CN104120460B - A kind of method removing electrolytic copper foil Ni-Ti anode surface scale - Google Patents
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale Download PDFInfo
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- CN104120460B CN104120460B CN201410314900.3A CN201410314900A CN104120460B CN 104120460 B CN104120460 B CN 104120460B CN 201410314900 A CN201410314900 A CN 201410314900A CN 104120460 B CN104120460 B CN 104120460B
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Abstract
The invention discloses a kind of method removing electrolytic copper foil Ni-Ti anode surface scale, comprise the following steps: 1) will be covered with the Ni-Ti anode of fouling and be placed in sodium chloride and fully soak in the mixed solution of calcium chloride, so that fouling becomes loose, then brush off this loose fouling；2) Ni-Ti anode processed through upper step is placed in reductant solution fully soaks, then scrub clean with brush；3) Ni-Ti anode processed through upper step is placed in the mixed solution of chelating agent and penetrating agent and fully soaks, then scrub clean with brush.The method low energy consumption of the present invention, low cost, simple to operate, mild condition, can effectively remove the fouling on electrolytic copper foil Ni-Ti anode surface, and the noble coatings of anode surface will not be destroyed.Can effectively extend anode electrolytic copper foil produce in service life.
Description
Technical field
The present invention relates to a kind of method removing electrolytic copper foil Ni-Ti anode surface scale.
Background technology
In electrolytic copper foil produces, due to the very big (6000A/m of anodic current density2～10000 A/m2), reaction condition is harsher, generally uses noble metallic oxide anode (predominantly analysis oxygen type titanio IrO2+Ta2O5System coated anode) as anode.In electrolytic process, the Pb of trace in electrolyte2+Constantly it is oxidized to Pb at anode surface4+, and with PbO2Form separates out, and is attached to anode surface；During power failure, the PbO of anode surface2It is reduced to again PbSO4Precipitation is attached to anode surface, causes anode surface gradually by PbO2、PbSO4Covering and adhere to, forming one layer of fine and close layer of scale, causing groove pressure to raise, power consumption increases.And layer of scale makes anode potential skewness, electrolysis production copper thickness out is uneven, and conforming product rate reduces.On the other hand, bad by fouling overlay area conduction, cause uncovered region the density of electric fluxline relatively to increase, anode potential strengthens, and accelerates the passivation of anode.Therefore in the middle of Copper Foil production technology, need to regularly remove anode, remove the fouling of anode surface so that production is stablized, effectively carried out.
In prior art, the method removing anode fouling conventional has: machinery removal method, acid cooking method, alkaline-heating method etc., machinery removal method, i.e. uses sharp-pointed, sharp instrument fouling directly to be stripped down from positive plate.Machinery removal method is simple to operate, but the time of consuming is long, and fouling is removed and the most totally and easily scraped anode substrate, destroys noble coatings.On the other hand, due to anode in manufacturing process through sandblasting roughening treatment, fouling is easy to stick to its surface, plus being electrolysed operation for a long time, fouling combines with anode surface noble coatings the most firmly, also part noble coatings matrix be can be peeled off while peeling off fouling with mechanical external force, waste and the destruction of coating caused.Acid cooking method (concentrated sulphuric acid, concentrated hydrochloric acid, concentrated nitric acid etc.) and alkaline-heating method at high temperature process positive plate, are dissolved to surface scale remove.This method severe operational environment, seriously and fouling removal efficiency is low for acid, alkali waste, and strong acid, highly basic also can corrode Titanium base and noble coatings simultaneously, does a lot of damage anode and waste.
Summary of the invention
It is an object of the invention to provide a kind of method removing electrolytic copper foil Ni-Ti anode surface scale.
The technical solution used in the present invention is:
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale, comprises the following steps:
1) will be covered with the Ni-Ti anode of fouling to be placed in sodium chloride and fully soak in the mixed solution of calcium chloride, so that fouling becomes loose, then brush off this loose fouling；
2) Ni-Ti anode processed through upper step is placed in reductant solution fully soaks, then scrub clean with brush；
3) Ni-Ti anode processed through upper step is placed in the mixed solution of chelating agent and penetrating agent and fully soaks, then scrub clean with brush.
In step 1), described sodium chloride is with the mixed solution of calcium chloride, and the mass concentration of sodium chloride is 20%～30%, and the mass concentration of calcium chloride is 4%～8%；The temperature of mixed solution is 30 DEG C～90 DEG C.
In step 1), the time fully soaked is 1～3h.
Step 2) in, the mass concentration of described reductant solution is 5%～20%；The temperature of reductant solution is 30 DEG C～90 DEG C；The time fully soaked is 1-3h.
Step 2) in, described reducing agent is Na2SO3And Na2At least one in S.
In step 3), in described chelating agent and the mixed solution of penetrating agent, the mass concentration of chelating agent is 5%～20%, and the mass concentration of penetrating agent is 0.1%～1.0%；The temperature of described mixed solution is 30 DEG C～90 DEG C；The time fully soaked is 1-3h.
In step 3), described chelating agent is at least one in Triammonium citrate, sodium citrate, sodium potassium tartrate tetrahydrate, sodium gluconate, glycerol, glycolic acid, EDETATE SODIUM, triethanolamine, tetrahydroxypropyl ethylenediamine.
In step 3), described penetrating agent is surfactant.
In step 3), described surfactant is nonionic surfactant.
In step 3), described nonionic surfactant is at least one in the polyoxyethylene ether of alkyl phenol, fatty alcohol-polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether FMEE, span, tween, Polyethylene Glycol.
The invention has the beneficial effects as follows: the method low energy consumption of the present invention, low cost, simple to operate, mild condition, can effectively remove the fouling on electrolytic copper foil Ni-Ti anode surface, and the noble coatings of anode surface will not be destroyed.Can effectively extend anode electrolytic copper foil produce in service life.
Accompanying drawing explanation
Fig. 1 is that original anode is soaking three forward and backward analysis oxygen polarization curves of step solution respectively, for comparing the cleanout fluid impact on coating electro-chemical activity.
Fig. 2 be electrolytic copper foil production process produces the positive plate of layer of scale before cleaning after under different electric current densities the relation curve of tank voltage change, for compare positive plate before cleaning after electric conductivity.
Detailed description of the invention
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale, comprises the following steps:
1) will be covered with the Ni-Ti anode of fouling to be placed in sodium chloride and fully soak in the mixed solution of calcium chloride, so that fouling becomes loose, then brush off this loose fouling；
2) Ni-Ti anode processed through upper step is placed in reductant solution fully soaks, then scrub clean with brush；
3) Ni-Ti anode processed through upper step is placed in the mixed solution of chelating agent and penetrating agent and fully soaks, then scrub clean with brush.
In step 1), described sodium chloride is with the mixed solution of calcium chloride, and the mass concentration of sodium chloride is 20%～30%, and the mass concentration of calcium chloride is 4%～8%；The temperature of mixed solution is 30 DEG C～90 DEG C.
In step 1), the time fully soaked is 1～3h；
Step 2) in, the time fully soaked is 1～3h；
In step 3), the time fully soaked is 1～3h；Step 2) in, the mass concentration of described reductant solution is 5%～20%；The temperature of reductant solution is 30 DEG C～90 DEG C.
Step 2) in, described reducing agent is Na2SO3And Na2At least one in S.
In step 3), in described chelating agent and the mixed solution of penetrating agent, the mass concentration of chelating agent is 5%～20%, and the mass concentration of penetrating agent is 0.1%～1.0%；The temperature of described mixed solution is 30 DEG C～90 DEG C.
In step 3), described chelating agent is at least one in Triammonium citrate, sodium citrate, sodium potassium tartrate tetrahydrate, sodium gluconate, glycerol, glycolic acid, EDETATE SODIUM, triethanolamine, tetrahydroxypropyl ethylenediamine；Preferably, described chelating agent is at least one in Triammonium citrate, sodium citrate.
In step 3), described penetrating agent is surfactant；Preferably, described penetrating agent is nonionic surfactant；It is further preferred that described penetrating agent is at least one in the polyoxyethylene ether of alkyl phenol, fatty alcohol-polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether FMEE, span, tween, Polyethylene Glycol；Further preferred, described penetrating agent is fatty alcohol-polyoxyethylene ether.
Below in conjunction with specific embodiment, the present invention is described further:
Embodiment
1
:
Will be covered with the titanium anode plate of fouling be placed in sodium chloride that mass fraction is 25% and 5% calcium chloride mixed solution in, after soaking 2.0h at temperature is 80 DEG C, taking-up hairbrush or plastic brushes are scrubbed can not removing to fouling.Positive plate is placed in the Na that mass concentration is 10% the most again2SO3In solution, after soaking 1h at 60 DEG C, taking-up hairbrush or plastic brushes scrub clean.Finally being placed in by positive plate in the mixed solution of fatty alcohol-polyoxyethylene ether that the Triammonium citrate that mass concentration is 10% with mass concentration is 0.5%, after soaking 1h at 70 DEG C, taking-up hairbrush or plastic brushes scrub clean, and now fouling is substantially completely removed totally.
Embodiment
2
:
Will be covered with the titanium anode plate of fouling be placed in sodium chloride that mass fraction is 28% and 4% calcium chloride mixed solution in, after soaking 2.5h at temperature is 70 DEG C, taking-up hairbrush or plastic brushes are scrubbed can not removing to fouling.Positive plate is placed in the Na of 10% the most again2In S solution, after soaking 1h at 70 DEG C, taking-up hairbrush or plastic brushes scrub clean.Finally being placed in by positive plate in the mixed solution of the sodium citrate of 8% and the fatty alcohol-polyoxyethylene ether of 0.8%, after soaking 1h at 80 DEG C, taking-up hairbrush or plastic brushes scrub clean, and now fouling is substantially completely removed totally.
Embodiment
3
:
Will be covered with the titanium anode plate of fouling be placed in sodium chloride that mass fraction is 24% and 6% calcium chloride mixed solution in, after soaking 1.5h at temperature is 90 DEG C, taking-up hairbrush or plastic brushes are scrubbed can not removing to fouling.Positive plate is placed in the Na of 8% the most again2SO3With Na2In the composition solution of S, after soaking 1.5h at 50 DEG C, taking-up hairbrush or plastic brushes scrub clean.Finally being placed in by positive plate in the mixed solution of the sodium citrate of 12% and the fatty alcohol-polyoxyethylene ether of 0.3%, after soaking 1.5h at 60 DEG C, taking-up hairbrush or plastic brushes scrub clean, and now fouling is substantially completely removed totally.
Fig. 1 is that original anode is soaking three forward and backward analysis oxygen polarization curves of step solution respectively, for comparing the cleanout fluid impact on coating electro-chemical activity.Fig. 2 be electrolytic copper foil production process produces the positive plate of layer of scale before cleaning after under different electric current densities the relation curve of tank voltage change, for compare positive plate before cleaning after electric conductivity.
Before Fig. 1 shows coated anode oxygen evolution potential after three step cleanout fluid soak and immersion the most unchanged, illustrate that anode electro catalytic activity is uninfluenced, coating is not affected by any destruction.
Fig. 2 shows, produces the positive plate of fouling, and its electric conductivity increases after cleaning.
Claims (10)
1. the method removing electrolytic copper foil Ni-Ti anode surface scale, it is characterised in that: comprise the following steps:
1) will be covered with the Ni-Ti anode of fouling to be placed in sodium chloride and fully soak in the mixed solution of calcium chloride, so that fouling becomes loose, then brush off this loose fouling；
2) Ni-Ti anode processed through upper step is placed in reductant solution fully soaks, then scrub clean with brush；
3) Ni-Ti anode processed through upper step is placed in the mixed solution of chelating agent and penetrating agent and fully soaks, then scrub clean with brush.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterized in that: in step 1), described sodium chloride is with the mixed solution of calcium chloride, and the mass concentration of sodium chloride is 20%～30%, and the mass concentration of calcium chloride is 4%～8%；The temperature of mixed solution is 30 DEG C～90 DEG C.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterised in that: in step 1), the time fully soaked is 1～3h.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterised in that: step 2) in, the mass concentration of described reductant solution is 5%～20%；The temperature of reductant solution is 30 DEG C～90 DEG C；The time fully soaked is 1-3h.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterised in that: step 2) in, described reducing agent is Na2SO3And Na2At least one in S.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterized in that: in step 3), in described chelating agent and the mixed solution of penetrating agent, the mass concentration of chelating agent is 5%～20%, and the mass concentration of penetrating agent is 0.1%～1.0%；The temperature of described mixed solution is 30 DEG C～90 DEG C；The time fully soaked is 1-3h.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterized in that: in step 3), described chelating agent is at least one in Triammonium citrate, sodium citrate, sodium potassium tartrate tetrahydrate, sodium gluconate, glycerol, glycolic acid, EDETATE SODIUM, triethanolamine, tetrahydroxypropyl ethylenediamine.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 1, it is characterised in that: in step 3), described penetrating agent is surfactant.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 8, it is characterised in that: in step 3), described surfactant is nonionic surfactant.
A kind of method removing electrolytic copper foil Ni-Ti anode surface scale the most according to claim 9, it is characterized in that: in step 3), described nonionic surfactant is at least one in the polyoxyethylene ether of alkyl phenol, fatty alcohol-polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether FMEE, span, tween, Polyethylene Glycol.
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| CN104775036B (en) * | 2015-05-12 | 2017-07-18 | 昆明贵益金属材料有限公司 | The method that noble metal is reclaimed from the waste and old Ni―Ti anode with noble coatings |
| CN106835163B (en) * | 2016-12-29 | 2018-11-23 | 铜陵有色金属集团股份有限公司 | Cleaning process for Ni―Ti anode surface noble metal plated film |
| CN108425122B (en) * | 2018-03-23 | 2020-01-21 | 江西铜业集团有限公司 | Method for removing scale on surface of titanium-based oxide coating anode for electrolytic copper foil |
| CN109112605B (en) * | 2018-08-28 | 2020-04-14 | 常州大学 | Regeneration treatment liquid and regeneration method of titanium-based iridium-tantalum oxide coating anode for electrolytic copper foil |
| CN109023399B (en) * | 2018-08-28 | 2020-08-14 | 常州大学 | Regeneration treatment liquid of titanium anode for electrolytic copper foil, preparation method thereof and regeneration method of titanium anode |
| CN111349961B (en) * | 2020-04-29 | 2021-05-07 | 宝鸡钛普锐斯钛阳极科技有限公司 | Method for cleaning waste titanium anode plate for foil forming machine and removing and recycling precious metal |
| CN111910189B (en) * | 2020-07-14 | 2021-12-17 | 广东省科学院稀有金属研究所 | Method for removing dirt on surface of noble metal oxide electrode |
| CN112011799A (en) * | 2020-08-18 | 2020-12-01 | 九江德福科技股份有限公司 | Additive for cleaning titanium anode plate of electrolytic cell and cleaning method |
| CN115305161B (en) * | 2022-07-22 | 2023-06-20 | 福建紫金铜箔科技有限公司 | Electrolytic copper foil anode plate cleaning agent and preparation method thereof |
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