
The concentration is adjusted to a range in which precipitation of nickel from the nickel-containing cadmium solution of the starting solution is suppressed,
Method for manufacturing cadmium metal.
前記始液のニッケルを含むカドミウム溶液に対する前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液のカドミウム濃度を、１．０～１０．０ｇ／Ｌの範囲となるように調整することを特徴とする、
請求項１に記載の金属カドミウムの製造方法。 The nickel-containing cadmium solution serving as the starting material is a nickel-containing cadmium solution having a cadmium content of 2.0% by mass or more and a nickel content of 0.002% by mass or less,
The cadmium concentration of the nickel-containing cadmium solution at the end of the zinc cementation with respect to the nickel-containing cadmium solution of the starting solution is adjusted to be in the range of 1.0 to 10.0 g/L. ,
A method for producing metal cadmium according to claim 1.
前記始液のニッケルを含むカドミウム溶液に対する前記亜鉛セメンテーションの終了時のニッケルを含むカドミウム溶液のカドミウム濃度を、１．４～１０．０ｇ／Ｌの範囲となるように調整することを特徴とする、
請求項１に記載の金属カドミウムの製造方法。 The cadmium solution containing nickel as an initial solution serving as the starting material is a cadmium solution containing nickel as an initial solution having a cadmium content of 7.0% by mass or more and a nickel content of 0.005% by mass or less,
The cadmium concentration of the nickel-containing cadmium solution at the end of the zinc cementation with respect to the nickel-containing cadmium solution of the starting solution is adjusted to be in the range of 1.4 to 10.0 g/L. ,
A method for producing metal cadmium according to claim 1.
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