JPH01139790A - Production of electrolytic bismuth having low silver content - Google Patents
Production of electrolytic bismuth having low silver contentInfo
- Publication number
- JPH01139790A JPH01139790A JP62297726A JP29772687A JPH01139790A JP H01139790 A JPH01139790 A JP H01139790A JP 62297726 A JP62297726 A JP 62297726A JP 29772687 A JP29772687 A JP 29772687A JP H01139790 A JPH01139790 A JP H01139790A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- electrolyte
- silver
- electrolytic
- dissolved oxygen
- 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
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052797 bismuth Inorganic materials 0.000 title claims description 46
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 230000001603 reducing effect Effects 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 40
- 238000011109 contamination Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910003638 H2SiF6 Inorganic materials 0.000 abstract 2
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 abstract 2
- 238000002386 leaching Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CCXYPVYRAOXCHB-UHFFFAOYSA-N bismuth silver Chemical compound [Ag].[Bi] CCXYPVYRAOXCHB-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 electrical contacts Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- Electrolytic Production Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、電解による低銀品位の電気ビスマスの製造法
に関するものであり、特には電解液中の溶存酸素及び或
は電解液の温度を管理することによる５、０ｐｐｍ以下
、一般に３〜４ ｐｐｍ以下、好ましくは１ ｐｐｍ以
下の低銀品位の電気ビスマスの製造法に関する。本発明
は、近時普及の著しい半導体、電気接点、触媒、低温は
んだ、導電性接着剤等の構成材料として或は添加剤とし
て用いられることの多くなったビスマスの銀品位の低減
を計るものであり、併せて原料たる鉛殿物からの銀回収
の徹底化を計るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing electric bismuth with a low silver grade by electrolysis, and in particular, by controlling the dissolved oxygen in the electrolyte and/or the temperature of the electrolyte. The following describes a method for producing electrical bismuth having a low silver grade of generally 3 to 4 ppm or less, preferably 1 ppm or less. The present invention aims to reduce the silver quality of bismuth, which is increasingly used as a constituent material or additive in semiconductors, electrical contacts, catalysts, low-temperature solders, conductive adhesives, etc., which have become increasingly popular in recent years. At the same time, the aim is to thoroughly recover silver from lead precipitates, which are raw materials.
′ へとその。頭載
ビスマスは鉛殿物を原料として回収される。鉛殿物には
鉛が２０〜４０％含まれており、幾つかの乾式製錬工程
を経由した後粗ビスマスを電解精製することにより電気
ビスマスが製造されている。例えば、鉛殿物はそれを電
気炉で還元することにより還元鉛とされ、その後アンチ
モン揮発炉において揮発法によりｓｂを５ｂ２０３とし
て回収する。ここで得られる鉛貴鉛は溶離炉において校
銀とビスマスを含む絞鉛に分離される。この校鉛は塩化
により鉛を除去して粗ビスマスとされる。この粗ビスマ
スはアノードに鋳造され、電解精製により電気ビスマス
とされる。最後に、電気ビスマスは、精製炉において脱
銅されて製品ビスマスとなる。′ to that. Overhead bismuth is recovered from lead precipitates. The lead precipitate contains 20 to 40% lead, and electric bismuth is produced by electrolytically refining crude bismuth after passing through several pyrometallurgical processes. For example, lead precipitate is reduced to reduced lead by reducing it in an electric furnace, and then sb is recovered as 5b203 by a volatilization method in an antimony volatilization furnace. The noble lead obtained here is separated into proof silver and drawn lead containing bismuth in a melting furnace. This proof lead is converted into crude bismuth by removing lead through chlorination. This crude bismuth is cast into an anode and electrorefined to produce electric bismuth. Finally, the electric bismuth is decoppered in a refining furnace to produce bismuth product.
ビスマス電解は、Ｂｉｚ （ＳｉＦｅ） ３＋ ＨｚＳ
ｉＦａ溶液を電解液としてチタン板或はステンレス板種
板上に純ビスマスを析出させることにより行なわれる。Bismuth electrolysis is Biz (SiFe) 3+ HzS
This is carried out by depositing pure bismuth on a titanium plate or stainless steel plate using an iFa solution as an electrolyte.
アノードのスライムだおれを防ぐためにアノード各−枚
に炉布製の袋が付けられる。電解液組成は一般には、
Ｂｉ” ３０〜１００ ｇ／１１１□Ｓ
＋Ｆｅ ２００〜４００ ｇ／ＩＣＩ濃度
５０〜１００ ｍｌ／１である。電解条件は例
えば、液温＝３５℃以上、Ｄｋ＝約６５Ａ／ｍ” ：電
圧＝０．４Ｖとされ、１４日１代取りで操業が行なわれ
ている。電解液は環流される。A furnace cloth bag is attached to each anode to prevent slime from dripping on the anode. The electrolyte composition is generally Bi” 30-100 g/111□S
+Fe 200-400 g/ICI concentration
It is 50-100 ml/1. The electrolytic conditions are, for example, liquid temperature = 35° C. or higher, Dk = approximately 65 A/m'', voltage = 0.4 V, and the operation is carried out with one generation every 14 days. The electrolytic solution is refluxed.
こうしたビスマス電解の通常操業においては、銀が０．
４ｍｇ／１以上、一般に０．５ ｍｇ／ｌ程度含まれて
いる。In normal operation of such bismuth electrolysis, silver is 0.
It is contained in an amount of 4 mg/l or more, generally around 0.5 mg/l.
最近、ビスマス材料に対する高純度化への要求からまた
銀を最大限に回収する目的から、電気ビスマス中のビス
マス含有量をもっと低減することへの要望が強くなって
いる。Recently, there has been a strong desire to further reduce the bismuth content in electric bismuth due to the demand for higher purity of bismuth materials and for the purpose of maximizing silver recovery.
現在、電解液に）ＩＣＩを添加し、
Ａｇ” ＋ ＣＩ−＝ ＡｇＣ１↓（ＣＩ濃度５０〜１
００ ｍｌ／１ ）の反応によりＡｇ”の混入防止を計
っている。しかし、電気ビスマスの銀品位を５ ｐｐｍ
以下に低減するには、これだけでは不十分であり、新た
な対策が必要である。Currently, by adding ICI (to the electrolyte), Ag" + CI- = AgC1↓ (CI concentration 50 to 1
00 ml/1) to prevent the contamination of Ag.
This alone is not sufficient to reduce the amount below, and new measures are required.
ｌ豆五且刀
本発明の目的は、電気ビスマスの銀品位を５ｐｐｍ以下
、好ましくは１ ｐｐｍ以下にまでも低減する技術を開
発することである。An object of the present invention is to develop a technique for reducing the silver content of electric bismuth to 5 ppm or less, preferably 1 ppm or less.
ｌ豆立且Ｉ
上記目的に向け、本発明者等は検討を重ねた結果、銀汚
染防止には上記塩化銀反応によるだけでは限界があり、
２Ａｇ◆１／２０□◆１ｌｚｓｉＦｓ＝ ＡｇｚＳｉＦ
ｅ ＋ Ｈ２Ｏの反応による銀溶出を極力抑制する必要
があるとの知見をここに初めて見出すに至った。更に、
ＨｚＳｉＦａ系電解液において、電解液の温度を低くす
る程、銀汚染を一層防止しうることも初めて確認された
。Toward the above objective, the present inventors have conducted repeated studies and found that there is a limit to preventing silver contamination only by the above silver chloride reaction, and 2Ag◆1/20□◆1lzsiFs=AgzSiF
This is the first time that we have discovered that it is necessary to suppress silver elution due to the e + H2O reaction as much as possible. Furthermore,
It was also confirmed for the first time that in a HzSiFa-based electrolyte, the lower the temperature of the electrolyte, the more silver contamination can be prevented.
この知見に基すいて、本発明は、
１）電気ビスマスを製造するビスマス電解において、電
解液中の溶存酸素を５．０ｍｇ／ｌ以下に保持すること
を特徴とする低銀品位の電気ビスマスの製造法、及び
２）電気ビスマスを製造するビスマス電解において、電
解液中の溶存酸素を５．０ｍｇ／ｌ以下に保持しそして
電解液の温度を４０℃以下に保持することを特徴とする
低銀品位の電気ビスマスの製造法を提供するものであり
、好ましい態様としては電解液中の溶存酸素をｌ ｍ
ｇ／ｌ以下に保持しそして電解液の温度を３０℃以下に
保持することにより銀品位は］ ｐｐｍ以下とされる。Based on this knowledge, the present invention provides: 1) In bismuth electrolysis for producing electric bismuth, dissolved oxygen in the electrolyte is maintained at 5.0 mg/l or less. 2) A low-silver electrolysis method for producing electric bismuth, characterized in that dissolved oxygen in the electrolyte is maintained at 5.0 mg/l or less and the temperature of the electrolyte is maintained at 40°C or less. The present invention provides a method for producing high-quality electric bismuth, and in a preferred embodiment, dissolved oxygen in the electrolyte is reduced to l m
By maintaining the silver content below g/l and keeping the temperature of the electrolyte below 30° C., the silver grade is kept below ppm.
免肚旦且盗璽韮ｌ
電気ビスマスへの銀混入については、物理的汚染と電気
化学的汚染の２大要囚があるが、本発明は電気化学的汚
染を防止するものである。There are two major concerns regarding silver contamination in electric bismuth: physical contamination and electrochemical contamination, but the present invention prevents electrochemical contamination.
アノードからの銀の溶出については次の２つの反応が考
えられる二
■Ａｇ″″＋ｅ ＝Ａｇ Ｅ” （ａｔ ２５℃）
＝ ＋ ０．７９９４Ｖ（Ｂｉ’″３＋ ３ｅ ＝ Ｂ
ｉ ＋０．３２Ｖ ）■ ２Ａｇ ＋ ｌ／２０□＋
ＨｚＳｉＦｇ＝ ＡｇｚＳｉＦｓ ” ）＋２０■の反
応についてはその平衡電位から判断して無視できるもの
と考えられる。■の反応によって溶出したＡｇ’″は負
極に達するまでにアノードスライムとして固定すれば電
気ビスマスの汚染は抑制できるが、このための方法とし
て、現在、電解液にＨＣＩを添加し、
■Ａｇ”＋ＣＩ−＝ ＡｇＣ１↓（ＣＩ濃度５０〜１０
０ ｍｌ／Ｉ ）の反応によりＡｇ”の混入防止を計っ
ている。しかし、電気ビスマスの銀品位を５ ｐｐｍ以
下に低減するには、これだけでは不十分であり、■の反
応による銀溶出を極力抑制する必要がある。Regarding the elution of silver from the anode, the following two reactions can be considered.2■Ag″″+e =Ag E″ (at 25°C)
= + 0.7994V (Bi'''3+ 3e = B
i +0.32V)■ 2Ag + l/20□+
HzSiFg=AgzSiFs")+20The reaction of ■ is considered to be negligible judging from its equilibrium potential.If the Ag'" eluted by the reaction of ■ is fixed as an anode slime before reaching the negative electrode, it will not contaminate the electric bismuth. However, the current method for this purpose is to add HCI to the electrolyte, and ■Ag"+CI-=AgC1↓ (CI concentration 50 to 10
0 ml/I) reaction to prevent the contamination of Ag''. However, this alone is not sufficient to reduce the silver content of electric bismuth to 5 ppm or less, and the silver elution caused by the reaction (2) is minimized. need to be suppressed.
アノードスライムを電解液（ＣＩ濃度５０ ｍｌ／Ｉ
）に浮遊させて、電解液中の溶存酸素を変化させた場合
の電解液中の溶存酸素と銀濃度との関係を第１図に示す
。両者間には、はぼ正比例関係が見られる。これが、本
発明の溶存酸素低減効果を裏付けるものと考えられる。The anode slime was mixed with an electrolyte solution (CI concentration 50 ml/I
) and the relationship between dissolved oxygen in the electrolyte and silver concentration is shown in FIG. 1 when the dissolved oxygen in the electrolyte is varied. A directly proportional relationship can be seen between the two. This is considered to support the dissolved oxygen reducing effect of the present invention.
次に、ＨｉＳｉＦｓ系電解液において、電解液の温度を
低くする程、銀汚染を一層防止しうることも本発明にお
いて初めて確認された。Next, it was also confirmed for the first time in the present invention that silver contamination can be further prevented as the temperature of the HiSiFs electrolyte is lowered.
第２図は、上記溶存酸素及び温度低減効果に基ずく電気
ビスマスの銀品位を示すグラフである。FIG. 2 is a graph showing the silver quality of electric bismuth based on the dissolved oxygen and temperature reduction effects.
これから、電解液中の溶存酸素を５．０ｍｇ／ｌ以下に
保持することにより５ ｐｐｍ以下の低銀品位の電気ビ
スマスの製造が可能とされ、特には、電解液中の溶存酸
素を５．０ｍｇ／ｌ以下に保持しそして電解液の温度を
４０℃以下、好ましくは３５℃以下に保持することによ
り安定して低銀品位の電気ビスマスを製造することが出
来る。驚くべきことに、電解液中の溶存酸素を１ ｍ
ｇ／ｌ以下に保持しそして電解液の温度を３０℃以下に
保持することにより銀品位はｌ ｐｐｍ以下にまでも低
減されつる。From now on, it is possible to produce electric bismuth with a low silver grade of 5 ppm or less by keeping the dissolved oxygen in the electrolyte at 5.0 mg/l or less. By maintaining the temperature of the electrolyte below 40°C, preferably below 35°C, electric bismuth with a low silver grade can be stably produced. Surprisingly, dissolved oxygen in the electrolyte was reduced to 1 m
By keeping the silver content below 1 ppm and keeping the temperature of the electrolyte below 30° C., the silver quality can be reduced to below 1 ppm.
電解液の温度を下げることは、電流密度を低下せしめ従
って電解効率を下げると同時に冷却コストを必要とする
ので、状況に応じて許容される程度まで電解液の温度を
下げたうえで、電解液中の溶存酸素の低減化を計ること
が好ましい。Lowering the temperature of the electrolyte lowers the current density and therefore lowers the electrolytic efficiency and requires cooling costs. It is preferable to reduce the amount of dissolved oxygen in the container.
電解液中の溶存酸素の低減化を計るためには、周囲空気
との接触或はその巻き込みを最大限に防止する次のよう
な対策が必要である：
１）電解液循環用ポンプをゲランドレスポンプに変更す
る（例えばマグネットポンプの使用）。In order to reduce dissolved oxygen in the electrolyte, it is necessary to take the following measures to prevent contact with the surrounding air or entrainment to the maximum extent possible: 1) Use a Guerandless pump for electrolyte circulation. Change to a pump (e.g. use a magnetic pump).
２）循環電解液の電解槽への返送に際しての或はその循
環経路において、液落下時の空気巻き込みを防止するた
め管先端を液中に浸漬状態とする。2) When returning the circulating electrolyte to the electrolytic cell or in the circulation route, the tip of the tube is immersed in the liquid to prevent air from being entrained when the liquid falls.
３）循環電解液の濾過時の空気巻き込みを防止するため
開放型フィルターを密閉型フィルターに変更する。3) Change the open type filter to a closed type filter to prevent air entrainment during filtration of the circulating electrolyte.
４）電解槽液表面の浮子、ポリプロピレンボール等によ
る被覆或は密閉蓋ないしカバーの採用により液表面と空
気との接触を防止する。4) Prevent contact between the liquid surface and air by coating the surface of the electrolytic cell liquid with a float, polypropylene balls, etc., or by using an airtight lid or cover.
こうした対策の下で電解液中の溶存酸素は充分に低減さ
れ得るが、電解液循環経路において、電解液を真空に曝
したり、ＣＯガス等のバブリングといった脱酸対策を講
じることも有用である。Although dissolved oxygen in the electrolyte can be sufficiently reduced under these measures, it is also useful to take deoxidizing measures such as exposing the electrolyte to a vacuum or bubbling CO gas or the like in the electrolyte circulation path.
温度管理は、電解槽自体のの温度コントロール或は液循
環経路での電解液温度調節によりもたらされる。Temperature control is achieved by controlling the temperature of the electrolytic cell itself or adjusting the temperature of the electrolyte in the liquid circulation path.
電解操業条件は、温度及び溶存酸素の管理を除いて、次
のような従来態様に従う、塩素による銀除去効果をも活
用するため、塩素濃度を７０〜１００ｇ／Ｉ と高めに
なし且つか過を強化することが推奨される。The electrolytic operation conditions, except for temperature and dissolved oxygen management, are as follows: In order to take advantage of the silver removal effect of chlorine, the chlorine concentration is high (70 to 100 g/I) and there is no filtration. Reinforcement is recommended.
電解液組成
り１４３３０〜１００ ｇ／１
）１ｉＳｊＦａ ２００〜４００
ｇ／ＩＣ１濃度 ５０〜１００ ｍｌ／１電
解条件
Ｄｋ ５８〜？ＯＡ／ｍ２
摺電圧 ０．３５〜０．４５Ｖ
アノード 炉布製袋装着
カソード ステンレス鋼
環流量 １〜４ １／ｍｉｎ槽こうして低銀品
位の電気ビスマスがカソード上に電着され、これを剥取
り、精製炉にて脱銅処理を施された後、製品ビスマスが
得られる。Electrolyte composition 14330-100 g/1) 1iSjFa 200-400
g/IC1 concentration 50-100 ml/1 Electrolytic conditions Dk 58-? OA/m2 Sliding voltage 0.35~0.45V Anode Furnace cloth bag attached cathode Stainless steel circulation flow rate 1~4 1/min bath Thus, low silver grade electric bismuth is electrodeposited on the cathode, and this is peeled off. After being decoppered in a refining furnace, the bismuth product is obtained.
一方、電気ビスマス中に入らず、アノードスライムに残
留した銀は別途処理される。On the other hand, silver that does not enter the electric bismuth and remains in the anode slime is treated separately.
及豆立刀１
比較的簡易な対策により、５ ｐｐｍ以下特には１ｐｐ
ｍ以下の低銀品位の電気ビスマスの製造が可能とされ、
銀資源の回収の徹底化を計ると共に従来より高純度のビ
スマス材料を電子デバイスと関連して使用可能とした。Oimizu Tachito 1 Relatively simple measures can reduce the concentration to 5 ppm or less, especially 1 ppm.
It is said that it is possible to produce electric bismuth with a low silver grade of less than m.
In addition to thorough recovery of silver resources, we have made it possible to use bismuth materials with higher purity than before in connection with electronic devices.
Ｋ施ｌ
以下の条件にて電気ビスマスを製造した：電解液組成
りｉ” ７０〜８０ ｇ／ｌ＋（２ＳＩＦ
１１ ３００〜３５０ ｇ／ＩＣＩ濃度
８０ ｍｇ／ｌ電解条件
保有液量 ２２ｍ３
Ｄｋ ６５ Ａ／ｍ”
摺電圧 ０．４Ｖ
アノード か布製袋装着
寸法 約１ｍ２
カソード ステンレス鋼
寸法 約１ｍ”
環流量 ３ １／ｍｉｎ槽
極ライフ １４日
電解液溶存酸素量は０．５〜５．０ ｍｇ／Ｉの範囲で
そして電解液温度は１５〜４５℃の範囲で変更し、得ら
れた関係が、前出の第２図である。温度を１５℃に減す
ると、溶存酸素１．０ｍｇ／ｌで電気ビスマス銀含有量
は充分に１．０ｐｐｍ以下になる。温度を３０℃に減す
ると、溶存酸素０．５ｍｇ／Ｉで電気ビスマス銀含有１
は１．０ ｐｐｍ以下になる。現状の温度下での操業で
も、溶存酸素２．０ｍｇ／ｌ以下に管理することにより
容易に５ ｐｐｍ以下の低銀品位の電気ビスマスの製造
が可能であることがわかる。Electric bismuth was produced under the following conditions: Electrolyte composition i'' 70-80 g/l+(2SIF
11 300-350 g/ICI concentration
80 mg/l Electrolytic condition Retained liquid volume 22 m3 Dk 65 A/m" Sliding voltage 0.4 V Anode or cloth bag mounting dimensions Approx. 1 m2 Cathode Stainless steel dimensions Approx. 1 m" Circulating flow rate 3 1/min Cell electrode life 14 days Electrolyte The amount of dissolved oxygen was varied in the range of 0.5 to 5.0 mg/I, and the electrolyte temperature was varied in the range of 15 to 45°C, and the relationships obtained are shown in FIG. 2 above. When the temperature is reduced to 15° C., the electrical bismuth silver content is well below 1.0 ppm with dissolved oxygen of 1.0 mg/l. When the temperature is reduced to 30°C, electrical bismuth silver containing 1 with dissolved oxygen 0.5 mg/I
becomes 1.0 ppm or less. It can be seen that even under the current operating temperature, it is possible to easily produce electric bismuth with a low silver grade of 5 ppm or less by controlling dissolved oxygen to 2.0 mg/l or less.
製品ビスマスの分析値の一例を示す（ｐｐｍ） ：Ｂ
Ｉ ＡＬ −助 士 −劇 −科
９９９９ ％ ０．９２２１２
４×［の１８日
第１図は電解液中の溶存酸素と銀濃度との関係を示すグ
ラフであり、第２図は、溶存酸素及び温度と電気ビスマ
スの銀品位との関係をを示すグラフである。An example of the analysis value of bismuth product (ppm): B
Figure 1 is a graph showing the relationship between dissolved oxygen and silver concentration in the electrolyte, and Figure 2 is a graph showing the relationship between dissolved oxygen and silver concentration in the electrolyte. It is a graph showing the relationship between temperature and silver grade of electric bismuth.
ｊｌ“−１ ：、□、Ｉ寺。jl“-1 :, □, I temple.
代理人の氏名 倉 内 基 （１ 第１図 ３Ｉ− 溶存底引”Ｑ／ｌ） 第２図 簿存級引ｍｇ／ｌ ）Name of agent: Motoi Kurauchi (1 Figure 1 3I- Dissolved bottom pull”Q/l) Figure 2 Book balance mg/l)
Claims (1)
解液中の溶存酸素を５．０ｍｇ／ｌ以下に保持すること
を特徴とする低銀品位の電気ビスマスの製造法。 ２）電気ビスマスを製造するビスマス電解において、電
解液中の溶存酸素を５．０ｍｇ／ｌ以下に保持しそして
電解液の温度を４０℃以下に保持することを特徴とする
低銀品位の電気ビスマスの製造法。 ３）電解液中の溶存酸素を１ｍｇ／ｌ以下に保持しそし
て電解液の温度を３０℃以下に保持することにより銀品
位を１ｐｐｍ以下とした特許請求の範囲第２項記載の低
銀品位の電気ビスマスの製造法。[Scope of Claims] 1) A method for producing electric bismuth with a low silver grade, characterized in that dissolved oxygen in the electrolyte is maintained at 5.0 mg/l or less in bismuth electrolysis for producing electric bismuth. 2) Low silver grade electric bismuth characterized by maintaining dissolved oxygen in the electrolyte at 5.0 mg/l or less and maintaining the temperature of the electrolyte at 40°C or less in bismuth electrolysis for producing electric bismuth. manufacturing method. 3) The low silver grade according to claim 2, in which the dissolved oxygen in the electrolyte is kept at 1 mg/l or less and the temperature of the electrolyte is kept at 30° C. or less, thereby reducing the silver grade to 1 ppm or less. Method for producing electric bismuth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62297726A JPH01139790A (en) | 1987-11-27 | 1987-11-27 | Production of electrolytic bismuth having low silver content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62297726A JPH01139790A (en) | 1987-11-27 | 1987-11-27 | Production of electrolytic bismuth having low silver content |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01139790A true JPH01139790A (en) | 1989-06-01 |
Family
ID=17850381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62297726A Pending JPH01139790A (en) | 1987-11-27 | 1987-11-27 | Production of electrolytic bismuth having low silver content |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01139790A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019203199A (en) * | 2019-07-23 | 2019-11-28 | Ｊｘ金属株式会社 | Electrolytic method of bismuth |
-
1987
- 1987-11-27 JP JP62297726A patent/JPH01139790A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019203199A (en) * | 2019-07-23 | 2019-11-28 | Ｊｘ金属株式会社 | Electrolytic method of bismuth |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0068469B1 (en) | Refining copper-bearing material contaminated with nickel, antimony and/or tin | |
| JPS6327434B2 (en) | ||
| JP2642230B2 (en) | Manufacturing method of high purity tin | |
| US4287030A (en) | Process for producing high-purity indium | |
| GB2267716A (en) | Process for the direct electrochemical refining of copper scrap | |
| US4312724A (en) | Method for the recovery of lead from materials containing lead sulfide | |
| JP2623267B2 (en) | Manufacturing method of low-purity high-purity electrolytic copper | |
| JPH01139790A (en) | Production of electrolytic bismuth having low silver content | |
| JP2594799B2 (en) | Manufacturing method of low-purity high-purity electrolytic copper | |
| JP2019052329A (en) | Electrorefining method of low-grade copper anode, and electrolytic solution used therefor | |
| KR102237348B1 (en) | Recovery method of copper and precious metal by electrolysis of crude copper containing precious metal using copper chloride solution | |
| US3915818A (en) | Electrowinning process for the improved recovery of metal | |
| EP0219475A1 (en) | Electrowinning cell | |
| US3755111A (en) | Elimination of floating slime during electrolytic refining of copper | |
| US3382163A (en) | Method of electrolytic extraction of metals | |
| US4124460A (en) | Electrowinning of copper in presence of high concentration of iron | |
| US2839461A (en) | Electrolytic recovery of nickel | |
| JP2570076B2 (en) | Manufacturing method of high purity nickel | |
| US881527A (en) | Process for treating complex cobalt ores and for refining cobalt from nickel, arsenical, and silver-bearing ores. | |
| JPS63307291A (en) | Manufacture of high-purity copper | |
| KR100349445B1 (en) | Cementation apparatus of high purity copper | |
| JPH01219186A (en) | Method for refining indium | |
| CA1123778A (en) | Process and apparatus for the purification of gallium | |
| US1157830A (en) | Electrolytic refining of tin. | |
| JPS63297583A (en) | Manufacture of high-purity electrolytic copper |