JPS62256982A - Treatment of solution containing bismuth acidified with sulfuric acid - Google Patents
Treatment of solution containing bismuth acidified with sulfuric acidInfo
- Publication number
- JPS62256982A JPS62256982A JP61098685A JP9868586A JPS62256982A JP S62256982 A JPS62256982 A JP S62256982A JP 61098685 A JP61098685 A JP 61098685A JP 9868586 A JP9868586 A JP 9868586A JP S62256982 A JPS62256982 A JP S62256982A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- sulfuric acid
- soln
- activated carbon
- acidified
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 25
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims description 18
- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 antimono Chemical compound 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Water Treatment By Sorption (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業分野）
本発明は＠製錬の電解工程における電解液の硫酸酸性溶
液中に蓄積した不純物のうち、可溶性のビスマスを簡単
な操作で選択的に分離除去する方法に関するものである
。[Detailed Description of the Invention] (Industrial Field) The present invention is a method for selectively separating and removing soluble bismuth from among impurities accumulated in a sulfuric acid acidic electrolyte solution in the electrolytic process of smelting with a simple operation. It is related to.
（従来技術とその問題点）
鋼の電解ｖｌｖ製においては、陽極としてのアノード中
には目的金属の鉤以外に、金、銀、ニッケル、セレン、
テルル、ビスマス、砒素、アンチモノ等、数多くの金属
が含まれている。そのうち、一部は銅とともに溶出し、
一定８度以上に蓄積すると、銅とともに析出し、電気銅
の品質を低下させる。(Prior art and its problems) In the electrolytic VLV manufacturing of steel, in addition to the target metal hook, the anode contains gold, silver, nickel, selenium,
It contains many metals such as tellurium, bismuth, arsenic, and antimony. Some of this is eluted together with copper,
If it accumulates above a certain temperature of 8 degrees, it will precipitate along with the copper, reducing the quality of electrolytic copper.
そのため、これら溶出不純物を一定ｔ４度以下に保つた
め、電解液の浄液が必要となる。Therefore, in order to keep these eluted impurities below a certain t4 degree, purification of the electrolyte is required.
従来、銅電解液中のビスマスを分離する方法としては、
銅電解液を鉛などよりなる不溶性陽極を使用して電解し
、脱銅スライムとして除去する脱鋼電解法、鵡電解液に
炭酸す） ＋７ウムを添加する中和法、電解液中に硫化
水素ガスを吹き込んで硫化物沈殿として除去する硫化物
沈殿法、更Ｖｃは、上記アンチモノ等不純物の蓄積した
電解液を樽縮して硫酸銅結晶な晶出せしめ共沈した上記
不純物とともに除去するタンパン製造法などがある。し
かしながら、これらの方法では、いずれも除去すべき不
純物とともに、それよりはるかに多量の銅が随伴して除
去されるため、この銅を回収すべく銅製錬工程の前段に
再投入し、繰りこし処理するなど、不純物の系外除去と
いう目的からは満足のいくものではなかった。Conventionally, the method for separating bismuth in copper electrolyte is as follows:
A steel-removal electrolytic method in which a copper electrolyte is electrolyzed using an insoluble anode made of lead or the like and removed as copper-free slime, a neutralization method in which +7 um is added to the copper electrolyte, and hydrogen sulfide is added to the electrolyte. The sulfide precipitation method involves blowing gas to remove the sulfide precipitate, and the additional Vc is a tampan production method in which the electrolyte containing the above-mentioned anti-mono impurities is condensed in a barrel to form copper sulfate crystals, which are then removed along with the co-precipitated impurities. There are laws, etc. However, in all of these methods, a much larger amount of copper is removed together with the impurities that should be removed, so in order to recover this copper, it is reinjected into the first stage of the copper smelting process and recycled. This was not satisfactory from the purpose of removing impurities from the system.
その他の除去方法としては、特開昭５５−１０７７９３
号公報に、砒素、アンチモノ、ビスマスのうち、少くと
も砒素を含有する遊離硫酸７００１／！ｌｌ！以下の硫
酸酸性溶液に塩基性硫酸アンチモンまたは塩基性硫酸ビ
スマスの一万又は両者の混合物を添力Ｏ混合し生成する
沈殿を分離することを特徴とする硫酸酸性溶液中の砒素
、アンチモノ。Other removal methods include JP-A-55-107793
In the publication, free sulfuric acid 7001/! contains at least arsenic among arsenic, antimono, and bismuth. ll! Arsenic and antimony in the following sulfuric acid acidic solution, which is characterized by mixing basic antimony sulfate or basic bismuth sulfate or a mixture of both with an addition of O to the sulfuric acid acidic solution and separating the generated precipitate.
ビスマスの除去法、が開示されているが、この方法は浄
液目的物と同種の物質を電解液中に−１（に多４Ｊに溶
解させろため、操作を誤ると、逆に′＠電解液中上記不
純物ａ度を増加させる危険性がある。A method for removing bismuth has been disclosed, but this method involves dissolving the same type of substance as the object of purification into the electrolyte at -1 (to 4 J). There is a risk of increasing the above impurity level.
（ｋ＃明の目的）
本発明者らは上記の従来技術の問題点を解決し、：？：
Ｉ！解液中に含まれるビスマスを簡単な操作で分離、除
去し、膣な解液中のビスマス濃度を低減せしめる硫酸酸
性＠液中のビスマスの除去法を提供すべく検討した結果
、活性炭を電解液と接触させることにより非常に容易に
上記目的を達成しうろことを見出し、本発明に到達した
。(Objective of k#light) The present inventors solved the problems of the above-mentioned prior art, and:? :
I! As a result of our study to provide a method for removing bismuth from sulfuric acid solution, which can separate and remove the bismuth contained in the solution with simple operations and reduce the bismuth concentration in the solution, we found that activated carbon was used as an electrolyte solution. It has been discovered that the above object can be achieved very easily by contacting with the molecule, and the present invention has been achieved.
（発明の横５５り
すなわち、本発明の要旨とするところは、ビスマスを含
有する硫酸ａ性ｆ８液に活性炭を接触させ、該ビスマス
を該活性炭に吸着せしめることを特徴とするビスマスを
含有する硫酸酸性溶液の処理法、にある。(55th aspect of the invention, that is, the gist of the present invention is that a sulfuric acid containing bismuth is characterized in that activated carbon is brought into contact with a sulfuric acid a-based F8 liquid containing bismuth, and the bismuth is adsorbed on the activated carbon. A method for treating acidic solutions.
本発明において、活性炭をｌ？に解液と接触させるには
、活性炭をカラムに充填して層状とし、この層を通液さ
せる方法によってもよく、また活性炭を槽中で電解液と
攪拌する方法でもよく、さらにこれら二号法を併用して
もよい。又活性炭と接触する電解液温度は通常の電解３
度の６０℃でもよいが、活性炭による作用はビスマスの
吸着であるので液温は６０℃以下が好ましい。In the present invention, activated carbon is used in l? In order to bring the activated carbon into contact with the electrolyte, it may be possible to fill a column with activated carbon to form a layer and allow the liquid to pass through this layer, or by stirring the activated carbon with the electrolyte in a tank. may be used together. In addition, the temperature of the electrolytic solution in contact with activated carbon is the same as that of normal electrolysis 3.
The liquid temperature may be 60°C, but since the action of activated carbon is to adsorb bismuth, the liquid temperature is preferably 60°C or lower.
次に、本発明を実施例によって具体的に説明する。Next, the present invention will be specifically explained using examples.
以下の実施例は本発明の範囲を限定するものではない。The following examples are not intended to limit the scope of the invention.
実施例１
Ｃｕ ４２１ ／−ｅ ｐ Ｎ ｉ １５９ ／ （３
−Ａ ｓ ５．１１ ／ １３ 。Example 1 Cu 421 /-e p N i 159 / (3
-As 5.11/13.
Ｓ ｂ ４８０１１＋１７／Ａ、 Ｂ Ｌ ９３Ｗ／４
３．遊離硫酸２１０１／Ｊの銅電解液２００ｍ１を３０
０４の活栓つきの三角フラスコに採り、それぞれの該三
角フラスコに異なる活性炭を２０Ｊ添加し、２４時間攪
拌した。この攪拌処理は６０℃の恒温槽中に浸漬して行
なった。処理後の電解液中のビスマスの分析を行い、得
られた結果は第１表に示す。S b 48011+17/A, B L 93W/4
3. 200ml of free sulfuric acid 2101/J copper electrolyte
The mixture was placed in a No. 04 Erlenmeyer flask with a stopcock, and 20 J of different activated carbon was added to each Erlenmeyer flask and stirred for 24 hours. This stirring treatment was performed by immersing the sample in a constant temperature bath at 60°C. Bismuth in the electrolyte after treatment was analyzed, and the results are shown in Table 1.
実施例２
実施例１と同様の方法により、実施例１と同様な組成の
電解液を液温４０℃、６０℃、８０℃と変化させ、ツル
ミコール裂粉末活性炭を各々２０ｙ添加し、恒温槽中で
２４時間攪拌し、処理後の電解液中のビスマスの分析値
を第２表に示す。Example 2 Using the same method as in Example 1, an electrolytic solution having the same composition as in Example 1 was changed in temperature to 40°C, 60°C, and 80°C, 20y of Tsurumicol cracked powder activated carbon was added to each, and the solution was placed in a constant temperature bath. After stirring for 24 hours, the analytical values of bismuth in the electrolyte after treatment are shown in Table 2.
第１表
ｆｇ２表
以上の結果から明らかなよ５ｉＣ，本発明によって、ビ
スマスを簡便に地元１との選択性がよく分離することが
可能である。As is clear from the results shown in Table 1, fg, and Table 2, the present invention makes it possible to easily separate bismuth from local 1 with good selectivity.
（発明の効果）
本発明は上記の構設なとることによって、次の効果を示
す。(Effects of the Invention) By adopting the above structure, the present invention exhibits the following effects.
（１）活性炭と電、解液を接触するのみであるので従来
の中和法のように、遊離硫酸の消費、異種金属の液中へ
の混入がない。(1) Since only the activated carbon is brought into contact with the electrolytic solution, there is no consumption of free sulfuric acid and no mixing of different metals into the solution, unlike in conventional neutralization methods.
（２）電解液の浄液対象がビスマスの場合、本発明によ
りビスマスを除去した液は全１・もしくは一部をそのま
ま電解工程に送ることができ、丹パノ箸造工程や脱銅電
解工程の負荷を軽減できる。(2) When the target of electrolytic solution purification is bismuth, the solution from which bismuth has been removed according to the present invention can be sent in its entirety or in part to the electrolytic process as it is, and can be used in the Tanpano chopstick manufacturing process or copper removal electrolytic process. It can reduce the load.
Claims (1)
させ、該ビスマスを該活性炭に吸着せしめることを特徴
とするビスマスを含有する硫酸酸性溶液の処理法。(1) A method for treating a sulfuric acid acidic solution containing bismuth, which comprises bringing activated carbon into contact with the sulfuric acid acidic solution containing bismuth, and causing the bismuth to be adsorbed onto the activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098685A JPH0653948B2 (en) | 1986-04-28 | 1986-04-28 | Treatment method of sulfuric acid acidic solution containing bismuth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098685A JPH0653948B2 (en) | 1986-04-28 | 1986-04-28 | Treatment method of sulfuric acid acidic solution containing bismuth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62256982A true JPS62256982A (en) | 1987-11-09 |
| JPH0653948B2 JPH0653948B2 (en) | 1994-07-20 |
Family
ID=14226361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61098685A Expired - Lifetime JPH0653948B2 (en) | 1986-04-28 | 1986-04-28 | Treatment method of sulfuric acid acidic solution containing bismuth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653948B2 (en) |
-
1986
- 1986-04-28 JP JP61098685A patent/JPH0653948B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653948B2 (en) | 1994-07-20 |
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