CN102465313A - Method for pretreating lead base inert anode for electro-deposit copper - Google Patents
Method for pretreating lead base inert anode for electro-deposit copper Download PDFInfo
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- CN102465313A CN102465313A CN2010105479419A CN201010547941A CN102465313A CN 102465313 A CN102465313 A CN 102465313A CN 2010105479419 A CN2010105479419 A CN 2010105479419A CN 201010547941 A CN201010547941 A CN 201010547941A CN 102465313 A CN102465313 A CN 102465313A
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Abstract
The invention relates to a method for pretreating a lead base inert anode for electro-deposit copper. A pretreatment solution comprises cobaltous sulfate, sulfuric acid and distilled water, wherein the temperature of the pretreatment solution is 30-70 DEG C; the anode is to be pretreated, a cathode is a stainless steel plate, space between the anode and the cathode is 3-6cm, the circulating quantity of the pretreatment solution is 0.05-0.5V groove/h, V groove represents the volume of a pretreatment groove; and the pretreatment process is as follows: the current density of the anode is 50-400A/m<2>, and the pretreatment time is 8-24h. By adopting the pretreatment solution containing the cobaltous sulfate, parameters of the pretreatment process are optimized. The pretreatment process is simple, is convenient for operation, is beneficial to industrial application, and can be used for controlling oxygen evolution overpotential of the lead or lead alloy inert anode for the electro-deposit copper to be within 550mV. The lead or lead base anode treated by adopting the method is used as an anode for the electro-deposit copper, and remarkable effects are obtained on the aspects of reducing the content of lead as impurity of the cathode copper and reducing electricity consumption per ton of copper.
Description
Technical field
The present invention relates to a kind of electro deposited copper with lead or the pretreated method of LY inert anode, be used to reduce the overpotential for oxygen evolution of electro deposited copper with lead or LY inert anode.Belonging to electrification metallurgical is that a kind of technology is simple with inert anode supporting technology field, easy to operate, can significantly reduce the inert anode supporting technology of ton copper power consumption.
Background technology
Copper is pillar material important in the national economic development.Over past ten years, China's copper output annual increasing velocity is all more than 10%, and copper material output was 888.4 ten thousand tons in 2009, ranked first in the world.According to the copper characteristics of resources, the copper smelting process generally can be divided into two kinds of pyrogenic process and wet methods.The advantage of copper hydrometallurgy be can with refractory copper oxide ore and low-grade copper mine as raw material, flow process is simple, the process assembled scheme is many, production cost is low and scale is flexible.It is reported, build ore dressing-pyrometallurgical smelting process factory ton copper investment and be about 6.5 ten thousand yuan, be about 1.5 ten thousand yuan and build leaching-extraction-electrodeposition factory ton copper investment.So development copper hydrometallurgical technology obviously is an effective way that reduces the copper production cost.
The electrodeposition technology is occupied considerable status in the copper hydrometallurgy.At present, in copper electrodeposition production process, nearly all factory all adopts the Pb-Ca-Sn anode, but Pb-Ca-Sn anodic shortcoming is that overpotential for oxygen evolution surpasses 700mV, and the power consumption that causes the copper electrodeposition is up to 2000kWh/ ton copper.Because the power consumption of copper electrodeposition is too high, cause the cost of whole wet type copper smelting to increase, be unfavorable for the further popularization and the national energy-saving and emission-reduction implementation of China's copper hydrometallurgical technology.
Bath voltage is the important technology index of electrolytic deposition process, and it is made up of the volts lost that the contact resistance of copper sulfate decomposition voltage and electrolyte solution resistance, wiring, anode sludge resistance, pole plate resistance etc. cause.Wherein, the copper sulfate decomposition voltage is the major portion that constitutes bath voltage, accounts for 75～80% of bath voltage.Therefore, copper electrodeposition power consumption be reduced and the copper sulfate decomposition voltage must be reduced.And the decomposition voltage of copper sulfate is theoretical decomposition voltage and whole over voltage sums.The negative electrode over voltage value of copper electrodeposition is less, is merely 0.02～0.05V.The anode overpotential be oxygen on anode, separate out the institute cause that its value is about 0.75V, account for about 30% of anode total voltage, be the main root of useless power consumption.So will reduce bath voltage, the overpotential of separating out that reduces oxygen is the most important thing.Through calculating, the every reduction of bath voltage 0.1V, the power consumption of separating out 1 ton of cathode copper will reduce by 80～100kWh.
Select suitable anode pretreatment process be reduce oxygen separate out one of effective means of over voltage.Therefore, it is imperative to seek a kind of anode pretreatment process that can significantly reduce the inert anode overpotential for oxygen evolution.Anode preconditioning technique of the present invention promotes that through engineering approaches, industrialization and the mass-producing process of internal copper hydrometallurgical technology are significant, and the energy-conservation production of other metal electrodeposition is had important dissemination for national energy-saving and emission-reduction implementation.
Summary of the invention
The object of the present invention is to provide a kind of pretreatment process that can significantly reduce lead or LY inert anode overpotential for oxygen evolution in the copper electric effusion; Its technology is simple; Easy to operate, can electro deposited copper be reduced in the 550mV by 700mV with the overpotential for oxygen evolution of lead or LY inert anode.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
A kind of electro deposited copper comprises the steps: with the pretreatment process of lead base inert anode
(1) pretreatment fluid: be made up of rose vitriol, sulfuric acid and zero(ppm) water, the pretreatment fluid temperature is 30～70 ℃;
(2) pretreatment tank constitutes: anode is for treating the pre-treatment anode, and negative electrode is a stainless steel plate, and cathode and anode spacing is 3～6cm, and the pretreatment fluid internal circulating load is 0.05～0.5V
Groove/ h (V
GrooveBe meant the volume of pretreatment tank);
(3) pretreatment technology: anodic current density is 50～400A/m
2, pretreatment time is 8～24h.
A kind of optimized technical scheme is characterized in that: in the described pretreatment fluid, and CoSO
4Concentration be 0.1～3g/L, H
2SO
4Concentration be 2～80g/L.
A kind of optimized technical scheme is characterized in that: described negative electrode is the 316L stainless steel plate.
In the above-mentioned technology, anode is for treating pretreated lead or LY electrode, and negative electrode is the 316L stainless steel electrode.After pre-treatment was intact, water flushing anode surface immersed then and carries out the electrodeposition operation in the copper electric effusion.
Lead after handling with the present invention or LY inert anode be as the anode of copper electrolytic deposition process, on ton copper power consumption than having more advantage without pretreated lead or LY inert anode.Co on the anode surface
2+Adsorptive capacity increase, the corresponding quantity that has increased the electrochemical activity point in the unit surface on the electrode, so, the reduction of anode overpotential for oxygen evolution certainty.
By lead or the LY inert anode after the present invention's processing, owing to formed the big PbO of specific surface area at anode surface
2Layer (see figure 2) and a large amount of Co
2+Be adsorbed on PbO
2The surface causes the electrochemical activity number of spots on the anode of unit surface to increase, thereby effectively reduces the anodic overpotential for oxygen evolution.
The present invention adopts the pretreatment fluid that contains rose vitriol; Optimize the pretreatment technology parameter, pretreatment technology of the present invention is very simple, easy to operate; Help industrial applications, can the overpotential for oxygen evolution of electro deposited copper with lead or LY inert anode be controlled in the 550mV.Lead or lead-based anode with after this method processing are used anode as the copper electrodeposition, to reducing cathode copper impurity lead content, reduce a ton copper loss electricity aspect and have a significant effect.
Through accompanying drawing and embodiment the present invention is further specified below, but and do not mean that restriction protection domain of the present invention.
Description of drawings
Fig. 1 is the directly surface topography behind the electrolysis 8h in the copper electric effusion of Pb-Ca-Sn anode.
Fig. 2 is the Pb-Ca-Sn anode after pretreatment process of the present invention is handled, the surface topography in the copper electric effusion behind the electrolysis 8h.
Embodiment
The invention is further illustrated by the following examples, and among all embodiment, the composition of copper electric effusion is all identical with electrodeposition process, and anode is the Pb-0.08wt.%Ca-1wt.%Sn inert anode, and negative electrode is the 316L stainless steel plate, and concrete processing parameter is seen table 1.
The composition of table 1 copper electric effusion and electro deposited copper processing parameter
Comparative Examples
Compare for ease, this Comparative Examples adopts the anode do not do any pretreatment technology to carry out electrodeposition 240h by the said technology of table 1, and as blank embodiment, with the overpotential for oxygen evolution of alloy lead anode in the electrolytic deposition process as considering object.
Electrolysis is after 10 days in the copper electric effusion without the Pb-Ca-Sn anode of any processing, and its overpotential for oxygen evolution is stabilized in 720mV.
Embodiment 1
The pretreatment fluid of present embodiment is formed and the pretreatment technology parameter is seen table 2.
Adopt Pb-Ca-Sn anode after this pretreatment technology is handled as the anode of electro deposited copper, electrolysis is after 10 days in the copper electric effusion, and its overpotential for oxygen evolution is stabilized in 545mV.
The pretreatment fluid of table 2 embodiment 1 is formed and the pretreatment technology parameter
Embodiment 2
The pretreatment fluid of present embodiment is formed and the pretreatment technology parameter is seen table 3.
The pretreatment fluid of table 3 embodiment 2 is formed and the pretreatment technology parameter
Adopt Pb-Ca-Sn anode after this pretreatment technology is handled as the anode of electro deposited copper, electrolysis is after 10 days in the copper electric effusion, and its overpotential for oxygen evolution is stabilized in 530mV.
Embodiment 3
The pretreatment fluid of present embodiment is formed and the pretreatment technology parameter is seen table 4.
The pretreatment fluid of table 4 embodiment 3 is formed and the pretreatment technology parameter
Adopt Pb-Ca-Sn anode after this pretreatment technology is handled as the anode of electro deposited copper, electrolysis is after 10 days in the copper electric effusion, and its overpotential for oxygen evolution is stabilized in 510mV.
Embodiment 4
The pretreatment fluid of present embodiment is formed and the pretreatment technology parameter is seen table 5.
The pretreatment fluid of table 5 embodiment 4 is formed and the pretreatment technology parameter
Adopt Pb-Ca-Sn anode after this pretreatment technology is handled as the anode of electro deposited copper, electrolysis is after 10 days in the copper electric effusion, and its overpotential for oxygen evolution is stabilized in 540mV.
Embodiment 5
The pretreatment fluid of present embodiment is formed and the pretreatment technology parameter is seen table 6.
The pretreatment fluid of table 6 embodiment 5 is formed and the pretreatment technology parameter
Adopt Pb-Ca-Sn anode after this pretreatment technology is handled as the anode of electro deposited copper, electrolysis is after 10 days in the copper electric effusion, and its overpotential for oxygen evolution is stabilized in 550mV.
As shown in Figure 1, be the direct surface topography behind the electrolysis 8h in the copper electric effusion of Pb-Ca-Sn anode.Fig. 2 is the Pb-Ca-Sn anode after the pretreatment process of the embodiment of the invention 3 is handled, the surface topography in the copper electric effusion behind the electrolysis 8h.Can know that by figure after the long electrolysis of process, its surface is vesicular, and grain shape is irregular without pretreated Pb-Ca-Sn anode.And through CoSO
4Anode that solution-treated is crossed is through after the long electrolysis, and its surface microstructure becomes the taper of rule to be evenly distributed on the surface of electrode, and the anode handled of preplating, and its useful area obviously anodic useful area than untreated is big.Because the increase of the effective working area of anode has caused reducing of anode surface actual current density, thereby cause the decline of anode oxygen evolution potential.
Claims (3)
1. an electro deposited copper comprises the steps: with the pretreatment process of lead base inert anode
(1) pretreatment fluid: be made up of rose vitriol, sulfuric acid and zero(ppm) water, the pretreatment fluid temperature is 30～70 ℃;
(2) pretreatment tank constitutes: anode is for treating the pre-treatment anode, and negative electrode is a stainless steel plate, and cathode and anode spacing is 3～6cm, and the pretreatment fluid internal circulating load is 0.05～0.5V
Groove/ h, V
GrooveBe meant the volume of pretreatment tank;
(3) pretreatment technology: anodic current density is 50～400A/m
2, pretreatment time is 8～24h.
2. electro deposited copper according to claim 1 is characterized in that with the pretreatment process of lead base inert anode: in the described pretreatment fluid, and CoSO
4Concentration be 0.1～3g/L, H
2SO
4Concentration be 2～80g/L.
3. electro deposited copper according to claim 1 is characterized in that with the pretreatment process of lead base inert anode: described negative electrode is the 316L stainless steel plate.
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| CN2010105479419A CN102465313A (en) | 2010-11-17 | 2010-11-17 | Method for pretreating lead base inert anode for electro-deposit copper |
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| CN2010105479419A CN102465313A (en) | 2010-11-17 | 2010-11-17 | Method for pretreating lead base inert anode for electro-deposit copper |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512866A (en) * | 1983-10-04 | 1985-04-23 | Langley Robert C | Titanium-lead anode for use in electrolytic processes employing sulfuric acid |
| CN1187696A (en) * | 1996-12-31 | 1998-07-15 | 三星电管株式会社 | Hydrogen-occluding alloy pretreatment method, and its use |
| CN1924102A (en) * | 2006-09-05 | 2007-03-07 | 陕西科技大学 | Preparation method of lead dioxide porous electrode |
| US20070193879A1 (en) * | 2006-02-23 | 2007-08-23 | Prengaman David R | Alloy and anode for use in the electrowinning of metals |
| CN101538724A (en) * | 2009-04-28 | 2009-09-23 | 昆明理工恒达科技有限公司 | Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning |
-
2010
- 2010-11-17 CN CN2010105479419A patent/CN102465313A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512866A (en) * | 1983-10-04 | 1985-04-23 | Langley Robert C | Titanium-lead anode for use in electrolytic processes employing sulfuric acid |
| CN1187696A (en) * | 1996-12-31 | 1998-07-15 | 三星电管株式会社 | Hydrogen-occluding alloy pretreatment method, and its use |
| US20070193879A1 (en) * | 2006-02-23 | 2007-08-23 | Prengaman David R | Alloy and anode for use in the electrowinning of metals |
| CN1924102A (en) * | 2006-09-05 | 2007-03-07 | 陕西科技大学 | Preparation method of lead dioxide porous electrode |
| CN101538724A (en) * | 2009-04-28 | 2009-09-23 | 昆明理工恒达科技有限公司 | Method for preparing energy-saving metal-based ceramic inert anode material for nonferrous metal electrowinning |
Non-Patent Citations (3)
| Title |
|---|
| SANDRO CATTARIN ET AL.: "Electrodeposition of PbO2+CoOx composites by simultaneous oxidation of Pb2+ and Co2+ and their use as anodes for O2 evolution", 《ELECTROCHIMICA ACTA》 * |
| 葛鹏: "锌电积中新型铅基阳极的研究", 《西安建筑科技大学硕士学位论文》 * |
| 陈步明: "电沉积掺杂二氧化铅表面的研究进展", 《中国有色金属学报》 * |
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Owner name: NANDAN SOUTH NONFERROUS METALS CO., LTD. Effective date: 20130910 |
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Effective date of registration: 20130910 Address after: 100088, 2, Xinjie street, Haidian District, Beijing Applicant after: General Research Institute for Nonferrous Metals Applicant after: NANDAN COUNTY NANFANG NON-FERROUS METALS CO., LTD. Address before: 100088, 2, Xinjie street, Haidian District, Beijing Applicant before: General Research Institute for Nonferrous Metals |
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Application publication date: 20120523 |