WO2011105149A1 - Electrolytic copper refining device, and electrolytic copper refining method using same - Google Patents
Electrolytic copper refining device, and electrolytic copper refining method using same Download PDFInfo
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- WO2011105149A1 WO2011105149A1 PCT/JP2011/051209 JP2011051209W WO2011105149A1 WO 2011105149 A1 WO2011105149 A1 WO 2011105149A1 JP 2011051209 W JP2011051209 W JP 2011051209W WO 2011105149 A1 WO2011105149 A1 WO 2011105149A1
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- glue
- electrolytic
- tank
- supply unit
- copper
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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 9
- 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
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000003292 glue Substances 0.000 claims description 126
- 239000008151 electrolyte solution Substances 0.000 claims description 41
- 238000000746 purification Methods 0.000 claims description 32
- 238000004090 dissolution Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 108010010803 Gelatin Proteins 0.000 abstract 3
- 229920000159 gelatin Polymers 0.000 abstract 3
- 239000008273 gelatin Substances 0.000 abstract 3
- 235000019322 gelatine Nutrition 0.000 abstract 3
- 235000011852 gelatine desserts Nutrition 0.000 abstract 3
- 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
- 238000010586 diagram Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- -1 generally Substances 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
Images
Classifications
-
- 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
Definitions
- the present invention relates to a copper electrolytic purification apparatus and a copper electrolytic purification method using the same.
- glue for improving the appearance of the surface of electrolytic copper is added to the electrolytic solution supplied to the electrolytic cell (for example, Patent Document 1 or 2).
- 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.
- FIG. 2 shows a schematic diagram of a conventional general copper electrolytic purification apparatus 20.
- the conventional copper electrolytic purification apparatus 20 includes an electrolytic bath 27, an electrolytic solution supply unit 21 that supplies an electrolytic solution to the electrolytic bath 27, an additive bath 22 that is provided with an additive that supplies the electrolytic solution supply unit 21, and an additive
- the glue is first made into an aqueous solution in the glue dissolving tank 23 and then mixed with these additives in the additive tank 22 to which thiourea, hydrochloric acid and sulfuric acid are supplied.
- an additive solution is prepared in the additive tank 22 and supplied to the electrolytic solution supply unit 21.
- the electrolytic solution containing the additive solution is supplied from the electrolytic solution supply unit 21 to the electrolytic bath 27. ing.
- batch measurement is performed on the glue and the work of feeding into the glue dissolution tank 23 in a predetermined work time (usually once a day). Furthermore, the adjustment of the additive solution is performed at the same frequency.
- 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.
- the glue 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.
- an object of the present invention is to provide a copper electrolytic purification apparatus and a copper electrolytic purification method using the same, which can produce high-quality electrolytic copper at a favorable manufacturing cost.
- 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
- an electrolytic purification apparatus for copper provided with an agent tank and a glue dissolution tank that continuously supplies an aqueous solution of glue produced by continuously dissolving glue.
- the apparatus further includes a glue supply unit for continuously supplying glue to the glue dissolving tank.
- the additive excluding glue includes thiourea and hydrochloric acid.
- 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.
- the amount of glue used when preparing the aqueous solution of glue is continuously measured simultaneously with the continuous supply and continuous dissolution of glue.
- 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.
- the copper electrolytic purification apparatus 10 includes a copper electrolytic tank 17, an electrolytic solution supply unit 11, an additive tank 12, a glue dissolution tank 13, a thiourea dissolution tank 14, a hydrochloric acid tank 15, and a glue supply part 16. And. Between the electrolytic solution supply unit 11 and the additive tank 12, between the electrolytic solution supply unit 11 and the glue dissolution tank 13, between the additive tank 12 and the thiourea dissolution tank 14, and between the additive tank 12 and the hydrochloric acid tank 15. Between the electrolytic solution supply unit 11 and the electrolytic cell 17, pumps p 1 to p 5 serving as solution supply power are provided.
- the additive tank 12 contains an aqueous solution of thiourea supplied from the thiourea dissolution tank 14 by the pump p3 and hydrochloric acid supplied from the hydrochloric acid tank 15 by the pump p4.
- the glue supply unit 16 measures and cuts out the stored glue and supplies it to the glue dissolving tank 13.
- the glue dissolution tank 13 contains an aqueous solution of glue formed by mixing glue supplied from the glue supply unit 16 and hot water from a hot water supply unit (not shown).
- the electrolytic solution supply unit 11 includes an electrolytic solution, an aqueous solution of glue supplied from the glue dissolution tank 13 by the pump p2, and an additive solution supplied from the additive tank 12 by the pump p1.
- the additive solution is composed of hydrochloric acid containing thiourea.
- the electrolytic cell 17 is provided with rough copper serving as an anode and a copper base plate serving as a cathode for refining electrolytic copper used as a product by electrodepositing copper on the electrodeposition surface with a predetermined interval. It has been. Further, the electrolytic solution is supplied to the electrolytic cell 17 from the electrolytic solution supply unit 11 by the pump p5.
- various types of base plates can be used as the cathode according to the application. For example, when electrolysis is performed by the permanent cathode method (PC method), a SUS plate or the like may be used.
- an aqueous solution of thiourea having a predetermined concentration is prepared in the thiourea dissolution tank 14.
- a hydrochloric acid tank 15 is prepared with a predetermined concentration of hydrochloric acid.
- an aqueous solution of thiourea and hydrochloric acid are supplied to the additive tank 12 using the pumps p3 and p4 and mixed with stirring.
- hydrochloric acid containing thiourea in the additive tank 12 is supplied to the electrolyte solution supply unit 11 using the pump p1.
- the supply of hydrochloric acid containing thiourea from the additive tank 12 to the electrolyte solution supply unit 11 may be performed in a batch manner. That is, in the additive tank 12, an aqueous solution of thiourea and hydrochloric acid, for example, one day mixed and stored at a time may be supplied to the electrolytic solution supply unit 11.
- the glue supply unit 16 measures and cuts out the stored glue and continuously supplies it to the glue dissolving tank 13. Hot water from a hot water supply unit (not shown) is also continuously supplied to the glue dissolution tank 13. The supplied glue is stirred together with warm water in the glue dissolution tank 13 and dissolved in about 10 minutes, and an aqueous solution of glue is generated. Continuously, an aqueous glue solution is supplied to the electrolyte solution supply unit 11 using the pump p2. At this time, the glue is measured by the glue supply unit 16 at the same time as the glue is supplied, the glue is dissolved in the glue dissolution tank 13, and the glue aqueous solution is supplied from the glue dissolution tank 13 to the electrolyte supply part 11. You may carry out continuously.
- the hydrochloric acid containing thiourea supplied from the additive tank 12 and the aqueous solution of glue continuously supplied from the glue dissolving tank 13 are stirred and mixed together with the electrolyte in the electrolyte supply section 11. Subsequently, an electrolytic solution containing thiourea, hydrochloric acid and glue is supplied from the electrolytic solution supply unit 11 to the electrolytic cell 17 by the pump p5, and copper is subjected to electrolytic purification in the electrolytic cell 17 using this electrolytic solution.
- an aqueous solution of glue prepared by continuously dissolving glue supplied continuously from the glue supply unit 16 in the glue dissolving tank 13 is continuously supplied to the electrolyte supply unit 11.
- the glue is not decomposed by the acid, and the glue can be used efficiently.
- it is not necessary to supply sulfuric acid for preventing the corrosion of glue to the additive tank 12. Therefore, the manufacturing cost is good.
- the continuously supplied glue is continuously dissolved and continuously supplied to the electrolyte supply unit 11
- the time during which the glue is dissolved in the water before being supplied to the electrolyte supply unit 11 is short. Therefore, corrosion of glue can be suppressed and good quality electrolytic copper can be provided.
- the amount of glue used when preparing the aqueous solution of glue is continuously measured simultaneously with the continuous supply and dissolution of glue, the production efficiency is improved.
- Example 2 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 ⁇ thickness 10 mm 53 mother boards were provided with an interval of 100 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.
- an aqueous solution of thiourea and hydrochloric acid were supplied to the additive tank and mixed with stirring.
- the liquid temperature in the additive tank was kept at 20-30 ° C.
- 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.
- 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.
- the generated aqueous glue solution was continuously supplied to the electrolyte supply unit.
- the liquid temperature in the glue dissolution tank was maintained at 35 to 45 ° C.
- 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.
- 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.
- 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 ⁇ thickness 10 mm 53 mother boards were provided with an interval of 100 mm.
- 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.
- 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. The liquid temperature in the additive tank was kept at 20-30 ° C.
- 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.
- 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.
- Electrolytic purification apparatus 11 Electrolyte supply part 12 Additive tank 13 Glue dissolution tank 14 Thiourea dissolution tank 15 Hydrochloric acid tank 16 Glue supply part 17 Electrolysis tank p1-p5 Pump
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Abstract
Description
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
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
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
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
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. The liquid temperature in the additive tank was kept at 20-30 ° C. 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. The liquid temperature in the glue dissolution tank was maintained at 35 to 45 ° C.
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. The liquid temperature in the additive tank was kept at 20-30 ° C. 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.
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)
- 銅の電解槽と、
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. - 前記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た請求項1に記載の銅の電解精製装置。 The copper electrolytic refining apparatus according to claim 1, further comprising a glue supply unit for continuously supplying glue to the glue dissolving tank.
- 前記膠を除く添加剤は、チオ尿素及び塩酸を含む請求項1又は2に記載の銅の電解精製装置。 3. The copper electrolytic purification apparatus according to claim 1 or 2, wherein the additive excluding the glue contains thiourea and hydrochloric acid.
- 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、
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: - 膠の水溶液を作製する際に用いる膠の計量を、前記膠の連続供給及び連続溶解と同時に連続して行う請求項4に記載の銅の電解精製方法。 The method for electrolytic purification of copper according to claim 4, wherein the amount of glue used in preparing the aqueous solution of glue is continuously measured simultaneously with the continuous supply and continuous dissolution of the glue.
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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 |
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 |
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 |
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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 |
JP2005307343A (en) * | 2004-03-23 | 2005-11-04 | Mitsubishi Materials Corp | High-purity electrolytic copper and its production method |
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