JP2011174113A - Electrolytic refiner for copper and electrolytic refining method for copper using the same - Google Patents
Electrolytic refiner for copper and electrolytic refining method for copper using the same Download PDFInfo
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- JP2011174113A JP2011174113A JP2010037390A JP2010037390A JP2011174113A JP 2011174113 A JP2011174113 A JP 2011174113A JP 2010037390 A JP2010037390 A JP 2010037390A JP 2010037390 A JP2010037390 A JP 2010037390A JP 2011174113 A JP2011174113 A JP 2011174113A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 57
- 239000010949 copper Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000007670 refining Methods 0.000 title claims abstract description 7
- 239000003292 glue Substances 0.000 claims abstract description 128
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 74
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000654 additive Substances 0.000 claims abstract description 53
- 230000000996 additive effect Effects 0.000 claims abstract description 49
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 48
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004090 dissolution Methods 0.000 claims abstract description 28
- 238000000746 purification Methods 0.000 claims description 32
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
本発明は、銅の電解精製装置及びそれを用いた銅の電解精製方法に関する。 The present invention relates to a copper electrolytic purification apparatus and a copper electrolytic purification method using the same.
銅の電解精製では、一般に、電解槽に供給する電解液に、電気銅表面の外観を向上させるための膠を添加している（例えば、特許文献１又は２）。また、この電解液には、膠の他に、電気銅表面の外観を向上させるためのチオ尿素及び塩酸、さらには膠の腐食防止のための硫酸が添加されている。 In electrolytic refining of copper, glue for improving the appearance of the surface of electrolytic copper is generally added to the electrolytic solution supplied to the electrolytic cell (for example, Patent Document 1 or 2). In addition to the glue, thiourea and hydrochloric acid for improving the appearance of the electrolytic copper surface, and sulfuric acid for preventing the corrosion of the glue are added to the electrolytic solution.
図２は、従来の一般的な銅の電解精製装置２０の模式図を示している。従来の銅の電解精製装置２０は、電解槽２７、電解槽２７へ電解液を供給する電解液供給部２１、電解液供給部２１へ供給する添加剤が設けられた添加剤槽２２、添加剤槽２２へ供給する膠の水溶液が調整される膠溶液槽２３、添加剤槽２２へ供給するチオ尿素が設けられたチオ尿素溶解槽２４、添加剤槽２２へ供給する塩酸が設けられた塩酸槽２５、添加剤槽２２へ供給する硫酸が設けられた硫酸槽２６、及び、これらの各槽間に設けられたポンプｐ’１〜ｐ’６を備えている。電解精製装置２０において、膠は、まず、膠溶解槽２３で水溶液とした後、チオ尿素、塩酸及び硫酸が供給された添加剤槽２２にてそれらの添加剤と混合させる。このようにして添加剤槽２２で添加剤溶液を作製し、これを電解液供給部２１へ供給した後、電解液供給部２１から添加剤溶液が含まれた電解液を電解槽２７へ供給している。また、膠溶解槽２３で膠の水溶液を作製する際は、膠の計量や膠溶解槽２３への投入作業を人力で所定の作業時間（通常１日に１回）でバッチ処理を行っており、さらに添加剤溶液の調整についても同じ頻度で行っている。
FIG. 2 shows a schematic view of a conventional general copper electrolytic purification apparatus 20. The conventional copper electrolytic purification apparatus 20 includes an
しかしながら、膠の水溶液を添加剤溶液中に混合する場合、添加剤溶液には、塩酸や硫酸が含まれており、動物性タンパク質で高分子物質の膠がこれらの酸により分解され低分子化する。また、膠を塩酸や硫酸と混合させず、中性の水溶液中で、単独で電解液供給部へ添加させる場合、膠は腐食しやすいという性質を有する。 However, when an aqueous solution of glue is mixed into the additive solution, the additive solution contains hydrochloric acid and sulfuric acid, and the polymer substance glue in animal protein is decomposed by these acids to lower the molecular weight. . Further, when the glue is added to the electrolytic solution supply unit alone in a neutral aqueous solution without being mixed with hydrochloric acid or sulfuric acid, the glue has a property of being easily corroded.
このように、酸による低分子化した膠、又は、腐食した膠が電解液に添加された場合、電気銅に対する膠効果の低下により、製品外観の不良や不純物品位の増加という品質劣化に繋がる。また、電気銅の品質を維持するために、酸分解、もしくは腐食された膠の影響を回避するために、膠の添加量を増やした場合には、電解液中に過剰添加された膠による電解液抵抗の増加が起こり、印加電圧を高電圧化しなければならず、消費電力の増大に繋がり、問題となる。 As described above, when glue with a low molecular weight due to acid or corrosive glue is added to the electrolytic solution, the glue effect on the electrolytic copper is reduced, leading to quality deterioration such as defective product appearance and increased impurity quality. In addition, in order to maintain the quality of electrolytic copper, in order to avoid the influence of acid decomposition or corroded glue, if the amount of glue added is increased, electrolysis by glue added excessively in the electrolyte An increase in liquid resistance occurs, the applied voltage must be increased, leading to an increase in power consumption, which is a problem.
そこで、本発明は、品質の良好な電気銅を良好な製造コストで作製できる銅の電解精製装置及びそれを用いた銅の電解精製方法を提供することを課題とする。 Then, this invention makes it a subject to provide the electrolytic purification apparatus of copper which can produce high quality electrolytic copper with favorable manufacturing cost, and the electrolytic purification method of copper using the same.
本発明者は、鋭意検討した結果、膠を酸と混合させず、他の添加剤とは別に単独で電解液供給部へ添加し、且つ、膠の計量、溶解、添加の各工程を連続して実施することにより、酸による分解を抑制でき、新鮮な高分子状態の膠の水溶液を電解液中に添加でき、品質の良好な電気銅を良好な製造コストで作製できることを見出した。 As a result of intensive studies, the inventor did not mix the glue with the acid, added it alone to the electrolyte supply unit separately from other additives, and continued the steps of measuring, dissolving, and adding glue. It has been found that the decomposition by acid can be suppressed, a fresh polymer glue aqueous solution can be added to the electrolyte, and high-quality electrolytic copper can be produced at a good production cost.
以上の知見を基礎として完成した本発明は一側面において、銅の電解槽と、電解槽へ電解液を供給する電解液供給部と、膠を除く添加剤を前記電解液供給部へ供給する添加剤槽と、電解精製中に膠を連続的に溶解し、電解液供給部へ連続して供給することを可能とした膠溶解槽とを備えた銅の電解精製装置である。 The present invention completed on the basis of the above knowledge is, in one aspect, a copper electrolytic cell, an electrolytic solution supply unit that supplies the electrolytic solution to the electrolytic cell, and an additive that supplies additives other than glue to the electrolytic solution supply unit It is an electrolytic purification apparatus for copper provided with an agent tank and a glue dissolution tank capable of continuously dissolving glue during electrolytic purification and continuously supplying it to an electrolyte supply section.
本発明に係る銅の電解精製装置の一実施形態においては、膠溶解槽に膠を連続して供給する膠供給部をさらに備える。 In one embodiment of the copper electrolytic purification apparatus according to the present invention, the apparatus further includes a glue supply unit that continuously supplies glue to the glue dissolving tank.
本発明に係る銅の電解精製装置の別の一実施形態においては、膠を除く添加剤は、チオ尿素及び塩酸を含む。 In another embodiment of the copper electrolytic purification apparatus according to the present invention, the additive excluding glue includes thiourea and hydrochloric acid.
本発明は別の一側面において、膠を除く添加剤を電解液供給部へ供給する工程と、電解精製中に膠を連続的に溶解し、電解液供給部へ連続して供給する工程と、膠を除く添加剤と膠の水溶液とを含む電解液を、電解液供給部から銅の電解槽へ供給する工程とを含む銅の電解精製方法である。 In another aspect of the present invention, the step of supplying an additive excluding glue to the electrolyte supply unit, the step of continuously dissolving glue during electrolytic purification, and continuously supplying to the electrolyte supply unit, A method for electrolytically purifying copper, comprising a step of supplying an electrolytic solution containing an additive excluding glue and an aqueous solution of glue from an electrolytic solution supply unit to a copper electrolytic cell.
本発明に係る銅の電解精製方法の一実施形態においては、膠の水溶液を作製する際に用いる膠の計量を、膠の連続供給及び連続溶解と同時に連続して行う。 In one embodiment of the copper electrolytic purification method according to the present invention, the amount of glue used in preparing the aqueous solution of glue is continuously measured simultaneously with the continuous supply and continuous dissolution of glue.
本発明によれば、膠を酸と混合させず、他の添加剤とは別に単独で電解液供給部へ添加し、且つ、膠の計量、溶解、添加の各工程を連続して実施することが可能となり、酸による分解を抑制でき、新鮮な高分子状態の膠の水溶液を電解液中に添加でき、良好な品質の電気銅を作製できる。また、高分子状態で膠を添加できる装置および方法であるため、過剰に膠を添加する必要がない。従って、低消費電力化に寄与し、さらに、従来、膠の腐蝕防止用に使用していた硫酸を使用する必要がなくなるため、製造コストの低減にも寄与する。 According to the present invention, the glue is not mixed with the acid, separately from the other additives, added alone to the electrolyte supply unit, and the steps of measuring, dissolving, and adding the glue are continuously performed. Therefore, decomposition by acid can be suppressed, and an aqueous solution of glue in a fresh polymer state can be added to the electrolytic solution, and good quality electrolytic copper can be produced. Further, since the apparatus and method can add glue in a polymer state, it is not necessary to add glue excessively. Therefore, it contributes to low power consumption, and further contributes to a reduction in manufacturing cost because it is no longer necessary to use sulfuric acid that has been conventionally used for preventing the corrosion of glue.
（銅の電解精製装置）
銅の電解精製装置１０は、銅の電解槽１７と、電解液供給部１１と、添加剤槽１２と、膠溶解槽１３と、チオ尿素溶解槽１４と、塩酸槽１５と、膠供給部１６とを備えている。電解液供給部１１と添加剤槽１２との間、電解液供給部１１と膠溶解槽１３との間、添加剤槽１２とチオ尿素溶解槽１４との間、添加剤槽１２と塩酸槽１５との間、電解液供給部１１と電解槽１７との間には、それぞれ溶液の供給動力となるポンプｐ１〜ｐ５が設けられている。
(Electrolytic purification equipment for copper)
The copper
添加剤槽１２には、チオ尿素溶解槽１４からポンプｐ３によって供給されたチオ尿素の水溶液と、塩酸槽１５からポンプｐ４によって供給された塩酸とが含まれている。
The
膠供給部１６は、貯蔵している膠を計量して切り出し、膠溶解槽１３へ供給する。膠溶解槽１３には、膠供給部１６から供給された膠と不図示の温水供給部からの温水とが混合されて形成された膠の水溶液が含まれている。
The
電解液供給部１１には、電解液と、膠溶解槽１３からポンプｐ２によって供給された膠の水溶液と、添加剤槽１２からポンプｐ１によって供給された添加剤溶液とが含まれている。添加剤溶液は、チオ尿素を含む塩酸で構成されている。
The electrolytic
電解槽１７には、陽極となる粗銅と、電着面に銅を電着させることにより、製品となる電気銅を精製するための陰極となる銅製の母板とが、所定間隔を空けて設けられている。また、電解槽１７には、電解液供給部１１からポンプｐ５によって電解液が供給されている。ここで、陰極となる母板には、用途に合わせて種々のものを用いることができ、例えば、パーマネントカソード法（ＰＣ法）で電気分解を行う場合は、ＳＵＳ板等を用いても良い。
The
（銅の電解精製方法）
次に、電解精製装置１０を用いた銅の電解精製方法について説明する。
まず、図１に示した電解精製装置１０において、チオ尿素溶解槽１４に所定濃度のチオ尿素の水溶液を作製しておく。また、塩酸槽１５に所定濃度の塩酸を作製しておく。
続いて、チオ尿素の水溶液及び塩酸を、ポンプｐ３及びｐ４を用いて添加剤槽１２へ供給して撹拌混合する。
(Method for electrolytic purification of copper)
Next, a copper electrolytic purification method using the
First, in the
Subsequently, an aqueous solution of thiourea and hydrochloric acid are supplied to the
次に、添加剤槽１２内のチオ尿素を含む塩酸をポンプｐ１を用いて電解液供給部１１へ供給する。
ここで、添加剤槽１２から電解液供給部１１へのチオ尿素を含む塩酸の供給は、バッチ式で行ってもよい。すなわち、添加剤槽１２で、チオ尿素の水溶液及び塩酸の例えば一日分を一度に混合して貯蔵しておいたものを、電解液供給部１１へ供給してもよい。また、当該供給は、連続式で行ってもよい。すなわち、添加剤槽１２で、チオ尿素の水溶液及び塩酸を連続して混合し、必要量をその都度電解液供給部１１へ供給してもよい。
Next, hydrochloric acid containing thiourea in the
Here, the supply of hydrochloric acid containing thiourea from the
一方、膠供給部１６では、貯蔵している膠を計量して切り出し、膠溶解槽１３へ連続して供給する。不図示の温水供給部からの温水も、膠溶解槽１３へ連続して供給する。供給された膠は、温水と共に膠溶解槽１３内で撹拌されて１０分程度で溶解し、膠の水溶液が生成する。これと連続して、膠の水溶液を、ポンプｐ２を用いて電解液供給部１１へ供給する。
また、このとき、膠供給部１６による膠の計量を、膠の供給、膠溶解槽１３での膠の溶解、及び、膠溶解槽１３から電解液供給部１１への膠の水溶液の供給と同時に連続して行ってもよい。
On the other hand, the
At this time, the glue is measured by the
添加剤槽１２から供給されたチオ尿素を含む塩酸、及び、膠溶解槽１３から連続供給される膠の水溶液は、電解液供給部１１内で電解液と共に撹拌・混合される。続いて、電解液供給部１１から電解槽１７へ、チオ尿素、塩酸及び膠を含む電解液をポンプｐ５によって供給し、この電解液を用いて電解槽１７内で銅の電解精製を行う。
The hydrochloric acid containing thiourea supplied from the
本発明では、上述のように、膠供給部１６から連続して供給される膠を膠溶解槽１３内で連続的に溶解することにより作製した膠の水溶液を、電解液供給部１１へ連続的に供給している。このように、添加剤槽１２で塩酸と混合することなく、溶解した膠が直接電解液供給部１１へ供給されるため、酸による膠の分解が無く、膠を効率的に使用することができる。また、膠の腐食防止のための硫酸を添加剤槽１２へ供給する必要がなくなる。従って、製造コストが良好となる。また、連続して供給される膠を連続的に溶解し、電解液供給部１１へ連続的に供給するため、電解液供給部１１へ供給するまでに膠が水に溶解している時間が短く、膠の腐食を抑制でき、良好な品質の電気銅を提供することができる。また、膠の水溶液を作製する際に用いる膠の計量を、膠の連続供給及び連続溶解と同時に連続して行うため、製造効率が良好となる。
In the present invention, as described above, an aqueous solution of glue prepared by continuously dissolving glue supplied continuously from the
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
（実施例）
実施例として、図１に示す構成の銅の電解精製装置を準備し、これを用いて銅の電解精製を行った。
具体的には、まず、長さ１２８０ｍｍ×幅５５５０ｍｍ×深さ１３４０ｍｍの電解槽に、縦１０６０ｍｍ×横９９０ｍｍ×厚さ４５ｍｍの粗銅板を５４枚、及び、縦１０４０ｍｍ×横１０４０ｍｍ×厚さ１０ｍｍの母板を５３枚、それぞれ１００ｍｍの間隔を空けて設けた。
次に、チオ尿素溶解槽に０．８３ｍｏｌ／Ｌのチオ尿素の水溶液を設け、塩酸槽に９．６ｍｏｌ／Ｌの塩酸を設けた。
次に、チオ尿素の水溶液及び塩酸を、添加剤槽へ供給して撹拌混合した。また、添加剤槽内の液温は、２０〜３０℃に保持した。添加剤槽内のチオ尿素を含む塩酸は、このようにして作り貯めをしておき、その内の必要量を電解液供給部へ供給した。
膠供給部では、貯蔵している膠を計量して切り出し、膠溶解槽へ連続して供給すると共に、温水供給部から温水も膠溶解槽へ連続して供給した。供給された膠は、温水と共に膠溶解槽内で撹拌されて１０分程度で溶解した。このとき、膠の水溶液は、濃度が０．５ｍｍｏｌとなるように調整した。続いて、生成した膠の水溶液を連続して、電解液供給部へ供給した。また、膠溶解槽内の液温は、３５〜４５℃に保持した。
続いて、電解液供給部内で、添加剤槽からのチオ尿素を含む塩酸、及び、膠溶解槽から連続供給される膠の水溶液を、電解液と共に撹拌・混合した。続いて、電解液供給部から電解槽へ、チオ尿素、塩酸及び膠を含む電解液を供給し、この電解液を用いて電解槽内で、２１０時間、電流密度３２０Ａ／ｍ2にて銅の電解精製を行った。
上述の実施例により、６３５０ｔの電気銅を得た。これに要した膠使用量は３５０ｋｇであり、消費電力量は３７０ｋＷｈであった。
(Example)
As an example, a copper electrolytic purification apparatus having the configuration shown in FIG. 1 was prepared, and copper was subjected to electrolytic purification using this.
Specifically, first, in an electrolytic cell having a length of 1280 mm × width of 5550 mm × depth of 1340 mm, 54 rough copper plates of length 1060 mm × width 990 mm × thickness 45 mm, and length 1040 mm × width 1040 mm ×
Next, an aqueous solution of 0.83 mol / L thiourea was provided in the thiourea dissolution tank, and 9.6 mol / L hydrochloric acid was provided in the hydrochloric acid tank.
Next, an aqueous solution of thiourea and hydrochloric acid were supplied to the additive tank and mixed with stirring. Moreover, the liquid temperature in an additive tank was hold | maintained at 20-30 degreeC. The hydrochloric acid containing thiourea in the additive tank was made and stored in this manner, and the required amount thereof was supplied to the electrolyte supply section.
In the glue supply section, the stored glue was weighed and cut out and continuously supplied to the glue dissolution tank, and hot water was also continuously supplied from the hot water supply section to the glue dissolution tank. The supplied glue was stirred together with warm water in a glue dissolution tank and dissolved in about 10 minutes. At this time, the aqueous glue solution was adjusted to a concentration of 0.5 mmol. Subsequently, the generated aqueous glue solution was continuously supplied to the electrolyte supply unit. Moreover, the liquid temperature in a glue dissolution tank was hold | maintained at 35-45 degreeC.
Subsequently, hydrochloric acid containing thiourea from the additive tank and an aqueous solution of glue continuously supplied from the glue dissolution tank were stirred and mixed together with the electrolyte in the electrolyte supply section. Subsequently, an electrolytic solution containing thiourea, hydrochloric acid and glue is supplied from the electrolytic solution supply unit to the electrolytic cell, and the electrolytic solution is used for 210 hours in an electrolytic cell at a current density of 320 A / m 2 . Electrolytic purification was performed.
According to the above-described example, 6350 t of electrolytic copper was obtained. The amount of glue used for this was 350 kg, and the power consumption was 370 kWh.
（比較例）
比較例として、図２に示す構成の銅の電解精製装置を準備し、これを用いて銅の電解精製を行った。
具体的には、まず、長さ１２８０ｍｍ×幅５５５０ｍｍ×深さ１３４０ｍｍの電解槽に、縦１０６０ｍｍ×横９９０ｍｍ×厚さ４５ｍｍの粗銅板を５４枚、及び、縦１０４０ｍｍ×横１０４０ｍｍ×厚さ１０ｍｍの母板を５３枚、それぞれ１００ｍｍの間隔を空けて設けた。
次に、膠溶解槽に３ｍｍｏｌ／Ｌの膠の水溶液を設け、チオ尿素溶解槽に０．８５ｍｏｌ／Ｌのチオ尿素の水溶液を設け、塩酸槽に１０．０ｍｏｌ／Ｌの塩酸を設け、硫酸槽に１０．０ｍｏｌ／Ｌの硫酸を設けた。
次に、膠の水溶液、チオ尿素の水溶液、塩酸及び硫酸を、添加剤槽へ供給して撹拌混合した。また、添加剤槽内の液温は、２０〜３０℃に保持した。添加剤槽内の膠の水溶液、チオ尿素の水溶液、塩酸及び硫酸は、このようにして作り貯めをしておき、その内の必要量を電解液供給部へ供給した。
続いて、電解液供給部内で、添加剤槽からの膠の水溶液、チオ尿素の水溶液、塩酸及び硫酸の混合液を、電解液と共に撹拌・混合した。続いて、電解液供給部から電解槽へ、膠、チオ尿素、塩酸及び硫酸を含む電解液を供給し、この電解液を用いて電解槽内で、２１０時間、電流密度３２０Ａ／ｍ2にて銅の電解精製を行った。
上述の比較例により、６３５０ｔの電気銅を得た。これに要した膠使用量は４１０ｋｇであり、消費電力量は３７８ｋＷｈであった。
(Comparative example)
As a comparative example, a copper electrolytic purification apparatus having the configuration shown in FIG. 2 was prepared, and the copper electrolytic purification was performed using this apparatus.
Specifically, first, in an electrolytic cell having a length of 1280 mm × width of 5550 mm × depth of 1340 mm, 54 rough copper plates of length 1060 mm × width 990 mm × thickness 45 mm, and length 1040 mm × width 1040 mm ×
Next, an aqueous solution of 3 mmol / L glue is provided in the glue dissolving tank, an aqueous solution of 0.85 mol / L thiourea is provided in the thiourea dissolving tank, 10.0 mol / L hydrochloric acid is provided in the hydrochloric acid tank, and a sulfuric acid tank Was provided with 10.0 mol / L sulfuric acid.
Next, an aqueous solution of glue, an aqueous solution of thiourea, hydrochloric acid and sulfuric acid were supplied to the additive tank and mixed with stirring. Moreover, the liquid temperature in an additive tank was hold | maintained at 20-30 degreeC. The aqueous solution of glue, the aqueous solution of thiourea, hydrochloric acid and sulfuric acid in the additive tank were prepared and stored in this way, and the required amount thereof was supplied to the electrolyte supply unit.
Subsequently, the aqueous solution of glue, the aqueous solution of thiourea, and the mixed solution of hydrochloric acid and sulfuric acid from the additive tank were stirred and mixed together with the electrolytic solution in the electrolytic solution supply unit. Subsequently, an electrolytic solution containing glue, thiourea, hydrochloric acid and sulfuric acid is supplied from the electrolytic solution supply unit to the electrolytic cell, and the electrolytic solution is used in the electrolytic cell for 210 hours at a current density of 320 A / m 2 . Copper electrolytic purification was performed.
According to the comparative example described above, 6350 t of electrolytic copper was obtained. The amount of glue used for this was 410 kg, and the power consumption was 378 kWh.
１０ 電解精製装置
１１ 電解液供給部
１２ 添加剤槽
１３ 膠溶解槽
１４ チオ尿素溶解槽
１５ 塩酸槽
１６ 膠供給部
１７ 電解槽
ｐ１〜ｐ５ ポンプ
DESCRIPTION OF
Claims (5)
前記電解槽へ電解液を供給する電解液供給部と、
膠を除く添加剤を前記電解液供給部へ供給する添加剤槽と、
膠を連続的に溶解して作製した膠の水溶液を、前記電解液供給部へ連続的に供給する膠溶解槽と、
を備えた銅の電解精製装置。 A copper electrolytic cell;
An electrolytic solution supply unit for supplying an electrolytic solution to the electrolytic cell;
An additive tank for supplying an additive excluding glue to the electrolyte supply unit;
An aqueous solution of glue produced by continuously dissolving glue, a glue dissolution tank for continuously feeding the electrolyte supply part;
A copper electrolytic refining device.
電解精製中に膠を連続的に溶解し、電解液供給部へ連続して供給する工程と、
前記膠を除く添加剤と前記膠の水溶液とを含む電解液を、前記電解液供給部から銅の電解槽へ供給する工程と、
を含む銅の電解精製方法。 Supplying an additive excluding glue to the electrolyte supply unit;
A step of continuously dissolving glue during electrolytic purification and continuously supplying it to an electrolyte supply unit;
Supplying an electrolytic solution containing an additive excluding the glue and an aqueous solution of the glue from the electrolyte supply section to a copper electrolytic cell;
A method for electrolytic purification of copper, comprising:
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| JP2010037390A JP5275273B2 (en) | 2010-02-23 | 2010-02-23 | Copper electrolytic purification apparatus and copper electrolytic purification method using the same |
| KR1020117027925A KR101351105B1 (en) | 2010-02-23 | 2011-01-24 | Electrolytic copper refining device, and electrolytic copper refining method using same |
| AU2011219212A AU2011219212B2 (en) | 2010-02-23 | 2011-01-24 | Copper electrorefining equipment and copper electrorefining method using the same |
| PCT/JP2011/051209 WO2011105149A1 (en) | 2010-02-23 | 2011-01-24 | Electrolytic copper refining device, and electrolytic copper refining method using same |
| CL2012002253A CL2012002253A1 (en) | 2010-02-23 | 2012-08-14 | Electro copper refining equipment comprising an electrolytic copper bath, an electrolyte supply part, an additive bath supplying additives, and a tail dissolution bath, continuously supplying aqueous glue solution; and method for electro refining. |
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| JP2010037390A JP5275273B2 (en) | 2010-02-23 | 2010-02-23 | Copper electrolytic purification apparatus and copper electrolytic purification method using the same |
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| CN106011930A (en) * | 2016-07-28 | 2016-10-12 | 河南豫光金铅股份有限公司 | Continuous preparation method of refining electrolytic solution for copper electrolysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188969A (en) * | 1993-10-22 | 1995-07-25 | Gould Electron Inc | Electrodeposited copper foil and its preparation |
| JPH08304338A (en) * | 1995-05-08 | 1996-11-22 | Sumitomo Metal Mining Co Ltd | Operation control method of glue addition quantity into electrolyte in copper electrolytic refining |
| JP2002055097A (en) * | 2000-08-10 | 2002-02-20 | Sumitomo Metal Mining Co Ltd | Method for determination sulfonic acid type anionic surfactant in copper electrolytic solution |
| JP2005307343A (en) * | 2004-03-23 | 2005-11-04 | Mitsubishi Materials Corp | High-purity electrolytic copper and its production method |
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| KR890002750B1 (en) * | 1984-05-31 | 1989-07-26 | 아사코 인코포레이팃드 | Electrolytic method for copper refining |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188969A (en) * | 1993-10-22 | 1995-07-25 | Gould Electron Inc | Electrodeposited copper foil and its preparation |
| JP2002129373A (en) * | 1993-10-22 | 2002-05-09 | Ga Tek Inc | Electrodeposited copper foil and manufacturing method therefor |
| JPH08304338A (en) * | 1995-05-08 | 1996-11-22 | Sumitomo Metal Mining Co Ltd | Operation control method of glue addition quantity into electrolyte in copper electrolytic refining |
| JP2002055097A (en) * | 2000-08-10 | 2002-02-20 | Sumitomo Metal Mining Co Ltd | Method for determination sulfonic acid type anionic surfactant in copper electrolytic solution |
| JP2005307343A (en) * | 2004-03-23 | 2005-11-04 | Mitsubishi Materials Corp | High-purity electrolytic copper and its production method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106011930A (en) * | 2016-07-28 | 2016-10-12 | 河南豫光金铅股份有限公司 | Continuous preparation method of refining electrolytic solution for copper electrolysis |
| CN106011930B (en) * | 2016-07-28 | 2018-09-25 | 河南豫光金铅股份有限公司 | A kind of continuous preparation method of cupric electrolysis refining electrolyte |
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| JP5275273B2 (en) | 2013-08-28 |
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