JPS63277782A - Method for recovering metallic tin from tin sludge - Google Patents
Method for recovering metallic tin from tin sludgeInfo
- Publication number
- JPS63277782A JPS63277782A JP11247387A JP11247387A JPS63277782A JP S63277782 A JPS63277782 A JP S63277782A JP 11247387 A JP11247387 A JP 11247387A JP 11247387 A JP11247387 A JP 11247387A JP S63277782 A JPS63277782 A JP S63277782A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- sludge
- filtrate
- soln
- ions
- 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.)
- Pending
Links
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010802 sludge Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910001432 tin ion Inorganic materials 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 235000010323 ascorbic acid Nutrition 0.000 abstract description 4
- 239000011668 ascorbic acid Substances 0.000 abstract description 4
- 239000002659 electrodeposit Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 150000004679 hydroxides Chemical class 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 2
- 229960005055 sodium ascorbate Drugs 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 239000004320 sodium erythorbate Substances 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、錫スラジに還元剤を添加して電解精製を行い
安価に錫スラジから金属錫を回収する方・法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for recovering metallic tin from tin sludge at low cost by adding a reducing agent to tin sludge and performing electrolytic refining.
〈従来の技術〉
−ｉに、錫メッキ浴からは、第２錫塩あるいは第１錫塩
と第２錫塩との両者を含む錫スラジが析出し沈積する。<Prior Art> -i, tin sludge containing a stannic salt or both a stannic salt and a stannic salt is precipitated and deposited from a tin plating bath.
従来、錫スラジは錫精錬時の副原料として処理されるか
、または湿式電解法により金属錫として回収されている
。前者では錫スラジに含有する他の有害成分の揮散を招
き問題が生じ好ましくなく、後者では工程が複雑で設備
的負担が大きくやはり問題であった。こ、の問題を解消
する方法として特公昭５９−１４０９４号公報に「スラ
リから金属錫を回収する方法」が開示されている。この
技術は第２図に示すように錫メンキスラジを水溶液でス
ラリー状に調整し、加熱したＮ、ＯＨを添加し化学反応
を行わせ、沈殿物Ｆａ （ＯＨ） ｘをろ過し、このろ
液のｐＨを調整し電解を行って錫を電着させ金属錫を回
収するものである。Conventionally, tin sludge has been treated as an auxiliary raw material during tin refining or recovered as metallic tin by wet electrolysis. The former method is undesirable as it causes the volatilization of other harmful components contained in the tin sludge, while the latter method is also problematic because the process is complicated and the equipment is burdened heavily. As a method for solving this problem, Japanese Patent Publication No. 59-14094 discloses a method for recovering metallic tin from slurry. This technology, as shown in Figure 2, prepares tin chloride into a slurry with an aqueous solution, adds heated N and OH to cause a chemical reaction, filters the precipitate Fa (OH) x, and extracts the filtrate. The pH is adjusted and electrolysis is performed to electrodeposit tin and recover metallic tin.
しかし、この方法では４価錫イオンを直接電解還元する
ため電気コストがかかりすぎて問題であった。However, this method has a problem in that the electricity cost is too high because tetravalent tin ions are directly electrolytically reduced.
〈発明が解決しようとする問題点〉
本発明は、従来の方法には前述のような問題があったの
で、錫スラジから電解還元によって金属錫を安価に回収
する方法を提供するためになされたものである。<Problems to be Solved by the Invention> The present invention was made in order to provide a method for recovering metallic tin from tin sludge at low cost by electrolytic reduction, since the conventional methods had the above-mentioned problems. It is something.
〈問題点を解決するための手段〉
本発明者らは、金属錫を安価に回収する方法について鋭
意研究を重ねた結果、還元剤で４価錫イオンを２価錫イ
オンに還元した後、電解精製することによって目的を達
成できるとの知見をえ、この知見にもとづいて本発明を
なすに至った。<Means for Solving the Problems> As a result of intensive research into methods for recovering metallic tin at low cost, the present inventors discovered that after reducing tetravalent tin ions to divalent tin ions using a reducing agent, electrolysis was performed. We have found that the objective can be achieved through purification, and based on this knowledge, we have accomplished the present invention.
本発明は、第２錫塩あるいは第１錫塩と第２錫塩との両
者を含む錫スラジから金属錫を回収する方法において、
錫スラジを水溶液に溶解、ろ過し、さらにろ液を苛性ソ
ーダで処理し、ろ過後、ろ液に還元剤を添加し４価錫イ
オンの全部あるいは一部を２価錫イオンに還元した後、
電解精製し錫を電着させる錫スラジからの金属錫の回収
方法である。The present invention provides a method for recovering metallic tin from tin sludge containing a stannic salt or both a stannic salt and a stannic salt.
The tin sludge is dissolved in an aqueous solution and filtered, and the filtrate is further treated with caustic soda. After filtration, a reducing agent is added to the filtrate to reduce all or part of the tetravalent tin ions to divalent tin ions.
This is a method for recovering metallic tin from tin sludge that is electrorefined and electrodeposited.
以下に、本発明について説明する。The present invention will be explained below.
賜メッキ浴において高速電気錫メツキラインでは鉄鋼の
シート、ストリップが高速で流れており、浴が撹拌され
浴中に空気中の酸素を溶解、捕捉される。浴中の２価錫
イオンは酸化され錯体の形状をした４価錫イオンとなり
溶解度により錯塩は沈殿し錫スラジとなる。この錫スラ
ジを電解還元によって金属錫のみ回収するもので、第１
図に本発明の錫スラジからの錫回収方法の一例を示した
。In the plating bath, sheets or strips of steel are flowing at high speed in the high-speed electric tinning line, and the bath is agitated to dissolve and trap oxygen in the air. Divalent tin ions in the bath are oxidized to become tetravalent tin ions in the form of a complex, and depending on the solubility, the complex salt precipitates to form tin sludge. Only metallic tin is recovered from this tin sludge through electrolytic reduction.
The figure shows an example of the method of recovering tin from tin sludge according to the present invention.
まず錫スラジを水溶液に溶解するが、このとき酸あるい
はアルカ・りを加えたり撹拌および加熱すれば錫スラジ
は容易に溶解される。First, tin sludge is dissolved in an aqueous solution, and at this time, the tin sludge can be easily dissolved by adding acid or alkali, stirring, and heating.
ここでえられた錫スラジ溶液をろ過し不溶解物を除去す
る。このろ液中の鉄などの重金属を沈殿除去するために
苛性ソーダで処理し、ろ過する。The tin sludge solution obtained here is filtered to remove insoluble matter. This filtrate is treated with caustic soda to precipitate and remove heavy metals such as iron, and then filtered.
得られたろ液のＰＨを調整し還元剤を添加して４価錫イ
オンを２価錫イオンに還元する。この溶液より電解還元
によって金属錫を回収する。The pH of the obtained filtrate is adjusted and a reducing agent is added to reduce tetravalent tin ions to divalent tin ions. Metallic tin is recovered from this solution by electrolytic reduction.
なお、−例としてハロゲン錫メッキの錫スラジと苛性ソ
ーダの反応式を示す。As an example, a reaction formula between tin sludge of halogen tin plating and caustic soda is shown.
Ｎ−！Ｓ−Ｆ＆ ＋ ４ Ｎ−０Ｈ−＋５−（ＯＨ）
ａ ＋ ６ Ｎ−Ｆ・・・・・・・（１）Ｓ−（ＯＨ）
ａ ＋ ２ Ｎ−０Ｈ−４ＮａｚＳ、Ｏ＜ ＋ ３
ＨｘＯ・・・・・・−（２）なお、不純物の除去方法と
しては、水酸化物としての沈殿除去のみでなく、蓚酸塩
のような溶解度の小さい塩として沈殿除去する方法もあ
る。N-! S-F&+4 N-0H-+5-(OH)
a + 6 N-F・・・・・・(1) S-(OH)
a + 2 N-0H-4NazS, O< + 3
HxO...-(2) Note that as a method for removing impurities, there is not only a method of precipitating removal as hydroxide, but also a method of precipitating removal as a salt with low solubility such as oxalate.
還元剤添加前のＰＨ１１整は、還元剤が分解しない程度
で、かつ十分な還元効果を発揮しうる程度であることが
肝要である。還元剤の添加量は、錫スラジ中の錫含有量
によって調整する。It is important that the pH level before adding the reducing agent be adjusted to such an extent that the reducing agent does not decompose and that a sufficient reducing effect can be exerted. The amount of reducing agent added is adjusted depending on the tin content in the tin sludge.
また第１図の工程のうちＡで示したろ過工程を省き、不
溶解物を、下記（３）式のように熱アルカリ分解し、重
金属化合物として沈殿除去することもできる。Furthermore, it is also possible to omit the filtration step shown by A among the steps in FIG. 1, and to perform thermal alkaline decomposition of the insoluble matter as shown in the following formula (3), and to precipitate and remove it as a heavy metal compound.
Ｆ−ａ ［Ｆａ（ＣＮ）＆ ］ ｓ ＋ １２ＮｓＯＨ
→４ Ｆａ（ＯＨ）ｓ＋３Ｎ−ｎ ［Ｆ、（ＣＮ）＆］
ｓ−・−・−・−（３）本発明に使用できる還元剤の
一例を以下に示す。Fa [Fa (CN) & ] s + 12NsOH
→4 Fa(OH)s+3N-n [F, (CN)&]
s-・-・-・-(3) An example of the reducing agent that can be used in the present invention is shown below.
Ｌ−アスコルビン酸
０− ＣＯＣ（ＯＨ） −Ｃ（ＯＨ） ＣＩＩＣＨ（Ｏ
Ｈ） ＣＨｔＯＨＬ−一一一一一一」
Ｌアスコルビン酸ナトリウム
ＨＯＣＨＩＣＨ（Ｏ）ｌ）ＣＨＣ（ＯＮ、） −Ｃ（Ｏ
ｌｌ） Ｃｏ。L-Ascorbic acid 0- COC(OH) -C(OH) CIICH(O
H) CHtOHL-11111' L Sodium Ascorbate HOCHICH(O)l)CHC(ON,) -C(O
ll) Co.
ｌ５Ｏ−アスコルビン酸ナトリウム（エリソルビン酸ナ
トリウム）
１１０ｃＩ（ｔｃｔｌ （ＯＨ） ＣｌＩＣ（ＯＮ 、
） −、Ｃ（Ｏｆ（） Ｃｏ。15O-Sodium ascorbate (sodium erythorbate) 110cI (tctl (OH) ClIC (ON,
) −, C(Of() Co.
し−一一一一一一一」
還元剤としては、鋳造の際に分解あるいは気化し鋳造物
中に残らないことが肝要である。It is important that the reducing agent does not decompose or vaporize during casting and does not remain in the casting.
〈実施例〉
還元剤（例：アスコルビン酸）の添加によって錫スラジ
水溶液中、の４価錫イオンが２価錫イオンに還元され、
さらに電解還元により金属錫が回収されたことをｔ！認
した実施例を以下に示す。<Example> By adding a reducing agent (e.g. ascorbic acid), the tetravalent tin ions in the tin sludge aqueous solution were reduced to divalent tin ions,
Furthermore, it was confirmed that metal tin was recovered by electrolytic reduction! The approved examples are shown below.
ハロゲン電気錫メッキ浴の底部に沈積している錫スラジ
約１００ｇを５％苛性ソーダ溶液１４！（８０’Ｃ）に
溶解させろ過した。このろ液に塩酸を添加しＰＨを約４
に調整しアスコルビン酸５０ｇを添加した。Approximately 100g of tin sludge deposited at the bottom of the halogen electrolytic tin plating bath was dissolved in 5% caustic soda solution14! (80'C) and filtered. Add hydrochloric acid to this filtrate to adjust the pH to approximately 4.
50 g of ascorbic acid was added.
このときのアスコルビン酸添加前後の各成分濃度を第１
表に示した。The concentration of each component before and after the addition of ascorbic acid at this time is
Shown in the table.
この結果、スラジ中の４価錫イオンが２価錫イオンに還
元されることがｌｉｌ認された。さらにこの２価錫イオ
ンの多い溶液を電解精製して金属錫かえられたが、この
ときの電力使用量は従来の電解方法に比べて約１／２と
半減した。As a result, it was confirmed that the tetravalent tin ions in the sludge were reduced to divalent tin ions. Furthermore, this solution containing a large amount of divalent tin ions was electrolytically refined to replace metallic tin, and the amount of electricity used at this time was halved to about 1/2 compared to the conventional electrolytic method.
第 １ 表
〈発明の効果〉
本発明によると、従来の方法に比べて電力使用量は約１
／２となり、結局従来の２／３以下のコストで金属錫を
回収することができるようになった。Table 1 <Effects of the invention> According to the present invention, the power consumption is reduced by about 1% compared to the conventional method.
/2, making it possible to recover metal tin at less than 2/3 of the conventional cost.
第１図は、本発明の金属錫回収工程図、第２図は、従来
の電解法による金属錫回収工程図である。
第 ２ 図FIG. 1 is a process diagram for recovering metallic tin according to the present invention, and FIG. 2 is a process diagram for recovering metallic tin using a conventional electrolytic method. Figure 2
Claims (1)
スラジから金属錫を回収する方法において、錫スラジを
水溶液に溶解、ろ過し、さらにろ液を苛性ソーダで処理
し、ろ過後、ろ液に還元剤を添加し４価錫イオンの全部
あるいは一部を２価錫イオンに還元した後、電解精製し
錫を電着させることを特徴とする錫スラジからの金属錫
の回収方法。In a method for recovering metallic tin from tin sludge containing a stannic salt or both a stannic salt and a stannic salt, the tin sludge is dissolved in an aqueous solution and filtered, and the filtrate is further treated with caustic soda and filtered. After that, a reducing agent is added to the filtrate to reduce all or part of the tetravalent tin ions to divalent tin ions, and then the tin is electrolytically purified and tin is electrodeposited.Collection of metallic tin from tin sludge. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11247387A JPS63277782A (en) | 1987-05-11 | 1987-05-11 | Method for recovering metallic tin from tin sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11247387A JPS63277782A (en) | 1987-05-11 | 1987-05-11 | Method for recovering metallic tin from tin sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63277782A true JPS63277782A (en) | 1988-11-15 |
Family
ID=14587516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11247387A Pending JPS63277782A (en) | 1987-05-11 | 1987-05-11 | Method for recovering metallic tin from tin sludge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63277782A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110349A (en) * | 1998-03-25 | 2000-08-29 | Kawasaki Steel Corporation | Method for recovering metallic tin from electroplating sludge |
| KR20000058674A (en) * | 2000-06-23 | 2000-10-05 | 김주형 | The method of extracting tin of high purity from dregs |
-
1987
- 1987-05-11 JP JP11247387A patent/JPS63277782A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6110349A (en) * | 1998-03-25 | 2000-08-29 | Kawasaki Steel Corporation | Method for recovering metallic tin from electroplating sludge |
| KR20000058674A (en) * | 2000-06-23 | 2000-10-05 | 김주형 | The method of extracting tin of high purity from dregs |
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