CN113755900A - Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis - Google Patents

Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis Download PDF

Info

Publication number
CN113755900A
CN113755900A CN202110934618.5A CN202110934618A CN113755900A CN 113755900 A CN113755900 A CN 113755900A CN 202110934618 A CN202110934618 A CN 202110934618A CN 113755900 A CN113755900 A CN 113755900A
Authority
CN
China
Prior art keywords
anode
lead
manganese
membrane
old
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110934618.5A
Other languages
Chinese (zh)
Other versions
CN113755900B (en
Inventor
段宁
徐夫元
降林华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tongji University
Original Assignee
Tongji University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tongji University filed Critical Tongji University
Priority to CN202110934618.5A priority Critical patent/CN113755900B/en
Publication of CN113755900A publication Critical patent/CN113755900A/en
Application granted granted Critical
Publication of CN113755900B publication Critical patent/CN113755900B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • 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
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • 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
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention provides a method for regulating and controlling remanufactured membrane by an old lead-based anode for electrolyzing zinc and manganese, which mainly comprises the following steps: s1, pretreating, and scraping anode mud; s2, performing electroreduction treatment to realize film structure and phase pre-regulation; s3, performing electrooxidation treatment to realize new bond reconstruction, structure reconstruction and phase transformation; s4, hoisting the remanufactured membrane anode out of the tank for use; the method makes full use of the original manganese-containing lead-containing inner membrane component on the surface of the old anode, carries out membrane phase reconstruction through electro-reduction-oxidation, and promotes the lead substrateForms firmer and more stable combination with the film layer, and has dense, continuous, uniform and stable epitaxial growth and contains gamma-MnO2The new film layer improves the lead sealing and mud reducing effects of the old anode, prolongs the service life of the old anode and realizes pollution reduction and efficiency improvement.

Description

Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis
Technical Field
The application relates to the field of hydrometallurgy, in particular to a method for regulating and controlling remanufactured films of old lead-based anodes for electrolyzing zinc and manganese.
Background
In the hydrometallurgical industries of electrolytic zinc, electrolytic manganese and the like, a lead plate with the lead content of more than 99% is generally adopted as an anode, anode lead is continuously corroded and dissolved out in electrolyte under the electrolysis condition of high temperature and high acid, high-concentration lead-containing wastewater is generated, manganese ions in the electrolyte are subjected to catalytic oxidation on the surface of the anode, manganese dioxide is generated and mixed with part of lead released by the anode, a large amount of anode mud dangerous waste is formed, and serious resource loss, environmental pollution and health damage are caused.
Through prefabricating one deck protection rete to lead-based anode surface, can follow the source and realize blocking of anode lead corrosion, reduce the useless production of anode slime danger simultaneously from the source, reach accuse lead and subtract the synergistic effect of mud, realize resource saving, source decrement and risk prevention and control. However, in the process of long-term electrolytic production and use of the anode plate after membrane preparation or the anode plate without membrane preparation treatment, anode mud with locally crust on the surface or gradually adhered to the surface is loosened, lead corrosion cannot be effectively blocked structurally, the activity of mud reduction cannot be well exerted in crystal form, the good lead sealing and mud reduction effect is difficult to maintain for a long time, membrane preparation treatment on an old lead-based anode is urgently needed to be carried out again at regular intervals, the long-term activity of the lead sealing and mud reduction is improved and maintained, and the service life of the anode plate is prolonged.
Patent CN 110129835A has disclosed a lead-based alloy anode lead corrosion membrane sealing method, through carrying out prefabricated membrane processing to the lead-based alloy board, restrain the corrosion loss of positive pole components such as lead in the electrolysis use from the source, but the preliminary treatment to anode slime is brush board processing or scraper blade processing, simple preliminary treatment only, hardly guarantee to locate the positive pole slime clean up on lead-based alloy anode surface, and in the in-process of long-term electrolysis production use, the combining ability of lead base and sedimentary deposit reduces, carry out membrane processing on the basis of original sedimentary deposit, can directly influence rete and basement cohesion, easily cause the rete skinning, the phenomenon that drops takes place, this can seriously influence the life of lead-based alloy anode.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a method for regulating and controlling the remanufacturing of a film by an old lead-based anode for electrolytic zinc and manganese, the method fully utilizes the original manganese-containing lead-containing inner film component on the surface of the old anode, carries out film phase reconstruction through electro-reduction-oxidation, promotes the formation of firmer and more stable combination between a lead substrate and a film layer, epitaxially grows a new film layer which is compact, continuous, uniform and stable and contains gamma-MnO 2, promotes the lead sealing and mud reducing effects of the old anode, prolongs the service life of the old anode, and realizes pollution reduction and efficiency improvement.
The technical scheme of the invention is as follows: a method for regulating and controlling remanufactured membrane by an old lead-based anode for electrolyzing zinc and manganese comprises the following steps:
s1, preprocessing: lifting the old lead-based anode plate out of the electrolytic bath, uniformly scraping a loose and damaged anode mud layer on the surface of the old anode, uniformly washing the surface of the anode by adopting spray water with a pressing needle, and removing the adhesive such as floating mud, dust and the like on the surface of the anode;
s2, electro-reduction treatment: taking the old lead-based anode obtained in the step S1 as a cathode, putting the old lead-based anode in a first membrane-making solution of a membrane-making tank, and electrifying for electroreduction treatment to obtain a lead-based anode plate with an intermediate layer and a protective layer which are low-oxidation-state oxides;
s3, electro-oxidation treatment: adjusting the lead-based anode plate obtained in the step S2 into an anode, enabling the cathode to be a high-purity graphite plate, placing the high-purity graphite plate into a second membrane-making solution of a membrane-making tank, electrifying and carrying out electro-oxidation treatment to obtain a re-membrane-made lead-based anode plate with a PbO2 intermediate layer and a gamma-MnO 2 protective layer, wherein the thickness of the gamma-MnO 2 protective layer is 10-50 μm;
s4, electrolytic production: the re-filmed lead-based anode plate obtained in the step S3 is lifted out of the film making tank and transferred into an electrolytic tank for electrolytic production, so that lead sealing and mud reduction are realized; and repeating the steps S1-S3 for the old lead-based anode which needs to be made into a film again after being used in the electrolytic cell for 20-60 days.
In the step S1, the anode mud layer is scraped to the surface of the manganese-containing inner membrane layer, and the thickness of the surface of the manganese-containing inner membrane layer is 20-50 um.
In the step S2, the first membrane-forming solution is a sulfuric acid solution with a concentration of 30-90 g/L.
In the step S2, the distance between the cathode and the anode is 90-120mm, the cathode current density is 20-60A/m2, the temperature is 25-45 ℃, and the electrolysis is carried out for 60-90 min.
In the step S2, the intermediate layer PbO2 is reduced to lead low-oxidation-state oxide, which is one or two of PbO and Pb3O 4.
The protective layer MnO2 is reduced into a low-oxidation-state oxide of manganese, and the low-oxidation-state oxide of manganese is one or more of manganese monoxide (MnO), manganese sesquioxide (Mn203) and manganous manganic oxide Mn3O 4.
In the step S3, the second membrane-forming solution comprises MnSO4 with the concentration of 50-150g/L and H2SO4 with the concentration of 10-50 g/L.
The parameters of the electrooxidation treatment in step S3 of the present invention are: the distance between the cathode and the anode is 90-120mm, the current density of the anode is 30-50A/m2, the temperature is 80-98 ℃, and the electrolysis is carried out for 20-30 min.
The concentration of impurity ions contained in the membrane preparation tank solution filled in the membrane preparation tank is not more than 10mg/L, otherwise, the membrane preparation solution is subjected to impurity removal treatment, or fresh membrane preparation solution is replaced again.
The impurity ions of the invention comprise one or more of iron, cobalt, nickel and copper.
The invention has the following beneficial effects:
(1) before the intermediate layer and the protective layer are oxidized and deposited, the old lead-based anode is pretreated, and the intermediate layer and the protective layer are directly deposited on the failed electrode again mainly in consideration of the fact that the combination of the residual deposited layer and the lead substrate is damaged, so that the service life of the anode plate can be greatly shortened, and the purposes of sealing lead and reducing mud can not be realized; meanwhile, the film layer on the surface of the old anode plate is directly and completely scraped, so that the lead substrate is easily damaged by people, and the lead loss and pollution are increased.
(2) The method adopts electroreduction treatment, can fully utilize the original manganese-containing lead-containing inner membrane components on the surface of the old anode, reduces MnO2 and PbO2 on the old lead-based cathode plate into low-valent manganese oxide and low-valent lead oxide, and oxidizes the low-valent lead oxide formed in the electroreduction stage on the surface of the old lead-based anode plate into PbO2 after the cathode and the anode are adjusted, so that the formed nascent PbO2 can be used as a bridge beam for strongly connecting the lead substrate and the active MnO2 components, and the binding force is obviously increased compared with that between the metal lead substrate and MnO2, so that the treatment mode of reduction and reoxidation improves the stability of the anode, effectively prolongs the service time of a reproduced membrane plate, and reduces the frequency of slotting.
(3) According to the invention, MnO2 on the old lead-based cathode plate is reduced to low-valence manganese oxide at a low temperature, and then oxidation treatment is carried out, so that the low-valence manganese oxide and Mn2+ in the membrane making liquid can be preferentially subjected to oxidation reaction to generate MnO2, and the generation of Mn2+ oxidized to MnO 4-can be effectively avoided, thereby improving the current use efficiency; meanwhile, because the low-valence manganese oxide on the surface of the old lead-based anode plate is easier to generate an oxidation reaction than Mn2+, the oxidation time can be effectively shortened, so that the low-valence manganese oxide and Mn2+ can quickly generate a compact MnO2 film layer on the surface of PbO2, and the obtained MnO2 film layer has strong bonding force, good conductivity and higher mud reduction activity.
(4) The old anode plate of the invention can carry out film layer structure and phase pre-regulation and control through electro-reduction-electro-oxidation, realizes equal reconstruction of film phase structure and matter, leads the exposed partial porous area in the film layer to be filled and filled by newly deposited gamma-MnO 2, leads the interface of the film layer and the lead substrate to be oxidized again due to lead and manganese, and epitaxially grows a dense, continuous, uniform and stable new film layer containing gamma-MnO 2, generates new coupling bonds of Pb-O-Mn, Pb-O-Pb, Mn-O-Mn and the like, and promotes firmer and more stable combination of the lead substrate and the film layer.
(5) Compared with the prior art that the surface film layer is directly scraped off and then the anode oxidation film making method is adopted, the remanufactured film anode prepared by the method is prolonged to more than 20 days from 10 days in the electrolytic use process, the instability damage phenomena such as bubbling and peeling begin to appear on the surface of the anode, and the surface of the remanufactured film anode plate is more stable, the corrosion amount of anode lead and the reduction rate of the hazardous waste production amount of anode mud are both improved by more than 15%, the lead sealing and mud reducing effects of the prior anode can be remarkably improved, and the service life of the remanufactured film anode is prolonged.
(6) The invention eliminates the adverse effect on the cathode zinc electrodeposition efficiency and the bath pressure by weakening lead and the suspended anode mud, improves the yield and the purity of zinc, reduces the bath pressure, and realizes pollution reduction and efficiency improvement.
Drawings
FIG. 1 is a schematic view of an initial old lead-based anode prior to treatment in a remanufacturing process provided by the present invention;
FIG. 2 is a schematic view of a lead-based anode after a stripping rinse process in a remanufactured membrane process provided by the present invention;
FIG. 3 is a schematic diagram of a lead-based anode treated by a conventional method for remanufacturing a membrane according to the present invention after a cathodic electroreduction regulation treatment;
FIG. 4 is a schematic diagram of an old lead-based anode treated by the remanufacturing method according to the invention after anode electrooxidation regulation.
FIG. 5 is a microscopic electron micrograph of the surface film layer of the re-filmed anode of example 3 of the present invention.
FIG. 6 is a cyclic voltammogram of the reproduced membrane anode of example 3 of the present invention.
Detailed Description
The present invention is described in detail below with reference to the attached drawings and embodiments, and it is obvious that the described embodiments are only a part of embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
The method for regulating and remanufacturing the film by the old lead-based anode for electrolyzing the zinc and the manganese is explained in detail by combining specific preferred embodiments.
Example 1
The method for remanufacturing the film by regulating and controlling the old lead-based anode for electrolyzing zinc and manganese, provided by the embodiment, comprises the following steps of:
s1, preprocessing: the old lead-based anode plate which is used in the electrolytic tank and needs to be subjected to surface film preparation again after 20-60 days of service as shown in figure 1 is lifted out of the electrolytic tank, a loose damaged anode mud layer on the surface of the old anode is uniformly removed, a manganese-containing film layer with the thickness of 20-50um away from the surface of an anode lead substrate is ensured not to be scraped, and the lead substrate is prevented from being damaged; adopting a pressurized needle to spray and wash the anode plate surface uniformly, removing the adhesive substances such as floating mud, dust and the like on the plate surface, and obtaining the treated old lead-based anode as shown in figure 2;
s2, electro-reduction treatment: taking the old lead-based anode obtained from S1 as a cathode, wherein the anode is an alloy material containing more than 95% of lead, placing the old lead-based anode in a sulfuric acid solution with the concentration of 90g/L, setting the distance between the cathode and the anode to be 90mm, the current density of the cathode to be 20A/m2, electrolyzing at 25 ℃ for 90min, and reducing MnO2 and PbO2 in the surface film layer and the interface surface of the surface film layer and the lead-based substrate into low-oxidation-state Mn3O4 and PbO, wherein the treated old lead-based anode is shown in figure 3;
the concentration of impurity ions contained in membrane preparation tank liquid filled in the membrane preparation tank is not more than 10mg/L, otherwise, the membrane preparation liquid is subjected to impurity removal treatment, or fresh membrane preparation liquid is replaced again; the impurity ions include one or more of iron, cobalt, nickel and copper.
S3, electro-oxidation treatment: switching the old anode plate after the electro-reduction treatment as shown in figure 3 into an anode cathode which is a high-purity graphite plate, placing the old anode plate into MnSO4 with the concentration of 50g/L and H2SO4 with the concentration of 10g/L, and electrifying and electrolyzing for 30min at 80 ℃ under the electrolysis condition that the current density of the anode is 30A/m 2; electrifying for electro-oxidation treatment to obtain a re-filmed lead-based anode plate with a PbO2 intermediate layer and a gamma-MnO 2 protective layer, wherein the thickness of the gamma-MnO 2 protective layer is 30 μm, and the electro-oxidized old lead-based anode is shown in FIG. 4;
s4, electrolytic production: the re-filmed lead-based anode plate obtained in the step S3 is lifted out of the film making tank and transferred into an electrolytic tank for electrolytic production, so that lead sealing and mud reduction are realized; and repeating the steps S1-S3 for the old lead-based anode which needs to be made into a film again after being used in the electrolytic cell for 20-60 days.
Example 2
The method for remanufacturing the film by regulating and controlling the old lead-based anode for electrolyzing zinc and manganese, provided by the embodiment, comprises the following steps of:
s1, preprocessing: the old lead-based anode plate which is used in the electrolytic tank and needs to be subjected to surface film preparation again after 20-60 days of service as shown in figure 1 is lifted out of the electrolytic tank, a loose damaged anode mud layer on the surface of the old anode is uniformly removed, a manganese-containing film layer with the thickness of 20-50um away from the surface of an anode lead substrate is ensured not to be scraped, and the lead substrate is prevented from being damaged; adopting a pressurized needle to spray and wash the anode plate surface uniformly, removing the adhesive substances such as floating mud, dust and the like on the plate surface, and obtaining the treated old lead-based anode as shown in figure 2;
s2, electro-reduction treatment: taking the old lead-based anode obtained from S1 as a cathode, wherein the anode is made of an alloy material containing more than 95% of lead, placing the old lead-based anode in a sulfuric acid solution with the concentration of 30g/L, setting the distance between the cathode and the anode to be 120mm, setting the current density of the cathode to be 60A/m2, electrolyzing at 45 ℃ for 60min, reducing the surface film layer MnO2 and PbO2 in the interface of the old lead-based anode and the lead-based substrate into low-oxidation-state Mn2O3 and PbO, and obtaining the treated old lead-based anode as shown in FIG. 3;
the concentration of impurity ions contained in membrane preparation tank liquid filled in the membrane preparation tank is not more than 10mg/L, otherwise, the membrane preparation liquid is subjected to impurity removal treatment, or fresh membrane preparation liquid is replaced again; the impurity ions include one or more of iron, cobalt, nickel and copper.
S3, electro-oxidation treatment: switching the old anode plate after the electro-reduction treatment as shown in figure 3 into an anode cathode which is a high-purity graphite plate, placing the old anode plate into MnSO4 with the concentration of 150g/L and H2SO4 with the concentration of 50g/L, and electrifying and electrolyzing for 20min at 98 ℃ under the electrolysis condition that the anode current density is 50A/m 2; electrifying for electro-oxidation treatment to obtain a re-filmed lead-based anode plate with a PbO2 intermediate layer and a gamma-MnO 2 protective layer, wherein the thickness of the gamma-MnO 2 protective layer is 10 μm, and the electro-oxidized old lead-based anode is shown in FIG. 4;
s4, electrolytic production: the re-filmed lead-based anode plate obtained in the step S3 is lifted out of the film making tank and transferred into an electrolytic tank for electrolytic production, so that lead sealing and mud reduction are realized; and repeating the steps S1-S3 for the old lead-based anode which needs to be made into a film again after being used in the electrolytic cell for 20-60 days.
Example 3
The method for remanufacturing the film by regulating and controlling the old lead-based anode for electrolyzing zinc and manganese, provided by the embodiment, comprises the following steps of:
s1, preprocessing: the old lead-based anode plate which is used in the electrolytic tank and needs to be subjected to surface film preparation again after 20-60 days of service as shown in figure 1 is lifted out of the electrolytic tank, a loose damaged anode mud layer on the surface of the old anode is uniformly removed, a manganese-containing film layer with the thickness of 20-50um away from the surface of an anode lead substrate is ensured not to be scraped, and the lead substrate is prevented from being damaged; adopting a pressurized needle to spray and wash the anode plate surface uniformly, removing the adhesive substances such as floating mud, dust and the like on the plate surface, and obtaining the treated old lead-based anode as shown in figure 2;
s2, electro-reduction treatment: taking the old lead-based anode obtained from S1 as a cathode, wherein the anode is made of an alloy material containing more than 95% of lead, placing the old lead-based anode in a sulfuric acid solution with the concentration of 60g/L, setting the distance between the cathode and the anode to be 100mm, the current density of the cathode to be 35A/m2, electrolyzing at 30 ℃ for 70min, reducing the surface film layer MnO2 and PbO2 in the interface with the lead-based substrate to be low-oxidation-state Mn2O3 and Pb2O3, and obtaining the treated old lead-based anode as shown in FIG. 3;
the concentration of impurity ions contained in membrane preparation tank liquid filled in the membrane preparation tank is not more than 10mg/L, otherwise, the membrane preparation liquid is subjected to impurity removal treatment, or fresh membrane preparation liquid is replaced again; the impurity ions include one or more of iron, cobalt, nickel and copper.
S3, electro-oxidation treatment: switching the old anode plate after the electro-reduction treatment as shown in figure 3 into an anode cathode which is a high-purity graphite plate, placing the old anode plate into MnSO4 with the concentration of 100g/L and H2SO4 with the concentration of 40g/L, and electrifying and electrolyzing for 25min at 93 ℃ under the electrolysis condition that the anode current density is 40A/m 2; electrifying for electro-oxidation treatment to obtain a re-filmed lead-based anode plate with a PbO2 intermediate layer and a gamma-MnO 2 protective layer, wherein the thickness of the gamma-MnO 2 protective layer is 50 μm, and the electro-oxidized old lead-based anode is shown in FIG. 4;
s4, electrolytic production: the re-filmed lead-based anode plate obtained in the step S3 is lifted out of the film making tank and transferred into an electrolytic tank for electrolytic production, so that lead sealing and mud reduction are realized; and repeating the steps S1-S3 for the old lead-based anode which needs to be made into a film again after being used in the electrolytic cell for 20-60 days.
As shown in fig. 5, the anode surface film layer prepared by the method is compact and continuous, can effectively prevent the corrosion of the electrolyte to the lead substrate, and as shown in fig. 6, after the film is manufactured, lead is sealed in the film, and the lead dissolution peak disappears.
The technical principle of the present invention is described above in conjunction with specific embodiments, which are only a part of embodiments of the present invention, not all embodiments. The description is specific and detailed to explain the present application and is not intended to limit the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A method for regulating and controlling remanufacturing of a film by an old lead-based anode for electrolyzing zinc and manganese is characterized by comprising the following steps:
s1, preprocessing: lifting the old lead-based anode plate out of the electrolytic bath, uniformly scraping a loose and damaged anode mud layer on the surface of the old anode, uniformly washing the surface of the anode by adopting spray water with a pressing needle, and removing the adhesive such as floating mud, dust and the like on the surface of the anode;
s2, electro-reduction treatment: taking the old lead-based anode obtained in the step S1 as a cathode, putting the old lead-based anode in a first membrane-making solution of a membrane-making tank, and electrifying for electroreduction treatment to obtain a lead-based anode plate with an intermediate layer and a protective layer which are low-oxidation-state oxides;
s3, electro-oxidation treatment: adjusting the lead-based anode plate obtained in the step S2 to be an anode, placing the cathode to be a high-purity graphite plate in a second membrane-making solution of a membrane-making tank, electrifying for electro-oxidation treatment to obtain a middle layer of PbO2The protective layer is gamma-MnO2The remanufactured film lead-based anode plate of (1), the gamma-MnO2The thickness of the protective layer is 10-50 μm;
s4, electrolytic production: the re-filmed lead-based anode plate obtained in the step S3 is lifted out of the film making tank and transferred into an electrolytic tank for electrolytic production, so that lead sealing and mud reduction are realized; and repeating the steps S1-S3 for the old lead-based anode which needs to be made into a film again after being used in the electrolytic cell for 20-60 days.
2. The method for regulating and remanufacturing the anode of the old lead-based anode for zinc and manganese electrolysis according to claim 1, wherein the anode slime layer is scraped to the surface of the manganese-containing inner membrane layer in step S1, and the thickness of the surface of the manganese-containing inner membrane layer is 20-50 um.
3. The method for regulating and remanufacturing the electrolytic zinc-manganese used old lead-based anode according to claim 1, wherein the first membrane forming solution in the step S2 is a sulfuric acid solution with a concentration of 30-90 g/L.
4. The method for remanufacturing a film by regulating and controlling an old lead-based anode for electrolyzing zinc and manganese according to claim 1, wherein the distance between the cathode and the anode in the step S2 is 90-120mm, and the current density of the cathode is 20-60A/m2Electrolyzing at 25-45 deg.C for 60-90 min.
5. The method for controlled re-filming of old lead-based anode for zinc-manganese electrolysis as claimed in claim 1, wherein said intermediate layer PbO is used in step S22Is reduced to lead suboxide of PbO and Pb3O4One or two of them.
6. The method for regulating and reproducing the film of the old lead-based anode used for electrolyzing Zn and Mn as claimed in claim 1, wherein the protection layer MnO is2Reduced to manganese suboxide, wherein the manganese suboxide is manganese monoxide (MnO) or manganese sesquioxide (Mn)203) Manganese (III) oxide (Mn)3O4One or more of them.
7. The method for regulating and remanufacturing the film according to claim 1, wherein the second film forming solution in the step S3 comprises MnSO with a concentration of 50-150g/L4And H with a concentration of 10-50g/L2SO4。
8. The method for regulating and remanufacturing the film by the old lead-based anode for electrolyzing the zinc and the manganese according to claim 1, wherein the parameters of the electro-oxidation treatment in the step S3 are as follows: the distance between the cathode and the anode is 90-120mm, and the current density of the anode is 30-50A/m2Electrifying and electrolyzing for 20-30min at the temperature of 80-98 ℃.
9. The method for regulating and controlling the remanufactured membrane of the old lead-based anode for electrolyzing zinc and manganese according to claim 1, wherein the concentration of impurity ions contained in membrane-making tank solution filled in the membrane-making tank is not more than 10mg/L, otherwise, the membrane-making solution is subjected to impurity removal treatment or replaced by fresh membrane-making solution.
10. The electrolytic zinc manganese spent lead-based anode conditioned remanufacturing process of claim 9, wherein the impurity ions comprise one or more of iron, cobalt, nickel and copper.
CN202110934618.5A 2021-08-16 2021-08-16 Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis Active CN113755900B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110934618.5A CN113755900B (en) 2021-08-16 2021-08-16 Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110934618.5A CN113755900B (en) 2021-08-16 2021-08-16 Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis

Publications (2)

Publication Number Publication Date
CN113755900A true CN113755900A (en) 2021-12-07
CN113755900B CN113755900B (en) 2023-02-28

Family

ID=78789366

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110934618.5A Active CN113755900B (en) 2021-08-16 2021-08-16 Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis

Country Status (1)

Country Link
CN (1) CN113755900B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
CN102173449A (en) * 2011-01-14 2011-09-07 同济大学 Method for preparing nanometer lead dioxide electrode
CN110129835A (en) * 2019-06-14 2019-08-16 中国环境科学研究院 A kind of lead based alloy anodes lead corrosion film encapsulation method
CN110241442A (en) * 2019-06-14 2019-09-17 中国环境科学研究院 A kind of high lead anode slurry heavy metal contaminants intelligence source reduction packaged technology

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101335370A (en) * 2008-07-11 2008-12-31 东莞市松山科技集团有限公司 Process implement full cycle regeneration of lead acid battery
CN102173449A (en) * 2011-01-14 2011-09-07 同济大学 Method for preparing nanometer lead dioxide electrode
CN110129835A (en) * 2019-06-14 2019-08-16 中国环境科学研究院 A kind of lead based alloy anodes lead corrosion film encapsulation method
CN110241442A (en) * 2019-06-14 2019-09-17 中国环境科学研究院 A kind of high lead anode slurry heavy metal contaminants intelligence source reduction packaged technology

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
葛鹏: "锌电积中新型铅基阳极的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Also Published As

Publication number Publication date
CN113755900B (en) 2023-02-28

Similar Documents

Publication Publication Date Title
CN107889511B (en) Closed loop system and method for recycling lead acid batteries
US2273798A (en) Electrolytic process
JP6604466B2 (en) Copper manufacturing method and copper manufacturing apparatus
CN109680301B (en) Anode plate for zinc electrolysis and preparation method thereof
CN102367577B (en) Method for preparing Na2[Pb(OH)4] solution and method for recycling lead from lead-containing waste
CN102268699B (en) Method for removing anode slime of porous anode
JP5669995B1 (en) Method and apparatus for processing Au-containing iodine-based etching solution
CA1169020A (en) Aqueous electrowinning of metals using fuel oxidizable at the anode
CN113755900B (en) Method for regulating and controlling remanufacturing of film by using old lead-based anode for zinc and manganese electrolysis
CN106835193A (en) A kind of Pb bases/3D PbO2/MeOx composite anodes and preparation method thereof
CN105132980B (en) A kind of lead silver alloy anode surface recombination ceramic film film build method
CN110129799A (en) Recycling method of tin stripping waste liquid based on sulfuric acid-ferric salt system
CN212770997U (en) Electrolysis device for preparing vanadium battery electrolyte
JPH1018073A (en) Electrolysis with addition of ultrasonic vibration
JPH0578880A (en) Preparation of iron foil through electro- deposition
RU2691967C1 (en) Method of making an electrode from reinforced lead dioxide
EP0033956B1 (en) Stable lead dioxide anode and method for production
CN110642339B (en) Porous Ti/IrO2-Nb2O5-Bi2O3Preparation method and application of electrode
CN113881967B (en) Impurity removal method for lead electrolyte
JP3294678B2 (en) Regeneration method of copper etchant
CN113584533B (en) Preparation method of carbon fiber titanium-based lead dioxide electrode
Expósito et al. Use of a hydrogen‐diffusion electrode in the electrochemical removal of lead from effluents of lead electrowinning processes
CN116676643A (en) Method for improving electrolytic stripping state of zinc
Malinowska et al. INDIUM RECOVERY FROM CBD BATH OF In2 (O, S) 3 THIN FILMS FOR CIS CELLS
CN115595440A (en) Preparation method for efficiently leaching refined lead of electrode from waste lead paste

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant