CN114540824B - Method for regenerating titanium anode plate by using waste acid solution - Google Patents
Method for regenerating titanium anode plate by using waste acid solution Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 108
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 57
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 230000001680 brushing effect Effects 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000000149 penetrating effect Effects 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 39
- 238000000576 coating method Methods 0.000 abstract description 39
- 238000011010 flushing procedure Methods 0.000 abstract description 8
- 238000002161 passivation Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 229910052741 iridium Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The application discloses a method for regenerating a titanium anode plate by using a waste acid solution. Firstly, putting the titanium anode plate into a waste acid solution for cleaning, then, firstly, flushing the titanium anode plate with clear water, coating the surface of the titanium anode plate with a hydrazine hydrate solution, repeatedly coating and cleaning until the surface of the anode plate is uniformly grey-white, and then, flushing the anode plate with clear water to obtain the treated titanium anode plate. The method is mild, simple and efficient, and can effectively utilize the waste acid for experiments or industry. Not only can rapidly remove the invalid coating, but also can remove TiO 2 The passivation layer is reduced, so that the polar plate substrate is not damaged. The method is suitable for titanium electrodes with various shapes and is suitable for wide popularization.
Description
Technical Field
The application belongs to the technical field of chemistry, and particularly relates to a method for regenerating a titanium anode plate by using a waste acid solution.
Background
The titanium anode (DSA) is a novel insoluble anode with valve-type metallic titanium as a matrix and noble metal element oxide coated on the surface. Compared with the traditional graphite electrode and lead-based alloy electrode, the anode has the advantages of stable size, low electricity consumption, long service life, high efficiency, no pollution and the like, and is widely applied to industries of chemical industry, environmental protection, electrometallurgy, electroplating, organic synthesis, cathodic protection and the like. The titanium anode has higher manufacturing cost, wherein the cost of the titanium substrate is about 40 percent, the cost of the surface coating is about 30-40 percent, more of the coating developed in recent years is replaced by alkali metal, the cost of the coating is continuously reduced, and if the titanium substrate can be repeatedly coated for multiple times, the service performance is not affected, and the preparation cost of the titanium anode can be greatly reduced.
The method for removing the coating comprises molten salt method, sulfuric acid electrolysis method, acid boiling method and mechanical method. The molten salt method is a method for immersing the spent titanium anode in mixed molten salt of alkaline substances and oxidizing substances to remove the old coating. Its advantages are short treating time, high consumption of raw materials, and high dissolving speed and cost of fused salt. The sulfuric acid electrolysis method is to place the disabled titanium anode in sulfuric acid medium to make electrolysis alternately as anode and cathode. Its advantages are less corrosion of Ti base and less consumption of sulfuric acid, and high consumption of electric energy. The acid digestion method is a method for treating the invalid anode at about 100 ℃ in 25% -30% hydrochloric acid or 60% sulfuric acid or other mixed acid medium. The method is simple and easy to implement, but the consumption of acid medium is large, the corrosion of titanium base is large, and the acid mist is serious. The mechanical method is a method for removing the coating by adopting a sand blasting method, and the method is simple to operate, has little titanium-based corrosion and has lower treatment capacity.
The prior art discloses a process for pre-oxidation treatment of titanium anodes, wherein the main substance adopted is a solution containing hydrofluoric acid (or fluoride ions). Hydrofluoric acid is a high-toxicity substance and is extremely volatile in the air; the fluorine ion and the complex of the titanium ion have strong stability and can be closely adsorbed on the surfaces of titanium and titanium alloy to isolate the titanium and titanium alloy matrix from air, so that passivation films cannot be generated on the surfaces of the titanium and titanium alloy matrix, and the passivation films are also the reason why most of the anodic oxidation, electroplating and other surface treatments of the titanium and titanium alloy are corroded by the solution containing hydrofluoric acid as a pretreatment means. Chinese patent application No. CN200710119681.3 discloses a substrate pretreatment process suitable for anodic oxidation of titanium and titanium alloy, which is electrochemical polishing treatment performed in a fluorine-free treatment solution, but the method is only suitable for the case that the surface of the titanium anode has no platinum group metal salt plating layer, and the scheme cannot be applied when the surface of the titanium anode has the platinum group metal salt plating layer.
Disclosure of Invention
In order to overcome the defects of the prior art, the application provides a recovery processing method of a titanium anode plate, which uses waste electrolyte to remove noble metal or active metal oxide on the surface of the titanium anode plate, has simple process flow, can effectively remove a failure coating and a passivation layer, and can coat the coating without re-etching the obtained regenerated titanium anode plate.
The application aims to provide a method for regenerating a titanium anode plate by using a waste acid solution.
The application aims at realizing the following steps of pretreatment and brushing cleaning, which concretely comprises the following steps:
A. pretreatment: putting the titanium anode plate into a waste acid solution, and performing ultrasonic vibration to obtain a treated titanium anode plate;
B. and (3) brushing and cleaning: and (3) washing the treated titanium anode plate with clear water, then brushing a hydrazine hydrate solution on the surface of the treated titanium anode plate, repeatedly brushing and cleaning until the surface of the anode plate is uniformly gray, and cleaning with clear water to obtain the regenerated titanium anode plate.
The specific operation method is as follows:
(1) Putting the titanium anode plate into a waste acid solution, and performing ultrasonic vibration;
(2) And (3) washing the titanium anode plate treated in the step (1) with clear water, then brushing a hydrazine hydrate solution on the surface of the titanium anode plate, repeatedly brushing and washing until the surface of the anode plate is uniformly gray and white, and washing the anode plate with clear water to obtain the treated titanium anode plate.
The waste acid solution is a mixed solution of zinc sulfate and sulfuric acid, and contains other electrolytic impurity components, and the concentration of the sulfuric acid is 140-200g/L.
The waste acid solution is oxalic acid solution for etching, and the concentration of oxalic acid is 8-12%.
The waste acid solution also contains an acid-resistant penetrating agent.
The acid-resistant penetrating agent is preferably fatty alcohol polyoxyethylene ether.
The concentration of the fatty alcohol polyoxyethylene ether in the mixed solution is 10-15%.
The temperature of the mixed solution is controlled to be 30-50 ℃, and the mixed solution containing the waste electrolyte can react without too high temperature.
The mixed solution containing oxalic acid is in a micro-boiling state.
The frequency of the ultrasonic vibration is 1000-1200Hz, and the time is 8-20min.
And (3) cleaning the titanium anode plate treated in the step (1) for 2-3 times by using a high-pressure water gun.
The concentration of the hydrazine hydrate solution is 8-15%. The hydrazine hydrate solution is an alkaline solution with strong reducibility, and can effectively reduce residual metal oxide and TiO attached to the surface of the titanium anode plate 2 And a passivation layer.
The application has the beneficial effects that:
the method is mild, simple and efficient, and can effectively utilize the waste acid for experiments or industry. Not only can rapidly remove the invalid coating, but also can remove TiO 2 The passivation layer is reduced, so that the polar plate substrate is not damaged. The method is suitable for titanium electrodes with various shapes and is suitable for wide popularization.
Drawings
FIG. 1 is a graph of enhanced life test of the regenerated, new and spent titanium anodes of example 3;
FIG. 2 is a graph of oxygen evolution polarization of the regenerated, fresh, and spent titanium anodes of example 3.
Detailed Description
The application is further described below with reference to examples and figures, but is not limited in any way, and any alterations or substitutions based on the teachings of the application are within the scope of the application.
The concentrations in the present application are mass percent concentrations unless specifically stated.
The method for regenerating the titanium anode plate by using the waste acid solution comprises the steps of pretreatment and brushing and cleaning, and specifically comprises the following steps:
A. pretreatment: putting the titanium anode plate into a waste acid solution, and performing ultrasonic vibration to obtain a treated titanium anode plate;
B. and (3) brushing and cleaning: and (3) washing the treated titanium anode plate with clear water, then brushing a hydrazine hydrate solution on the surface of the treated titanium anode plate, repeatedly brushing and cleaning until the surface of the anode plate is uniformly gray, and cleaning with clear water to obtain the regenerated titanium anode plate.
The waste acid solution is waste electrolyte for electrolytic zinc, the waste electrolyte for electrolytic zinc is a mixed solution of zinc sulfate and sulfuric acid, and the concentration of sulfuric acid is 140-200g/L.
The waste acid solution is oxalic acid solution for etching, and the concentration of oxalic acid is 8-12%.
The waste acid solution also contains an acid-resistant penetrating agent.
The acid-resistant penetrating agent is fatty alcohol polyoxyethylene ether.
The concentration of the acid-resistant penetrating agent in the waste acid solution is 10-15%.
When the waste acid solution is waste electrolyte for electrolytic zinc, the temperature of ultrasonic vibration is 30-50 ℃, the frequency of ultrasonic vibration is 1000-1200Hz, and the time of ultrasonic vibration is 8-20min.
When the waste acid solution is oxalic acid solution for etching, the temperature of ultrasonic oscillation is 80-95 ℃, the frequency of ultrasonic oscillation is 1000-1200Hz, and the time of ultrasonic oscillation is 8-20min.
The concentration of the hydrazine hydrate solution is 8-15%.
And B, cleaning with clear water for 2-3 times by adopting high-pressure clear water. The application is further illustrated by the following examples:
example 1
The coating of the titanium anode plate related to the embodiment is noble metal and alkali metal containing Ir, ru and Sn metal oxides. The specific recovery treatment method comprises the following steps:
(1) Putting the titanium anode plate into a mixed solution of waste electrolyte for electrolytic zinc and fatty alcohol polyoxyethylene ether, and carrying out ultrasonic vibration; the concentration of sulfuric acid in the mixed solution is 140g/L, the concentration of fatty polyoxyethylene ether is 12%, the reaction temperature is 45 ℃, the ultrasonic vibration frequency is 1000Hz, and the time is 10min;
(2) And (3) cleaning the titanium anode plate treated in the step (1) for 3 times by using a high-pressure water gun, brushing a layer of hydrazine hydrate solution with the concentration of 10% on the surface of the titanium anode plate, staying for 3 minutes, brushing off the coating by using a brush, flushing the coating by using clear water, finding that the local failure coating is not cleaned, brushing a layer of hydrazine hydrate solution with the concentration of 10% on the failure coating, staying for 3 minutes, brushing off the coating by using the brush, flushing the coating by using clear water, and obtaining the regenerated anode plate with the uniform gray-white surface color, thereby obtaining the treated titanium anode plate. Placing in alcohol solution for use.
Comparative example 1: the coating layer of the titanium anode plate according to this example is a noble metal and an alkali metal containing metal oxides of Ir, ru and Sn (same as example 1). The specific recovery treatment method was the same as in step (1) of example 1.
Example 2: the coating of the titanium anode plate related to the embodiment is noble metal and alkali metal containing Ir, ru and Co metal oxides. The specific recovery treatment method comprises the following steps:
(1) Putting the titanium anode plate into a mixed solution of oxalic acid solution for etching and fatty alcohol polyoxyethylene ether, and carrying out ultrasonic vibration; the concentration of oxalic acid in the mixed solution is 12%, the concentration of fatty polyoxyethylene ether is 10%, the temperature is in a micro-boiling state, the frequency of ultrasonic vibration is 1000Hz, and the time is 20min;
(2) And (3) washing the titanium anode plate treated in the step (1) with clear water, then coating hydrazine hydrate solution with the concentration of 8% on the surface of the titanium anode plate, repeatedly coating and washing until the surface of the anode plate is uniformly gray, and washing with clear water to obtain the treated titanium anode plate.
Comparative example 2: the coating of the titanium anode plate in this example is noble metal and alkali metal containing Ir, ru and Co metal oxides (same as in example 2). The specific recovery treatment method comprises the following steps: the specific recovery treatment method was the same as in step (1) of example 2.
Example 3: the coating of the titanium anode plate related to the embodiment is noble metal and alkali metal containing Ir, ru and Mn metal oxides. The specific recovery treatment method comprises the following steps:
(1) Putting the titanium anode plate into a mixed solution of waste electrolyte for electrolytic zinc and fatty alcohol polyoxyethylene ether, and carrying out ultrasonic vibration; the concentration of sulfuric acid in the mixed solution is 180g/L, the concentration of fatty polyoxyethylene ether is 13%, the reaction temperature is 40 ℃, the ultrasonic vibration frequency is 1200Hz, and the time is 20min;
(2) And (3) cleaning the titanium anode plate treated in the step (1) for 3 times by using a high-pressure water gun, brushing a layer of hydrazine hydrate solution with the concentration of 12% on the surface of the titanium anode plate, staying for 3 minutes, brushing off the coating by using a brush, flushing the coating by using clear water, finding that the local failure coating is not cleaned, brushing a layer of hydrazine hydrate solution with the concentration of 13% on the failure coating, staying for 3 minutes, brushing off the coating by using the brush, flushing the coating by using the clear water, and obtaining the regenerated anode plate with the uniform gray-white surface color, thereby obtaining the treated titanium anode plate. Placing in alcohol solution for use.
Comparative example 3: the coating of the titanium anode plate according to this example is a noble metal and an alkali metal containing metal oxides of Ir, ru and Mn (same as example 3). The specific recovery treatment method comprises the following steps: soaking the titanium anode plate in 10% oxalic acid solution at 100 ℃ for 1 hour, taking out, washing, drying, cooling and then repainting and repairing to obtain the regenerated titanium anode.
Example 4: the coating of the titanium anode plate according to this example is a noble metal and an alkali metal containing Ir, ru, mn, co metal oxide. The specific recovery treatment method comprises the following steps:
(1) Putting the titanium anode plate into a mixed solution of waste electrolyte for electrolytic zinc and fatty alcohol polyoxyethylene ether, and carrying out ultrasonic vibration; the concentration of sulfuric acid in the mixed solution is 200g/L, the concentration of fatty polyoxyethylene ether is 15%, the reaction temperature is 48 ℃, the ultrasonic vibration frequency is 1200Hz, and the time is 20min;
(2) And (3) cleaning the titanium anode plate treated in the step (1) for 3 times by using a high-pressure water gun, brushing a layer of hydrazine hydrate solution with 15% on the surface of the titanium anode plate, staying for 3 minutes, brushing off the coating by using a brush, flushing the coating by using clear water, finding that the local failure coating is not cleaned, brushing a layer of hydrazine hydrate solution with 15% on the failure coating, staying for 3 minutes, brushing off the coating by using the brush, flushing the coating by using clear water, and obtaining the regenerated anode plate with uniform gray-white surface color, thereby obtaining the treated titanium anode plate. Placing in alcohol solution for use.
The regenerated titanium anodes prepared in examples 1-4 and comparative examples 1-3 were subjected to a reinforcement life test on corresponding freshly prepared titanium anodes by: the coated anode was subjected to an electrode enhanced accelerated life test in a 1mol/L sulfuric acid solution at a current density of 1A/cm2, and the electrode was considered to be failed when the terminal voltage was increased to 10V. The total power-on time is the strengthening life time, and the result is shown in table 1, wherein the strengthening life test chart of the regenerated titanium anode prepared in example 2 and the corresponding new titanium anode and the failure titanium anode is shown in fig. 1:
table 1 results of enhanced life test of examples and comparative examples
As can be seen from table 1: the regenerated titanium anode prepared by the method is basically consistent with the corresponding regenerated titanium anode in strengthening service life, which shows that the regenerated titanium anode prepared by the method has good stability, while the regenerated titanium anode prepared by the comparative example has different degree of reduction in strengthening service life, which shows that the regenerated titanium anode prepared by the comparative example has weaker stability and poor coating binding force.
Table 2 cell voltage results for examples and comparative examples
As can be seen from table 2: the oxygen evolution potential and the chlorine evolution potential of the regenerated titanium anode prepared by the method are basically consistent with those of the corresponding newly prepared titanium anode, which shows that the regenerated titanium anode prepared by the method has good electrocatalytic activity. As can be seen from fig. 2, the regenerated titanium anode of example 3 has substantially the same oxygen evolution potential as the corresponding zinc-titanium anode.
The regenerated titanium anodes prepared in examples 1 to 4 and comparative examples 1 to 3 and the corresponding spent titanium anodes were weighed and measured for thickness, the results of which are shown in table 3 below:
TABLE 3 weight and thickness variation of spent and regenerated titanium anodes for the examples and comparative examples
Titanium anode size: 30mm×10mm×3mm
As can be seen from table 3: the weight and thickness of the regenerated titanium anode obtained before and after the repair of the failure titanium anode are basically unchanged, which indicates that the repair method of the application does not damage the titanium anode matrix.
Claims (5)
1. The method for regenerating the titanium anode plate by using the waste acid solution is characterized by comprising the steps of pretreatment and brushing and cleaning, and specifically comprises the following steps:
A. pretreatment: putting the titanium anode plate into a waste acid solution, wherein the waste acid solution is waste electrolyte for electrolytic zinc or oxalic acid solution for etching, the waste electrolyte for electrolytic zinc is a mixed solution of zinc sulfate and sulfuric acid, the sulfuric acid concentration is 140-200g/L, and the oxalic acid concentration of the oxalic acid solution for etching is 8-12%; the waste acid solution also comprises an acid-resistant penetrating agent fatty alcohol polyoxyethylene ether, wherein the concentration of the acid-resistant penetrating agent in the waste acid solution is 10-15%; ultrasonic vibration to obtain a treated titanium anode plate;
B. and (3) brushing and cleaning: and (3) washing the treated titanium anode plate with clear water, then brushing a hydrazine hydrate solution on the surface of the treated titanium anode plate, repeatedly brushing and cleaning until the surface of the anode plate is uniformly gray, and cleaning with clear water to obtain the regenerated titanium anode plate.
2. The method for regenerating a titanium anode plate by using a waste acid solution according to claim 1, wherein when the waste acid solution is a waste electrolyte for electrolytic zinc, the temperature of ultrasonic vibration is 30-50 ℃, the frequency of ultrasonic vibration is 1000-1200Hz, and the time of ultrasonic vibration is 8-20min.
3. The method for regenerating a titanium anode plate by using a waste acid solution according to claim 1, wherein when the waste acid solution is an oxalic acid solution for etching, the temperature of ultrasonic vibration is 80-95 ℃, the frequency of ultrasonic vibration is 1000-1200Hz, and the time of ultrasonic vibration is 8-20min.
4. The method for regenerating a titanium anode plate by using a waste acid solution according to claim 1, wherein the concentration of the hydrazine hydrate solution is 8-15%.
5. The method for regenerating a titanium anode plate by using a waste acid solution according to claim 1, wherein the clean water cleaning in the step B is performed for 2-3 times by using high-pressure clean water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210218315.8A CN114540824B (en) | 2022-03-08 | 2022-03-08 | Method for regenerating titanium anode plate by using waste acid solution |
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| WO2000022662A1 (en) * | 1998-10-12 | 2000-04-20 | Ekc Technology, Ltd | Inhibition of titanium corrosion |
| CN108193213A (en) * | 2018-01-04 | 2018-06-22 | 沈阳欧施盾新材料科技有限公司 | It is a kind of using anodic oxidation waste sulfate suitable for the electrochemical deoiling liquid of aluminium alloy and its application |
| CN111349961A (en) * | 2020-04-29 | 2020-06-30 | 宝鸡市昌立特种金属有限公司 | Method for cleaning waste titanium anode plate for foil forming machine and removing and recycling precious metal |
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| WO2000022662A1 (en) * | 1998-10-12 | 2000-04-20 | Ekc Technology, Ltd | Inhibition of titanium corrosion |
| CN108193213A (en) * | 2018-01-04 | 2018-06-22 | 沈阳欧施盾新材料科技有限公司 | It is a kind of using anodic oxidation waste sulfate suitable for the electrochemical deoiling liquid of aluminium alloy and its application |
| CN111349961A (en) * | 2020-04-29 | 2020-06-30 | 宝鸡市昌立特种金属有限公司 | Method for cleaning waste titanium anode plate for foil forming machine and removing and recycling precious metal |
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