JPH0253497B2 - - Google Patents
Info
- Publication number
- JPH0253497B2 JPH0253497B2 JP61112577A JP11257786A JPH0253497B2 JP H0253497 B2 JPH0253497 B2 JP H0253497B2 JP 61112577 A JP61112577 A JP 61112577A JP 11257786 A JP11257786 A JP 11257786A JP H0253497 B2 JPH0253497 B2 JP H0253497B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- reaction
- metal
- impurities
- liquid
- 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.)
- Expired - Lifetime
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 4
- 238000010405 reoxidation reaction Methods 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
発明の技術分野
本発明は、スズの回収法に関する。
特に高純度電気スズの製造に最適な方法であ
る。
発明の従来技術
従来スズの回収法としては、スズ含有物を水等
で浸出した後、Pb、Sb等の不純物を除去するた
め、硫化処理を行うか、あるいは、Snメタルで
置換を行い処理を行つていた。
しかしながら、硫化処理及びスズメタル置換に
よる浄液では、浄液後液中のSbが充分に除去で
きず、電解採取により得られた電気スズは、99.9
％以上純度を上げることができなかつた。
なぜならば、浄液後液中のSbは、貴な金属で
あるため、液中のSbは、ほとんど全量、電極反
応により析出し、電気Snを汚染するからである。
本発明者等は、従来技術の欠点を解決すべく鋭
意検討した結果以下の発明をなした。
発明の構成
本発明は、不純金属を含むスズ含有塩基性溶液
からスズを回収する方法において、還元用金属と
再酸化防止剤を含めて、液中の不純物を置換還元
し、析出した不純物を過等により除き、所定の
方法でスズを回収することを特徴とするスズの回
収法に関する。
また、その実施態様としては、反応を回転タイ
プの反応容器内で行わせることを特徴とする上記
記載のスズの回収法を提供する。
発明の具体的説明
本発明の対象処理液は、不純金属を含むスズ含
有塩基性溶液である。
例えば、鉛製錬等から発生するSn含有スカム
を水浸出したもの等である。
これらの溶液は、PH＝12以上ある塩基性であ
る。
強塩基性である場合は、スズは、スズ酸ソーダ
等の形態で存在している。
上記の対象液に、還元用金属を添加し、還元を
行うのであるがこの際、再酸化防止剤を加えてお
くことが重要である。
還元用金属としては、スズの回収であるため、
スズが好ましい。スズは、必要量だけ溶解してい
れば足りるため、メタリツクであることが好まし
い。さらに、純度の高いものが好ましい。即ち、
99.99％以上のものが好ましい。
再酸化防止剤としては、チオ硫酸ナトリウム
（Na2S2O3）ヒドラジン（N2H4）等を用いる。
これにより、還元析出したSb、Pbを再溶解さ
せないようにすることができる。
これらの処理により、不純物を析出せしめ、ス
ズは、溶解した状態となし得る。
この反応は、回転タイプの反応容器等を用い
て、溶液中に還元金属を流動させながら行わせる
ことが好ましい。例えば、回転槽タイプのものを
用いる。これにより、還元用金属の表面に析出し
た不純物を効率よく剥離し、常に還元用金属と液
中の不純物イオンとが接触出来るようにすること
により迅速に還元反応を促進するためである。
また還元用金属が、過剰に溶解せず好ましい還
元反応をなし得るためである。
特に反応時に、入口部を水平に保持した状態
で、回転させることが好ましい。
反応空間が広く、浸出液を浅いレベルで保持で
きるため、反応を速やかに行わしめるためであ
る。
また、反応温度は、60℃以上好ましくは、80℃
以上であることが好ましい。スズによる置換が好
ましく行われるからである。
析出した不純物は、過等により除き、純度の
高いスズの溶液を得ることができる。
過等とは、沈降法、過法、等不純晶出物を
除く手段全てを含むものである。
本発明で得られるスズ含有液を電解採取あるい
はH2還元等をすることにより、9.99％以上の高
純度の金属スズを回収することができる。また、
この精製液を硫酸等の中和剤で中和することによ
り、高純度の水酸化スズ及び酸化スズの回収をす
ることができる。
尚、Asが、メタル中に混入した場合は、ソー
ダ処理することが好ましい。
以上本発明を実施することにより、以下の効果
を得る。
発明の効果
(1) 99.99％以上の高純度の金属スズの回収が、
容易になし得る。
(2) 特に鉛製錬等で産出された不純物の多いスカ
ムから、高純度のスズ及びスズ塩を回収するに
適している。
(3) さらに浄液時間の短縮が可能である。
実施例 １
鉛製錬で産出されたスカムを水に溶解した。該
液をボールミル型の置換反応層にSnメタルとと
もに装入し、液を循環させることにより、置換反
応を起こさせる。
反応時に、酸化防止剤であるNa2S2O3・5H2O
を２ｇ／添加した。
反応温度は、80℃で行つた。
この結果表１のごとく、Pb、Sb、Cuの低い液
が得られた。
TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for recovering tin. This method is especially suitable for producing high-purity electric tin. Prior Art of the Invention Conventionally, tin recovery methods involve leaching tin-containing materials with water, etc., and then performing sulfurization treatment to remove impurities such as Pb and Sb, or replacing the tin with Sn metal. I was gone. However, in the purification process using sulfurization treatment and tin metal replacement, Sb in the liquid after purification cannot be sufficiently removed, and the electrolytic tin obtained by electrowinning is 99.9%
It was not possible to increase the purity by more than %. This is because Sb in the solution after purification is a noble metal, and almost all of the Sb in the solution is deposited by electrode reaction and contaminates the electrical Sn. The present inventors made the following invention as a result of intensive studies to solve the drawbacks of the prior art. Structure of the Invention The present invention is a method for recovering tin from a tin-containing basic solution containing an impure metal, in which impurities in the solution are reduced by substitution using a reducing metal and a reoxidation inhibitor, and precipitated impurities are removed by oxidation. This invention relates to a tin recovery method characterized by recovering tin by a predetermined method. Further, as an embodiment thereof, there is provided the above-mentioned tin recovery method, characterized in that the reaction is carried out in a rotating reaction vessel. DETAILED DESCRIPTION OF THE INVENTION The target treatment liquid of the present invention is a tin-containing basic solution containing impure metals. For example, Sn-containing scum generated from lead smelting and the like is leached with water. These solutions are basic with a pH of 12 or higher. If it is strongly basic, tin is present in the form of sodium stannate or the like. A reducing metal is added to the above-mentioned target liquid to perform reduction, and at this time, it is important to add a reoxidation inhibitor. Since the reducing metal is tin recovery,
Tin is preferred. Tin is preferably metallic, since it is sufficient to dissolve only the required amount. Furthermore, those with high purity are preferred. That is,
99.99% or more is preferable. As the reoxidation inhibitor, sodium thiosulfate (Na 2 S 2 O 3 ), hydrazine (N 2 H 4 ), etc. are used. This makes it possible to prevent Sb and Pb that have been reduced and precipitated from being redissolved. These treatments allow impurities to precipitate and tin to be in a dissolved state. This reaction is preferably carried out using a rotating type reaction vessel or the like while flowing the reduced metal into the solution. For example, a rotating tank type is used. This is to efficiently exfoliate the impurities deposited on the surface of the reducing metal and to ensure that the reducing metal always comes into contact with the impurity ions in the liquid, thereby rapidly promoting the reduction reaction. This is also because the reducing metal is not excessively dissolved and can perform a preferable reduction reaction. Particularly during the reaction, it is preferable to rotate the inlet section while holding it horizontally. This is because the reaction space is wide and the leachate can be held at a shallow level, allowing the reaction to occur quickly. In addition, the reaction temperature is 60°C or higher, preferably 80°C.
It is preferable that it is above. This is because substitution with tin is preferably performed. The precipitated impurities are removed by filtration or the like to obtain a highly pure tin solution. The term ``filtration'' includes all methods for removing impure crystallized substances, such as precipitation methods and filtration methods. Metallic tin with a high purity of 9.99% or more can be recovered by subjecting the tin-containing liquid obtained in the present invention to electrowinning or H 2 reduction. Also,
By neutralizing this purified liquid with a neutralizing agent such as sulfuric acid, highly pure tin hydroxide and tin oxide can be recovered. Note that if As is mixed into the metal, it is preferable to treat it with soda. By implementing the present invention as described above, the following effects can be obtained. Effects of the invention (1) Recovery of metallic tin with a purity of 99.99% or more
It can be done easily. (2) It is particularly suitable for recovering high-purity tin and tin salt from scum with many impurities produced in lead smelting. (3) Furthermore, it is possible to shorten the liquid purification time. Example 1 Scum produced in lead smelting was dissolved in water. The liquid is charged into a ball mill-type substitution reaction layer together with Sn metal, and the liquid is circulated to cause a substitution reaction. During the reaction, the antioxidant Na 2 S 2 O 3・5H 2 O
2g/added. The reaction temperature was 80°C. As a result, as shown in Table 1, a liquid with low Pb, Sb, and Cu was obtained.
【表】
上記処理液を電解採取により、金属スズを得
た。Asが70ppmあるため、ソーダ処理により処
理し、99.99％電気スズを得ることができた。
比較例
Na2S2O3・5H2Oを添加せずに還元処理した場
合は、Sbがほとんど、析出せず除去ができなか
つた。[Table] Metallic tin was obtained by electrowinning the above treatment solution. Since the As content was 70ppm, we were able to obtain 99.99% electrolytic tin by soda treatment. Comparative Example When reduction treatment was performed without adding Na 2 S 2 O 3 .5H 2 O, almost no Sb was precipitated and could not be removed.
Claims (1)
を回収する方法において、還元用金属と再酸化防
止剤を含めて、液中の不純物を置換還元し、析出
した不純物を過等により除き、所定の方法でス
ズを回収することを特徴とするスズの回収法。 ２ 反応を回転タイプの反応容器内で行わせるこ
とを特徴とする特許請求の範囲第１項記載のスズ
の回収法。[Scope of Claims] 1. A method for recovering tin from a tin-containing basic solution containing an impure metal, including a reducing metal and a reoxidation inhibitor, replacing and reducing impurities in the solution, and removing precipitated impurities by oxidation. A method for recovering tin, which is characterized by recovering tin by a predetermined method. 2. The tin recovery method according to claim 1, wherein the reaction is carried out in a rotating reaction vessel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11257786A JPS62270735A (en) | 1986-05-19 | 1986-05-19 | Recovering method for tin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11257786A JPS62270735A (en) | 1986-05-19 | 1986-05-19 | Recovering method for tin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62270735A JPS62270735A (en) | 1987-11-25 |
| JPH0253497B2 true JPH0253497B2 (en) | 1990-11-16 |
Family
ID=14590200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11257786A Granted JPS62270735A (en) | 1986-05-19 | 1986-05-19 | Recovering method for tin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62270735A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2642230B2 (en) * | 1990-07-19 | 1997-08-20 | 日鉱金属株式会社 | Manufacturing method of high purity tin |
| CN102776528B (en) * | 2011-05-11 | 2015-12-09 | 吉坤日矿日石金属株式会社 | The method of tin is reclaimed from arsenic containing solution |
| CN106929692B (en) * | 2016-12-14 | 2018-11-06 | 衡阳旺发锡业有限公司 | A kind of energy-efficient tin metallurgy equipment and its application process on the double molten tin inclined-planes of band |
| JP2019173134A (en) * | 2018-03-29 | 2019-10-10 | Ｊｘ金属株式会社 | MANUFACTURING METHOD OF Sn |
| CN108913912B (en) * | 2018-08-01 | 2020-11-13 | 济源职业技术学院 | Device for recovering copper from waste slag generated in copper smelting |
-
1986
- 1986-05-19 JP JP11257786A patent/JPS62270735A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62270735A (en) | 1987-11-25 |
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