Titanium-based lead dioxide composite anode plate for hydrometallurgy and preparation method of titanium-based lead dioxide composite anode plate

Abstract

The invention relates to a titanium-based lead dioxide composite anode plate for hydrometallurgy and a preparation method of the titanium-based lead dioxide composite anode plate, and belongs to the technical field of hydrometallurgy. The titanium mesh-based lead dioxide composite gradient plate comprises a Ti-Cu-stainless steel conductive beam, a titanium transition plate and a titanium mesh-based lead dioxide composite gradient plate body, and the titanium mesh-based lead dioxide composite gradient plate body comprises a longitudinal conductive reinforcing rib I, a longitudinal conductive reinforcing rib II, a transverse conductive reinforcing rib I, a transverse conductive reinforcing rib II, an annular conductive reinforcing rib and a titanium-based lead dioxide composite mesh plate. The titanium-based lead dioxide composite screen plate sequentially comprises a titanium mesh substrate, a gamma-MnO2-CaOx composite oxide bottom layer doped with cobalt-coated glass fiber powder / nano Al2O3 particles, a Pb-Co-Zr-SbOx oxide middle layer and a beta-PbO2-WOx composite oxide active layer doped with SrTiO3-SiO2-Ag composite ceramic powder from inside to outside. The conductive support sequentially comprises a titanium substrate, a Pb-Co-Zr-SbOx oxide middle layer and a SrTiO3-SiO2-Ag doped composite ceramic powder beta-PbO2-WOx composite oxide active layer from inside to outside. The lead dioxide plating layer of the anode plate is not prone to falling off, the oxygen evolution potential is low, the service life is long, and the electric efficiency is high.

Description

TECHNICAL FIELD

[0001] The application relates to a titanium-based lead dioxide composite anode plate for hydrometallurgy and a preparation method thereof, and belongs to the technical field of hydrometallurgy. BACKGROUND

[0002] In the process of extracting zinc, copper, nickel, cobalt and manganese by hydrometallurgy, cast lead alloy is widely used as an inert anode for non-ferrous metal electrodeposition due to its low cost and easy availability, and the shortcomings are as follows: high tank voltage (3.4-3.8V), low current efficiency (75-88%), high energy consumption (3400-4200 degrees / ton of zinc) in the electrodeposition process, short service life of the anode (0.5-1 year), easy dissolution of the anode lead into the cathode product, leading to the decline of the quality of the cathode product, and in addition, the oxide film naturally formed in the presence of high fluorine and chlorine ions is loose and easy to peel off, which seriously affects the service life.

[0003] The titanium-based metal oxide electrode belongs to insoluble anode material, and has excellent electrochemical performance and electrocatalytic activity, strong corrosion resistance and long service life. Although the conductivity of titanium is general, it has great strength and strong corrosion resistance, is almost not corroded by most organic acids such as dilute sulfuric acid, dilute hydrochloric acid and chlorine, and has much smaller mass than lead plate.

[0004] At present, the research on noble metal DSA mainly focuses on the research on noble metal oxide coatings such as ruthenium and iridium, among which the best coating of the oxygen evolution anode in the electrolysis industry is the IrO2-Ta2O5 composite oxide coating, which has high oxygen evolution electrocatalytic activity and electrochemical stability in aqueous solution and can work stably under strong acid solution and high current density. However, such electrodes have the defects of high production cost and short service life. The coating is easy to fail under the condition of containing fluorine ions.

[0005] A new type of inert lead dioxide anode with low cost is currently available. The preparation of the electrode generally selects titanium as the base material, and the electrode is prepared by basic processes such as roughening treatment of the surface of the base, plating of a bottom layer, an alpha-PbO2 intermediate layer and electroplating of beta-PbO2. The advantages of the electrode are that (1) it can be operated at a high current density; (2) it can inhibit the generation of mud; (3) it can improve the oxidation efficiency; (4) it has good corrosion resistance and long service life; (5) in zinc electrodeposition, no formation treatment is needed, the amount of lead mixed into zinc is reduced, the corrosion resistance to chlorine is good, chlorine can be removed, manganese residue is not generated, and the current efficiency for extracting zinc is high. However, the PbO2 electrode prepared by electroplating as an insoluble anode has the following problems in use: (1) the PbO2 deposition layer is not tightly combined with the surface of the electrode or the deposition layer is uneven; (2) the PbO2 deposition layer is prone to peeling or corrosion, and the service life is not long; (3) the current efficiency is low, although the electrocatalytic activity of the PbO2 electrode is high, the current efficiency in the application of non-ferrous metal electrodeposition is not very high; (4) lead ions are still generated, which reduces the quality of the cathode product.

[0006] The titanium-based net structure anode plate with horizontal and vertical reinforcing rib fence type has problems of insufficient stability of the anode plate, easy deformation of the whole, uneven current distribution of the composite rod, corrosion of the conductive beam and the like in use. Meanwhile, the titanium net is prone to deformation, the titanium net has large internal stress and uneven distribution of internal stress in use. SUMMARY

[0007] In view of the problems of the titanium-based metal oxide anode in a high-fluorine-chlorine-sulfuric acid solution system, such as easy deformation of the titanium net plate, easy peeling of the plating layer, uneven distribution of power lines of the titanium net anode, large thermal stress and the like, the application provides a titanium-based lead dioxide composite anode plate for hydrometallurgy and a preparation method thereof. Compared with a traditional titanium-based lead dioxide, the anode prepared by the application has a service life extended by 1 times, a cell voltage reduced by more than 15%, a current efficiency improved by more than 2% and a lead dioxide plating layer not easy to peel off in a high-fluorine-chlorine ion sulfuric acid electrolyte system without changing the structure of an electrolytic cell and operating specifications.

[0008] A titanium-based lead dioxide composite anode plate for hydrometallurgy comprises a Ti-Cu-stainless steel conductive beam 1, a titanium transition plate 2 and a titanium net-based lead dioxide composite gradient plate 3. The Ti-Cu-stainless steel conductive beam 1 is fixedly provided with a Cu-stainless steel conductive head 10 at both ends, and a titanium transition plate 2 is welded at the bottom end of the Ti-Cu-stainless steel conductive beam 1; the titanium transition plate 2 is symmetrically provided with a rectangular through hole at the top with respect to the center axis, and a titanium mesh-based lead dioxide composite gradient plate 3 is welded at the bottom end of the titanium transition plate 2; the titanium mesh-based lead dioxide composite gradient plate 3 comprises longitudinal conductive reinforcing ribs I 4, longitudinal conductive reinforcing ribs II 6, transverse conductive reinforcing ribs I 5, transverse conductive reinforcing ribs II 7, annular conductive reinforcing ribs 8, and a titanium-based lead dioxide composite mesh plate 9; the longitudinal conductive reinforcing ribs I 4 are arranged on both sides of the titanium-based lead dioxide composite mesh plate 9, the longitudinal conductive reinforcing ribs II 6 are vertically arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs I 5 are arranged at the bottom end of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs II 7 are horizontally arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the annular conductive reinforcing ribs 8 are arranged on the titanium-based lead dioxide composite mesh plate 9, the intersection of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 is the center of the annular conductive reinforcing ribs 8, and the end points of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 are connected with the annular conductive reinforcing ribs 8; the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 form a conductive support, and the titanium-based lead dioxide composite mesh plate 9 is welded in the area divided by the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 in the conductive support; The titanium-based lead dioxide composite mesh plate 9 comprises, from inside to outside, a titanium mesh base 91, a cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x (x is 1-2) composite oxide bottom layer 92, Pb-Co-Zr-SbO x (x is 1-3) oxide intermediate layer 93, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1-3) composite oxide active layer 94. The conductive support comprises, from inside to outside, a titanium base, a Pb-Co-Zr-SbO x (x is 1-3) oxide intermediate layer, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1-3) composite oxide active layer.

[0009] Preferably, the Ti-Cu-stainless steel conductive beam 1 comprises, from inside to outside, a stainless steel rod core 11, a copper layer 12, and a titanium layer 13; the height of the Ti-Cu-stainless steel conductive beam 1 is 40-80 mm, the thickness is 20-40 mm, the thickness of the copper layer 12 is 2-8 mm, and the thickness of the titanium layer 13 is 1-4 mm. The Cu-stainless steel conductive head 10 is integrally formed with the Ti-Cu-stainless steel conductive beam 1, and the Cu-stainless steel conductive head 10 comprises, from inside to outside, a stainless steel rod core 11 and a copper layer 12, and the thickness of the copper layer 12 is 2-8 mm.

[0010] Preferably, the cobalt-coated glass fiber powder / nano-Al2O3 particle-doped γ-MnO2-CaO x The cobalt-coated glass fiber powder content in the composite oxide bottom layer 92 is 0.1-0.8 wt.%, the nano-Al2O3 particle content is 1-8 wt.%, the Ca content is 0.8-2.0 wt.%, and the rest is γ-MnO2; the cobalt-coated glass fiber powder has a length-diameter of 1-10 μm and a short diameter of 5-30 nm, and the nano-Al2O3 particle has a particle size of 50-100 nm; The Pb-Co-Zr-SbO x The total molar amount of Pb, Co, Zr and Sb in the oxide intermediate layer 93 is 100%, and the molar amount of Pb is 25-60%, the molar amount of Co is 20-40%, the molar amount of Zr is 10-20%, and the molar amount of Sb is 10-15%; The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO

[0011] More preferably, the titanium mesh substrate 91 of the titanium-based lead dioxide composite mesh plate 9 has a long axis of 6-16 mm, a short axis of 3-10 mm, a cross-sectional thickness of 1.0-5.0 mm, and the cobalt-coated glass fiber powder / nano-Al2O3 particle-doped γ-MnO2-CaO x The thickness of the composite oxide bottom layer 92 is 5-10 μm, the Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer 93 is 5-20 μm, the SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The thickness of the composite oxide active layer 94 is 0.4-1.8 mm.

[0012] Preferably, the height of the titanium transition plate 2 is 100-400 mm, the thickness is 3-7 mm, the vertical height of the rectangular through hole is 100-300 mm, and the horizontal width is 50-200 mm.

[0013] Preferably, the titanium base section width of the longitudinal conductive reinforcing rib I 4 and the horizontal conductive reinforcing rib I 5 is 15-50 mm, and the thickness is 5-20 mm. x The thickness of the oxide intermediate layer is 5-20 μm, and the SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x The thickness of the composite oxide active layer is 0.4-1.8 mm. The titanium base section width of the longitudinal conductive reinforcing rib II 6, the horizontal conductive reinforcing rib II 7, and the annular conductive reinforcing rib 8 is 5-20 mm, and the thickness is 5-20 mm. x The thickness of the oxide intermediate layer is 5-20 μm, and the SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x The thickness of the composite oxide active layer is 0.4-1.8 mm.

[0014] The preparation method of the titanium-based lead dioxide composite anode plate for hydrometallurgy is as follows: 1) Titanium mesh base Co-doped glass fiber powder / nano Al2O3 particle γ-MnO2-CaO x Preparation of the composite oxide bottom layer: the titanium mesh base is subjected to sand blasting, leveling, oil removal, and phosphoric acid activation treatment to obtain a pretreated titanium mesh base, and the pretreated titanium mesh base is placed in a manganese nitrate composite plating solution to obtain a titanium mesh base Co-doped glass fiber powder / nano Al2O3 particle γ-MnO2-CaO x The composite oxide bottom layer; the manganese nitrate composite plating solution contains 50-200 g / L of manganese nitrate, 10-80 g / L of calcium nitrate, 10-60 g / L of nitric acid, 2-8 g / L of cobalt-coated glass fiber powder, and 5-20 g / L of nano Al2O3; 2) Titanium mesh base Pb-Co-Zr-SbO x Preparation of the oxide intermediate layer: Pb-Co-Zr-SbO x The precursor solution is uniformly coated on the titanium mesh base Co-doped glass fiber powder / nano Al2O3 particle γ-MnO2-CaO x The composite oxide bottom layer surface is dried at a temperature of 100-120 ℃, and then is placed in a sintering furnace at a temperature of 450-650 ℃ for 5-10 min, and the Pb-Co-Zr-SbO xThe precursor solution and sintering process, finally placed in the temperature of 450~650℃ sintering 1.0~2.0h, obtained the titanium network base Pb-Co-Zr-SbO x Oxide interlayer; 3) Titanium base Pb-Co-Zr-SbO of the conductive support x Oxide interlayer preparation: the titanium base of longitudinal conductive reinforcing rib I, longitudinal conductive reinforcing rib II, transverse conductive reinforcing rib I, transverse conductive reinforcing rib II and annular conductive reinforcing rib is pretreated by annealing, sand blasting, oil removal and oxalic acid treatment in turn, and the Pb-Co-Zr-SbO x The precursor solution is uniformly coated on the surface of the pretreated titanium base, dried at a temperature of 100~120℃, and then placed in the temperature of 450~650℃ sintering 5~10min, repeated 10~20 times to coat Pb-Co-Zr-SbO x The precursor solution and sintering process, finally placed in the temperature of 450~650℃ sintering 1.0~2.0h, obtained the titanium network base Pb-Co-Zr-SbO x Oxide interlayer; 4) Assembled titanium network base Pb-Co-Zr-SbO x Oxide interlayer plate: the Ti layer at both ends of the Ti-Cu-stainless steel conductive beam is milled to obtain a Cu-stainless steel conductive head; titanium network base Pb-Co-Zr-SbO x The oxide interlayer is cut and treated, and then combined with the titanium transition plate and the titanium base Pb-Co-Zr-SbO of the conductive support x The oxide interlayer is cut and treated, and then combined with the titanium transition plate and the titanium base Pb-Co-Zr-SbO of the conductive support x Oxide interlayer plate; 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x Preparation of composite oxide active layer: the titanium network base Pb-Co-Zr-SbO x The oxide interlayer plate is used as an anode, and the stainless steel mesh plate is used as a cathode, and a β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder is formed by electroplating in a lead methanesulfonate plating solution x Composite oxide active layer, obtained titanium base lead dioxide composite anode plate; the lead methanesulfonate plating solution contains 50~350g / L lead methanesulfonate, 10~100g / L methanesulfonic acid, 5~30g / L SrTiO3-SiO2-Ag composite ceramic powder and 10~50g / L sodium tungstate.

[0015] Preferably, the plating temperature of step 1) is 80-100℃, the mechanical stirring speed is 100-600 rpm, the anode current density is 1.0-4.0 A / dm 2 and the plating time is 10-60 min. The Pb-Co-Zr-SbO x The preparation method of the precursor solution: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate and antimony trichloride are dissolved in ethanol-n-butanol mixed solvent in proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1. The oxalic acid mass concentration of step 3) is 8%-12%. The plating temperature of step 5) is 60-100℃, the anode current density is 5-20 A / dm 2 , the plating time is 60-180 min, and the plating solution circulation amount is 5-20 L / min.

[0016] Preferably, the sandblasting of step 1) is to spray silicon carbide sand with a particle size of 40-80 mesh, the oil removal method is to place the titanium mesh substrate in a sodium hydroxide-sodium carbonate mixed solution at a temperature of 60-80℃ for 10-30 min, the sodium hydroxide-sodium carbonate mixed solution contains 5-10 g / L of sodium hydroxide and 10-50 g / L of sodium carbonate; the phosphoric acid activation treatment method is to polarize the oil-removed titanium mesh substrate in a sodium phosphate solution with graphite as the anode; the sodium phosphate solution contains 10-40 g / L of sodium phosphate, 5-20 g / L of sodium hydroxide and 0.01-0.2 g / L of sodium dodecyl sulfate, and the cathode current density of the polarization treatment is 5-10 A / dm 2 , the temperature is 80-100℃, and the time is 20-60 min. The step 1) is a preparation method of the cobalt-coated glass fiber powder: the glass fiber powder is placed in an ammonium fluoride solution, ultrasonic roughening is carried out at a temperature of 20-50 DEG C for 5-10 min, after washing with deionized water, the glass fiber powder is placed in a stannous chloride / hydrochloric acid mixed solution for sensitization for 5-10 min, after washing with deionized water, the glass fiber powder is placed in a silver nitrate solution for ultrasonic activation for 10-30 min, and after washing with deionized water, the activated glass fiber powder is obtained; the activated glass fiber powder is placed in a chemical cobalt plating solution, and chemical cobalt plating is carried out at a temperature of 50-80 DEG C for 30-120 min to obtain the cobalt-coated glass fiber powder; the concentration of the ammonium fluoride solution is 10-50 g / L, the concentration of stannous chloride in the stannous chloride / hydrochloric acid mixed solution is 5-10 g / L, the concentration of hydrochloric acid in the stannous chloride / hydrochloric acid mixed solution is 5-10 ml / L, the concentration of the silver nitrate solution is 3-5 g / L, the chemical cobalt plating solution contains 20-40 g / L of cobalt sulfate, 10-40 g / L of sodium hypophosphite, 5-20 g / L of disodium ethylenediaminetetraacetate, 40-80 g / L of trisodium citrate, and 0.01-0.1 g / L of polyvinylpyrrolidone; The step 5) is a preparation method of the SrTiO3-SiO2-Ag composite ceramic powder: SrTiO3 powder, nano-SiO2 powder and flaky Ag powder are added into an ethanol-water mixed solvent in a proportion, ultrasonic dispersion treatment is carried out for 10-30 min, centrifugal separation is carried out to obtain SrTiO3 / SiO2 / Ag mixed powder, the SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1000-1600 DEG C for 10-20 h, the furnace is cooled to room temperature, grinding is carried out, and the SrTiO3-SiO2-Ag composite ceramic powder is obtained.

[0017] The present application has the following advantages: (1) The titanium-based lead dioxide composite anode plate for hydrometallurgy has a low oxygen evolution potential, a long service life and a high electric efficiency, compared with a traditional titanium-based lead dioxide, under the condition that the electrolytic cell structure and operation specification are not changed and the electrolyte contains a high-fluorine-chlorine ion sulfuric acid electrolyte system, the service life of the anode prepared by the present application is prolonged by 1 times, the cell voltage is reduced by more than 15%, the current efficiency is increased by more than 2%, and the lead dioxide coating is not easy to fall off; (2) The γ-MnO2-CaOx composite oxide bottom layer doped with the cobalt-coated glass fiber powder and nano-Al2O3 particles has the characteristics of strong resistance to chlorine ions and fluorine ions, can inhibit the penetration of ions, prevent the passivation of titanium, avoid the falling off of the subsequent coating and cause uneven current density distribution, and finally cause the short service life of the electrode; (3) The titanium-based electrode produced by sand blasting roughening and phosphate treatment to generate titanium hydride has a long service life, and the fibrous γ-MnO2 with a more compact structure can be obtained by using the composite electrodeposition method in the manganese nitrate plating solution; (4) The thermal decomposition sintered Pb-Co-Zr-SbOx oxide intermediate layer has porosity, and can better connect the γ-MnO2-CaOx composite oxide bottom layer and the SrTiO3-SiO2-Ag doped composite ceramic powder β-PbO2-WOx composite oxide active layer, thereby prolonging the service life of the electrode; (5) The annular conductive reinforcing rib can make the current distribution of the plate more uniform, and can avoid PbO2 coating peeling caused by thermal stress and the bulging of the titanium mesh plate. (6) The titanium mesh based Pb-Co-Zr-SbOx oxide intermediate layer plate is assembled by using the electrical conductivity and catalytic activity of silver, the chlorine corrosion resistance of SiO2 and the catalytic activity of SrTiO3, the current conduction efficiency is high, the titanium based lead dioxide composite anode plate obtained by adopting the methyl sulfonic acid system to composite and deposit the β-PbO2-WOx composite oxide active layer has uniform current distribution and uniform thickness of the deposited coating, and the overall service life of the electrode is improved. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 It is a structure schematic diagram of the titanium based lead dioxide composite anode plate for hydrometallurgy. Figure 2 It is a sectional view schematic diagram of the intersection of the longitudinal conductive reinforcing rib I and the transverse conductive reinforcing rib I. Figure 3 It is a sectional view schematic diagram of the intersection of the longitudinal conductive reinforcing rib I and the transverse conductive reinforcing rib I. Figure 1 It is a sectional view schematic diagram of the intersection of the longitudinal conductive reinforcing rib I and the transverse conductive reinforcing rib I. In the figure, 1 is a Ti-Cu-stainless steel conductive beam, 11 is a stainless steel rod core, 12 is a copper layer, 13 is a titanium layer, 2 is a titanium transition plate, 3 is a titanium aluminum clad transition titanium plate, 4 is a longitudinal conductive reinforcing rib I, 5 is a transverse conductive reinforcing rib I, 6 is a longitudinal conductive reinforcing rib II, 7 is a transverse conductive reinforcing rib II, 8 is an annular conductive reinforcing rib, 9 is a titanium based lead dioxide composite mesh plate, 91 is a titanium mesh substrate, 92 is a γ-MnO2-CaOx composite oxide bottom layer doped with cobalt glass fiber powder / nano Al2O3 particles, 93 is a Pb-Co-Zr-SbOx oxide intermediate layer, 94 is a β-PbO2-WOx composite oxide active layer doped with SrTiO3-SiO2-Ag composite ceramic powder, and 10 is a Cu-stainless steel conductive head. x x x DETAILED DESCRIPTION

[0019] The application will be further described in detail below in combination with specific embodiments, but the protection scope of the application is not limited to the content described. SUMMARY ​​​A titanium-based lead dioxide composite anode plate for hydrometallurgy comprises a Ti-Cu-stainless steel conductive beam 1, a titanium transition plate 2, a titanium mesh-based lead dioxide composite gradient plate 3, The Ti-Cu-stainless steel conductive beam 1 is fixedly provided with Cu-stainless steel conductive heads 10 at both ends, and the bottom end of the Ti-Cu-stainless steel conductive beam 1 is welded with the titanium transition plate 2, the top of which is symmetrically provided with a rectangular through hole with respect to the center axis, and the bottom end of the titanium transition plate 2 is welded with the titanium mesh-based lead dioxide composite gradient plate 3, which comprises longitudinal conductive reinforcing ribs I 4, longitudinal conductive reinforcing ribs II 6, transverse conductive reinforcing ribs I 5, transverse conductive reinforcing ribs II 7, annular conductive reinforcing ribs 8, and a titanium-based lead dioxide composite mesh plate 9, wherein the longitudinal conductive reinforcing ribs I 4 are arranged on both sides of the titanium-based lead dioxide composite mesh plate 9, the longitudinal conductive reinforcing ribs II 6 are vertically arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs I 5 are arranged at the bottom end of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs II 7 are horizontally arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the annular conductive reinforcing ribs 8 are arranged on the titanium-based lead dioxide composite mesh plate 9, the intersection of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 is the center of the annular conductive reinforcing ribs 8, and the end points of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 are connected with the annular conductive reinforcing ribs 8; the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 form a conductive support, and the titanium-based lead dioxide composite mesh plate 9 is welded in the areas divided by the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 in the conductive support; The titanium-based lead dioxide composite mesh plate 9 comprises a titanium mesh substrate 91, a cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x (x is 1-2) composite oxide bottom layer 92, Pb-Co-Zr-SbO x (x is 1-3) oxide intermediate layer 93, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1-3) composite oxide active layer 94. The conductive support comprises a titanium substrate, a Pb-Co-Zr-SbO x (x is 1-3) oxide intermediate layer, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1-3) composite oxide active layer.

[0021] The Ti-Cu-stainless steel conductive beam 1 comprises, from inside to outside, a stainless steel rod core 11, a copper layer 12 and a titanium layer 13; the height of the Ti-Cu-stainless steel conductive beam 1 is 40-80 mm, the thickness is 20-40 mm, the thickness of the copper layer 12 is 2-8 mm, and the thickness of the titanium layer 13 is 1-4 mm. The Cu-stainless steel conductive head 10 is integrally formed with the Ti-Cu-stainless steel conductive beam 1, and the Cu-stainless steel conductive head 10 comprises, from inside to outside, a stainless steel rod core 11 and a copper layer 12; the thickness of the copper layer 12 is 2-8 mm.

[0022] The cobalt-coated glass fiber powder / nano-Al2O3 particle-doped γ-MnO2-CaO x The cobalt-coated glass fiber powder content in the composite oxide bottom layer 92 is 0.1-0.8 wt.%, the nano-Al2O3 particle content is 1-8 wt.%, the Ca content is 0.8-2.0 wt.%, and the balance is γ-MnO2; the length-diameter of the cobalt-coated glass fiber powder is 1-10 μm, the short diameter is 5-30 nm, and the nano-Al2O3 particle size is 50-100 nm; The Pb-Co-Zr-SbO x The total molar amount of Pb, Co, Zr and Sb in the oxide intermediate layer 93 is 100%, and the molar amount of Pb is 25-60%, the molar amount of Co is 20-40%, the molar amount of Zr is 10-20%, and the molar amount of Sb is 10-15%; The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO The SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO

[0023] The titanium-based lead dioxide composite mesh plate 9 has a titanium mesh base 91 with a long axis of 6-16 mm and a short axis of 3-10 mm, a cross-sectional thickness of 1.0-5.0 mm, and a cobalt-coated glass fiber powder / nano-Al2O3 particle-doped γ-MnO2-CaO x The thickness of the composite oxide bottom layer 92 is 5-10 μm, the Pb-Co-Zr-SbO xThe oxide intermediate layer 93 has a thickness of 5-20 μm, and is made of β-PbO2-WO x The composite oxide active layer 94 has a thickness of 0.4-1.8 mm.

[0024] The titanium transition plate 2 has a height of 100-400 mm, a thickness of 3-7 mm, a vertical height of the rectangular through hole of 100-300 mm, and a horizontal width of 50-200 mm.

[0025] The titanium base of the longitudinal conductive reinforcing rib I 4 and the horizontal conductive reinforcing rib I 5 has a cross-sectional width of 15-50 mm and a thickness of 5-20 mm, and is made of Pb-Co-Zr-SbO x The oxide intermediate layer has a thickness of 5-20 μm, and is made of β-PbO2-WO x The composite oxide active layer has a thickness of 0.4-1.8 mm. The titanium base of the longitudinal conductive reinforcing rib II 6, the horizontal conductive reinforcing rib II 7, and the annular conductive reinforcing rib 8 has a cross-sectional width of 5-20 mm and a thickness of 5-20 mm, and is made of Pb-Co-Zr-SbO x The oxide intermediate layer has a thickness of 5-20 μm, and is made of β-PbO2-WO x The composite oxide active layer has a thickness of 0.4-1.8 mm.

[0026] The preparation method of the titanium-based lead dioxide composite anode plate for hydrometallurgy comprises the following specific steps: 1) titanium mesh base cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x Preparation of the composite oxide bottom layer: the titanium mesh base is subjected to sand blasting, leveling, oil removal, and phosphoric acid activation treatment in sequence to obtain a pretreated titanium mesh base, and the pretreated titanium mesh base is placed in a manganese nitrate composite plating solution to obtain the titanium mesh base cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x The composite oxide bottom layer; the manganese nitrate composite plating solution contains 50-200 g / L of manganese nitrate, 10-80 g / L of calcium nitrate, 10-60 g / L of nitric acid, 2-8 g / L of cobalt-coated glass fiber powder, and 5-20 g / L of nano-Al2O3; the plating temperature is 80-100°C, the mechanical stirring speed is 100-600 rpm, the anode current density is 1.0-4.0 A / dm 2 and the plating time is 10-60 min. The sand blasting is a 40-80 mesh size silicon carbide sand, the oil removal method is: placed in a sodium hydroxide-sodium carbonate mixed solution at a temperature of 60-80℃ for 10-30min, the sodium hydroxide-sodium carbonate mixed solution contains 5-10g / L sodium hydroxide, 10-50g / L sodium carbonate; the phosphoric acid activation treatment method is: taking the oil removal treated titanium mesh substrate as a cathode, taking graphite as an anode, and polarizing in a sodium phosphate solution; the sodium phosphate solution contains 10-40g / L sodium phosphate, 5-20g / L sodium hydroxide, 0.01-0.2g / L sodium dodecyl sulfate, the cathode current density of the polarization treatment is 5-10 A / dm 2 , the temperature is 80-100℃, and the time is 20-60min; The preparation method of the cobalt-coated glass fiber powder is: placing the glass fiber powder in an ammonium fluoride solution, ultrasonic roughening for 5-10min at a temperature of 20-50℃, washing with deionized water, then placing in a stannous chloride / hydrochloric acid mixed solution for sensitization for 5-10min, washing with deionized water, then placing in a silver nitrate solution for ultrasonic activation for 10-30min, and washing with deionized water to obtain activated glass fiber powder; placing the activated glass fiber powder in a chemical cobalt plating solution, chemical plating for 30-120min at a temperature of 50-80℃ to obtain the cobalt-coated glass fiber powder; the ammonium fluoride solution has a concentration of 10-50g / L, the stannous chloride / hydrochloric acid mixed solution has a stannous chloride concentration of 5-10g / L and a hydrochloric acid concentration of 5-10ml / L, the silver nitrate solution has a concentration of 3-5g / L, and the chemical cobalt plating solution contains 20-40g / L cobalt sulfate, 10-40g / L sodium hypophosphite, 5-20g / L disodium ethylenediaminetetraacetate, 40-80g / L trisodium citrate, and 0.01-0.1g / L polyvinylpyrrolidone; 2) Pb-Co-Zr-SbO x oxide intermediate layer: placing the Pb-Co-Zr-SbO x precursor solution uniformly on the surface of the titanium mesh substrate doped with the cobalt-coated glass fiber powder / nano-Al2O3 particles, γ-MnO2-CaO x composite oxide bottom layer, drying at a temperature of 100-120℃, then sintering at a temperature of 450-650℃ for 5-10min, repeating the coating of the Pb-Co-Zr-SbO x precursor solution and sintering process, and finally sintering at a temperature of 450-650℃ for 1.0-2.0h to obtain the titanium mesh substrate Pb-Co-Zr-SbO x oxide intermediate layer; the Pb-Co-Zr-SbO x precursor solution: dissolving lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate, and antimony trichloride in an ethanol-n-butanol mixed solvent in proportion under ultrasonic and magnetic stirring to obtain the Pb-Co-Zr-SbOx precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 3) Titanium-based Pb-Co-Zr-SbO of the conductive support x Oxide interlayer preparation: the titanium base bodies of the longitudinal conductive reinforcing rib I, the longitudinal conductive reinforcing rib II, the transverse conductive reinforcing rib I, the transverse conductive reinforcing rib II, and the annular conductive reinforcing rib are sequentially subjected to annealing flattening, sand blasting, oil removal, and oxalic acid (mass concentration of 8% to 12%) treatment to obtain a pretreated titanium base body, and the Pb-Co-Zr-SbO x The precursor solution is uniformly coated on the surface of the pretreated titanium base body, dried at a temperature of 100 to 120°C, and then placed in a sintering furnace at a temperature of 450 to 650°C for 5 to 10 minutes. The Pb-Co-Zr-SbO x The precursor solution and the sintering process are repeated 10 to 20 times, and finally placed in a sintering furnace at a temperature of 450 to 650°C for 1.0 to 2.0 hours to obtain the titanium-based Pb-Co-Zr-SbO of the conductive support x Oxide interlayer; the Pb-Co-Zr-SbO x Method for preparing the precursor solution: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate, and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a certain proportion to obtain the Pb-Co-Zr-SbO x precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 4) Titanium mesh-based Pb-Co-Zr-SbO x Oxide interlayer plate: the Ti layer at both ends of the Ti-Cu-stainless steel conductive beam is milled to obtain a Cu-stainless steel conductive head; the titanium mesh-based Pb-Co-Zr-SbO x The oxide interlayer is cut and treated, and then combined with the titanium transition plate and the titanium-based Pb-Co-Zr-SbO of the conductive support x The oxide interlayer is cut and treated, and then combined with the titanium transition plate and the titanium-based Pb-Co-Zr-SbO of the conductive support x Oxide interlayer plate 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x Preparation of the composite oxide active layer: the titanium mesh-based Pb-Co-Zr-SbO x The oxide interlayer plate serves as the anode, and the stainless steel mesh plate serves as the cathode. The β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder is formed by electroplating in a lead methanesulfonate plating solution xThe composite oxide active layer is obtained by plating a titanium-based lead dioxide composite anode plate; the lead methyl sulfonate plating solution contains 50-350 g / L lead methyl sulfonate, 10-100 g / L methyl sulfonate, 5-30 g / L SrTiO3-SiO2-Ag composite ceramic powder and 10-50 g / L sodium tungstate; the plating temperature is 60-100 DEG C, the anode current density is 5-20 A / dm 2 , and the plating time is 60-180 min. The preparation method of the SrTiO3-SiO2-Ag composite ceramic powder is as follows: SrTiO3 powder, nano SiO2 powder and flaky Ag powder are added into an ethanol-water mixed solvent in a certain proportion, ultrasonic dispersion treatment is carried out for 10-30 min, centrifugal separation is carried out to obtain SrTiO3 / SiO2 / Ag mixed powder, the SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1000-1600 DEG C for 10-20 h, the furnace is cooled to room temperature, grinding is carried out, and SrTiO3-SiO2-Ag composite ceramic powder is obtained.

[0027] Example 1: In this example, a titanium-based lead dioxide composite anode plate for hydrometallurgy is prepared (see Figures 1-3 ), which comprises a Ti-Cu-stainless steel conductive beam 1, a titanium transition plate 2 and a titanium mesh-based lead dioxide composite gradient plate 3, The Ti-Cu-stainless steel conductive beam 1 is fixedly provided with a Cu-stainless steel conductive head 10 at both ends, and a titanium transition plate 2 is welded at the bottom end of the Ti-Cu-stainless steel conductive beam 1; the titanium transition plate 2 is symmetrically provided with a rectangular through hole at the top with respect to the center axis, and a titanium mesh-based lead dioxide composite gradient plate 3 is welded at the bottom end of the titanium transition plate 2; the titanium mesh-based lead dioxide composite gradient plate 3 comprises longitudinal conductive reinforcing ribs I 4, longitudinal conductive reinforcing ribs II 6, transverse conductive reinforcing ribs I 5, transverse conductive reinforcing ribs II 7, annular conductive reinforcing ribs 8, and a titanium-based lead dioxide composite mesh plate 9; the longitudinal conductive reinforcing ribs I 4 are arranged on both sides of the titanium-based lead dioxide composite mesh plate 9, the longitudinal conductive reinforcing ribs II 6 are vertically arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs I 5 are arranged at the bottom end of the titanium-based lead dioxide composite mesh plate 9, the transverse conductive reinforcing ribs II 7 are horizontally arranged in the middle of the titanium-based lead dioxide composite mesh plate 9, the annular conductive reinforcing ribs 8 are arranged on the titanium-based lead dioxide composite mesh plate 9, the intersection of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 is the center of the annular conductive reinforcing ribs 8, and the end points of the longitudinal conductive reinforcing ribs II 6 and the transverse conductive reinforcing ribs II 7 are connected with the annular conductive reinforcing ribs 8; the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 form a conductive support, and the titanium-based lead dioxide composite mesh plate 9 is welded in the area divided by the longitudinal conductive reinforcing ribs I 4, the longitudinal conductive reinforcing ribs II 6, the transverse conductive reinforcing ribs I 5, the transverse conductive reinforcing ribs II 7, and the annular conductive reinforcing ribs 8 in the conductive support; The titanium-based lead dioxide composite mesh plate 9 comprises, from inside to outside, a titanium mesh base 91, a cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x (x is 1) composite oxide bottom layer 92, Pb-Co-Zr-SbO x (x is 1) oxide intermediate layer 93, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1) composite oxide active layer 94; The conductive support comprises, from inside to outside, a titanium base, a Pb-Co-Zr-SbO x (x is 1) oxide intermediate layer, and SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x (x is 1) composite oxide active layer; The Ti-Cu-stainless steel conductive beam 1 comprises, from inside to outside, a stainless steel rod core 11, a copper layer 12, and a titanium layer 13; the height of the Ti-Cu-stainless steel conductive beam 1 is 40 mm, the thickness is 20 mm, the thickness of the copper layer 12 is 2 mm, and the thickness of the titanium layer 13 is 1 mm; The Cu-stainless steel conductive head 10 is integrally formed with the Ti-Cu-stainless steel conductive beam 1. The Cu-stainless steel conductive head 10 includes a stainless steel rod core 11 and a copper layer 12 from the inside to the outside. The copper layer 12 has a thickness of 2 mm. The cobalt-doped γ-MnO2-CaO coated glass fiber powder / nano-Al2O3 particles x (x is 1.0-1.3) The content of cobalt-coated glass fiber powder in the composite oxide bottom layer 92 is 0.1 wt.%, the content of nano-Al2O3 particles is 1 wt.%, the Ca content is 0.8 wt.%, and the balance is γ-MnO2; the particle size of the cobalt-coated glass fiber powder is 1 μm in long diameter and 5 nm in short diameter, and the particle size of the nano-Al2O3 particles is 50 nm; The Pb-Co-Zr-SbO x (x is 1.0 to 1.4) The total molar amount of Pb, Co, Zr, and Sb in the oxide intermediate layer 93 is 100%, and Pb accounts for 60%, Co accounts for 20%, Zr accounts for 10%, and Sb accounts for 10%; The β-PbO2-WO doped SrTiO3-SiO2-Ag composite ceramic powder x (x is 1.0-1.3) The content of SrTiO3-SiO2-Ag composite ceramic powder in the composite oxide active layer 94 is 0.5 wt.%, the content of W is 1 wt.%, and the balance is β-PbO2; The SrTiO3-SiO2-Ag composite ceramic powder has a SrTiO3 content of 60 wt.%, a SiO2 content of 20 wt.%, and an Ag content of 20 wt.%; a SrTiO3 particle size of 0.5 μm, a SiO2 particle size of 20 nm, and an Ag particle size of 1 μm; The titanium mesh matrix 91 of the titanium-based lead dioxide composite mesh plate 9 has a mesh length of 6 mm, a short axis of 3 mm, a cross-sectional thickness of 1.0 mm, and a cobalt-doped γ-MnO2-CaO coated with glass fiber powder / nano-Al2O3 particles. x The composite oxide base layer 92 has a thickness of 5 μm and is composed of Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer 93 is 5 μm, and the β-PbO2-WO x The thickness of the composite oxide active layer 94 is 0.4 mm; The titanium transition plate 2 has a height of 100 mm and a thickness of 3 mm. The vertical height of the rectangular through hole is 100 mm and the horizontal width is 50 mm. The titanium matrix cross-section width of the longitudinal conductive reinforcing ribs Ⅰ4 and the transverse conductive reinforcing ribs Ⅰ5 is 15 mm, the thickness is 5 mm, and the Pb-Co-Zr-SbO xThe thickness of the oxide intermediate layer is 5 μm, and the SrTiO3-SiO2-Ag composite ceramic powder is doped in β-PbO2-WO x The thickness of the composite oxide active layer is 0.4 mm. The titanium base section width of the longitudinal conductive reinforcing rib II 6, the transverse conductive reinforcing rib II 7 and the annular conductive reinforcing rib 8 is 5 mm, and the thickness is 5 mm, and the Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer is 5 μm, and the SrTiO3-SiO2-Ag composite ceramic powder is doped in β-PbO2-WO x The thickness of the composite oxide active layer is 0.4 mm. The preparation method of the titanium base lead dioxide composite anode plate for hydrometallurgy is specifically as follows: 1) The titanium mesh base cobalt-doped glass fiber powder / nano Al2O3 particle γ-MnO2-CaO x The preparation of the composite oxide bottom layer: the pretreated titanium mesh base is placed in a manganese nitrate composite plating solution to obtain the titanium mesh base cobalt-doped glass fiber powder / nano Al2O3 particle γ-MnO2-CaO by electroplating x The composite oxide bottom layer; the manganese nitrate in the manganese nitrate composite plating solution is 50 g / L, the calcium nitrate is 10 g / L, the nitric acid is 10 g / L, the cobalt-doped glass fiber powder is 2 g / L, and the nano Al2O3 is 5 g / L; the electroplating temperature is 80°C, the mechanical stirring speed is 100 rpm, the anode current density is 1.0 A / dm 2 , and the electroplating time is 10 min. The sand blasting is the sand blasting of silicon carbide sand with a particle size of 40 meshes, the oil removal method is: placing the titanium mesh base in a sodium hydroxide-sodium carbonate mixed solution for oil removal treatment at a temperature of 60°C for 10 min, the sodium hydroxide-sodium carbonate mixed solution contains 5 g / L of sodium hydroxide and 10 g / L of sodium carbonate; the phosphoric acid activation treatment method is: taking the titanium mesh base after oil removal treatment as a cathode, taking graphite as an anode, and polarizing in a sodium phosphate solution (the cathode current density is 5 A / dm 2 , the temperature is 80°C, and the time is 20 min); the sodium phosphate solution contains 10 g / L of sodium phosphate, 5 g / L of sodium hydroxide and 0.01 g / L of sodium dodecyl sulfate; The preparation method of the cobalt-coated glass fiber powder: the glass fiber powder is placed in an ammonium fluoride solution with a concentration of 10 g / L, ultrasonic roughening is performed for 5 min at a temperature of 20°C, after washing with deionized water, the glass fiber powder is placed in a stannous chloride / hydrochloric acid mixed solution (stannous chloride concentration of 5 g / L, hydrochloric acid concentration of 5 ml / L) for sensitization for 5 min, after washing with deionized water, the glass fiber powder is placed in a silver nitrate solution with a concentration of 3 g / L for ultrasonic activation for 10 min, and then washing with deionized water to obtain activated glass fiber powder; the activated glass fiber powder is placed in a chemical cobalt plating solution, and chemical cobalt plating is performed for 30 min at a temperature of 50°C to obtain the cobalt-coated glass fiber powder; the chemical cobalt plating solution contains 20 g / L of cobalt sulfate, 10 g / L of sodium hypophosphite, 5 g / L of disodium ethylenediaminetetraacetate, 40 g / L of trisodium citrate, and 0.01 g / L of polyvinylpyrrolidone; 2) Pb-Co-Zr-SbO on titanium mesh x Preparation of the oxide intermediate layer: Pb-Co-Zr-SbO x The precursor solution is uniformly coated on the surface of the titanium mesh substrate doped with cobalt-coated glass fiber powder / nano-Al2O3 particles, and γ-MnO2-CaO x The composite oxide bottom layer is dried at a temperature of 100°C, and then sintered at a temperature of 450°C for 5 min, and the coating of Pb-Co-Zr-SbO is repeated for 5 times x The precursor solution and the sintering process, and finally sintered at a temperature of 450°C for 1.0 h to obtain the Pb-Co-Zr-SbO on the titanium mesh x The oxide intermediate layer; the Pb-Co-Zr-SbO x The preparation method of the precursor solution: lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate, and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a certain proportion under ultrasonic and magnetic stirring to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 3) Pb-Co-Zr-SbO on titanium base of conductive support x Preparation of the oxide intermediate layer: the titanium base of the longitudinal conductive reinforcing rib I, the longitudinal conductive reinforcing rib II, the transverse conductive reinforcing rib I, the transverse conductive reinforcing rib II, and the annular conductive reinforcing rib is sequentially subjected to annealing and flattening, sandblasting, oil removal, and oxalic acid treatment (mass concentration of 8%) to obtain a pretreated titanium base, and Pb-Co-Zr-SbO x The precursor solution is uniformly coated on the surface of the pretreated titanium base, and dried at a temperature of 100°C, and then sintered at a temperature of 450°C for 10 min, and the coating of Pb-Co-Zr-SbO is repeated for 10 times x The precursor solution and the sintering process, and finally sintered at a temperature of 450°C for 1.0 h to obtain the Pb-Co-Zr-SbO on the titanium base of conductive support x The oxide intermediate layer; the Pb-Co-Zr-SbOx The preparation method of the precursor solution: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate and antimony trichloride were dissolved in ethanol-n-butanol mixed solvent in proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 4) Assemble the titanium mesh-based Pb-Co-Zr-SbO x Oxide interlayer plate: clean stainless steel rods are placed in copper pipes, extruded and drawn to form copper-coated stainless steel rods; then placed in oil-pretreated titanium pipes, extruded and drawn to be combined and oil-cooled at a temperature of 200°C to obtain Ti-Cu-stainless steel conductive beams, the Ti layer on both ends of the Ti-Cu-stainless steel conductive beams is milled off by a milling machine to obtain Cu-stainless steel conductive heads; titanium mesh-based Pb-Co-Zr-SbO x After the oxide interlayer is cut, the titanium mesh-based Pb-Co-Zr-SbO is combined with the titanium transition plate and the titanium-based Pb-Co-Zr-SbO of the conductive support x The oxide interlayer is assembled and welded to form a titanium mesh-based plate substrate, and the titanium transition plate of the titanium mesh-based plate substrate is welded at the bottom end of the Ti-Cu-stainless steel conductive beam to obtain the titanium mesh-based Pb-Co-Zr-SbO x Oxide interlayer plate 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x Preparation of the composite oxide active layer: titanium mesh-based Pb-Co-Zr-SbO x The oxide interlayer plate is an anode, and the stainless steel mesh plate is a cathode, which are electroplated in a lead methanesulfonate plating solution to form β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x The composite oxide active layer, to obtain a titanium-based lead dioxide composite anode plate; the lead methanesulfonate plating solution contains 50 g / L lead methanesulfonate, 10 g / L methanesulfonic acid, 5 g / L SrTiO3-SiO2-Ag composite ceramic powder, and 10 g / L sodium tungstate; the electroplating temperature is 60°C, the anode current density is 5 A / dm 2 , the electroplating time is 60 min, and the plating solution circulation amount is 5 L / min; The preparation method of the SrTiO3-SiO2-Ag composite ceramic powder is as follows: SrTiO3 powder, nano-SiO2 powder, and flaky Ag powder are added to an ethanol-water mixed solvent (volume ratio of 1:1) in proportion, ultrasonic dispersion treatment is performed for 10 min, centrifugal separation is performed to obtain SrTiO3 / SiO2 / Ag mixed powder, the SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1000°C for 10 h, the furnace is cooled to room temperature, and grinding is performed to a particle size of less than 10 μm to obtain SrTiO3-SiO2-Ag composite ceramic powder; The titanium-based lead dioxide composite anode plate prepared in the embodiment has the following advantages: compared with the traditional titanium-based lead dioxide, the anode life is prolonged by 1 times, the cell voltage is reduced by more than 15%, the current efficiency is increased by more than 2%, the lead dioxide coating is not easy to fall off, the oxygen evolution potential is low, the service life is long, and the electric efficiency is high, without changing the electrolytic cell structure, electrolyte composition and operation specification. 2+ The electrolysis conditions are as follows: the electrolyte is 50 g / L Zn 2 and 150 g / L sulfuric acid, the solution temperature is 40℃, and the anode current density is 500 A / m

[0028] Embodiment 2: The titanium-based lead dioxide composite anode plate for hydrometallurgy in the embodiment has basically the same structure as the titanium-based lead dioxide composite anode plate for hydrometallurgy in Embodiment 1, and the difference lies in that: The Ti-Cu-stainless steel conductive beam 1 comprises, from inside to outside, a stainless steel rod core 11, a copper layer 12 and a titanium layer 13; the height of the Ti-Cu-stainless steel conductive beam 1 is 80 mm, the thickness is 40 mm, the thickness of the copper layer 12 is 8 mm, and the thickness of the titanium layer 13 is 4 mm; The Cu-stainless steel conductive head 10 is integrally formed with the Ti-Cu-stainless steel conductive beam 1, and the Cu-stainless steel conductive head 10 comprises, from inside to outside, a stainless steel rod core 11 and a copper layer 12, and the thickness of the copper layer 12 is 8 mm; The γ-MnO2-CaO x (x is 1.7-2.1) composite oxide bottom layer 92, the content of the cobalt-coated glass fiber powder is 0.8 wt.%, the content of the nano-Al2O3 particles is 8 wt.%, the content of Ca is 2.0 wt.%, and the rest is γ-MnO2; the particle size of the cobalt-coated glass fiber powder is 10 μm in length and 30 nm in short diameter, and the particle size of the nano-Al2O3 particles is 100 nm; The Pb-Co-Zr-SbO x (x is 2.7-3.0) oxide intermediate layer 93, the total molar content of Pb, Co, Zr and Sb is 100%, and the content of Pb is 25%, the content of Co is 40%, the content of Zr is 20%, and the content of Sb is 15%; The β-PbO2-WO x (x is 2.6-3.0) composite oxide active layer 94, the content of the SrTiO3-SiO2-Ag composite ceramic powder is 8 wt.%, the content of W is 5 wt.%, and the rest is β-PbO2; The SrTiO3-SiO2-Ag composite ceramic powder contains 85wt.% of SrTiO3, 10wt.% of SiO2 and 15wt.% of Ag; the particle size of SrTiO3 is 5μm, the particle size of SiO2 is 80nm and the particle size of Ag is 5μm; The titanium mesh base body 91 of the titanium-based lead dioxide composite grid 9 has a long axis of 16mm and a short axis of 10mm, a cross-sectional thickness of 5.0mm, and a titanium mesh base body 91 is coated with a cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x The composite oxide bottom layer 92 has a thickness of 10μm, and is made of Pb-Co-Zr-SbO x The oxide intermediate layer 93 has a thickness of 20μm, and is made of SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The composite oxide active layer 94 has a thickness of 1.8mm. The titanium transition plate 2 has a height of 400mm and a thickness of 7mm, and the vertical height of the rectangular through hole is 300mm and the horizontal width is 200mm. The titanium base body of the longitudinal conductive reinforcing rib 14 and the horizontal conductive reinforcing rib 15 has a cross-sectional width of 50mm and a thickness of 20mm, and is made of Pb-Co-Zr-SbO x The oxide intermediate layer has a thickness of 20μm, and is made of SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The composite oxide active layer has a thickness of 1.8mm. The titanium base body of the longitudinal conductive reinforcing rib 16, the horizontal conductive reinforcing rib 17 and the annular conductive reinforcing rib 8 has a cross-sectional width of 20mm and a thickness of 20mm, and is made of Pb-Co-Zr-SbO x The oxide intermediate layer has a thickness of 20μm, and is made of SrTiO3-SiO2-Ag composite ceramic powder-doped β-PbO2-WO x The composite oxide active layer has a thickness of 1.8mm. The preparation method of the titanium-based lead dioxide composite anode plate for hydrometallurgy includes the following specific steps: 1) titanium mesh base cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x Preparation of the composite oxide bottom layer: the titanium mesh base body is subjected to sand blasting, leveling, oil removal and phosphoric acid activation to obtain a pretreated titanium mesh base body, and the pretreated titanium mesh base body is placed in a manganese nitrate composite plating solution to obtain a titanium mesh base cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO xComposite oxide bottom layer; the manganese nitrate composite plating solution contains 200g / L manganese nitrate, 80g / L calcium nitrate, 60g / L nitric acid, 8g / L cobalt-coated glass fiber powder, and 20g / L nano-Al2O3; the electroplating temperature is 100°C, the mechanical stirring speed is 600rpm, and the anode current density is 4.0A / dm 2 and the plating time is 60min; The sandblasting method is to blast silicon carbide sand with a particle size of 80 mesh. The degreasing method is to place the substrate in a sodium hydroxide-sodium carbonate mixed solution at a temperature of 80°C for degreasing for 30 minutes. The sodium hydroxide-sodium carbonate mixed solution contains 10g / L sodium hydroxide and 50g / L sodium carbonate. The phosphoric acid activation method is to use the degreasing titanium mesh substrate as the cathode and graphite as the anode, and polarize the substrate in a sodium phosphate solution (the cathode current density is 10A / dm 2 , temperature is 100°C, time is 60min); the sodium phosphate solution contains 40g / L sodium phosphate, 20g / L sodium hydroxide, and 0.2g / L sodium lauryl sulfate; The cobalt-coated glass fiber powder preparation method comprises placing the glass fiber powder in a 50 g / L ammonium fluoride solution, ultrasonically roughening the solution at 50° C. for 10 minutes, washing the solution with deionized water, sensitizing the solution in a stannous chloride / hydrochloric acid mixed solution (stannous chloride concentration: 10 g / L, hydrochloric acid concentration: 10 ml / L) for 10 minutes, washing the solution with deionized water, ultrasonically activating the solution in a 5 g / L silver nitrate solution for 30 minutes, and washing the solution with deionized water to obtain activated glass fiber powder; placing the activated glass fiber powder in an electroless cobalt plating solution, and electrolessly plating the solution at 80° C. for 120 minutes to obtain the cobalt-coated glass fiber powder; the electroless cobalt plating solution contains 40 g / L cobalt sulfate, 40 g / L sodium hypophosphite, 20 g / L disodium ethylenediaminetetraacetic acid, 80 g / L trisodium citrate, and 0.1 g / L polyvinylpyrrolidone; 2) Titanium mesh-based Pb-Co-Zr-SbO x Preparation of oxide intermediate layer: Pb-Co-Zr-SbO x The precursor liquid is evenly coated on the titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particles of γ-MnO2-CaO x The surface of the composite oxide bottom layer was dried at 120℃ and then sintered at 650℃ for 10min. The process was repeated 20 times to coat the Pb-Co-Zr-SbO x The precursor liquid and sintering process, finally placed at a temperature of 650 ° C for 2.0h, to obtain the titanium network based Pb-Co-Zr-SbO x Oxide intermediate layer; the Pb-Co-Zr-SbO xThe preparation method of the precursor solution is as follows: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 3) Titanium-based Pb-Co-Zr-SbO of the conductive support x The preparation of the oxide intermediate layer: the titanium bases of the longitudinal conductive reinforcing rib I, the longitudinal conductive reinforcing rib II, the transverse conductive reinforcing rib I, the transverse conductive reinforcing rib II and the annular conductive reinforcing rib are sequentially subjected to annealing leveling, sand blasting, oil removal, oxalic acid treatment (mass concentration of 12%) to obtain a pretreated titanium base, and Pb-Co-Zr-SbO x The Pb-Co-Zr-SbO is uniformly coated on the surface of the pretreated titanium base, dried at a temperature of 120℃, and then sintered at a temperature of 650℃ for 15 min, and the coating of Pb-Co-Zr-SbO is repeated for 20 times x The precursor solution and the sintering process, and finally sintered at a temperature of 650℃ for 2.0 h to obtain the titanium-based Pb-Co-Zr-SbO of the conductive support x The oxide intermediate layer; the Pb-Co-Zr-SbO x The preparation method of the precursor solution is as follows: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 4) Titanium mesh-based Pb-Co-Zr-SbO x The oxide intermediate layer electrode plate: a clean stainless steel rod is placed in a copper pipe and extruded and drawn to form a copper-coated stainless steel rod; then the copper-coated stainless steel rod is placed in a titanium pipe subjected to oil removal pretreatment, and is extruded and drawn to be combined and oil-cooled at a temperature of 300℃ to obtain a Ti-Cu-stainless steel conductive beam, and the Ti-Cu-stainless steel conductive beam is milled by a milling machine to mill off the surface Ti layer to obtain a Cu-stainless steel conductive head; and the titanium mesh-based Pb-Co-Zr-SbO x The oxide intermediate layer is cut and treated, and combined with the titanium transition plate and the titanium-based Pb-Co-Zr-SbO of the conductive support x The oxide intermediate layer is assembled and welded to form a titanium mesh-based electrode plate base, and the titanium transition plate of the titanium mesh-based electrode plate base is welded at the bottom end of the Ti-Cu-stainless steel conductive beam to obtain the titanium mesh-based Pb-Co-Zr-SbO x The oxide intermediate layer electrode plate 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x The preparation of the composite oxide active layer: the titanium mesh-based Pb-Co-Zr-SbO xThe oxide interlayer plate is an anode, the stainless steel mesh plate is a cathode, and the β-PbO2-WO is formed by electroplating in a lead methanesulfonate plating solution doped with SrTiO3-SiO2-Ag composite ceramic powder x The composite oxide active layer is obtained, and a titanium-based lead dioxide composite anode plate is obtained; the lead methanesulfonate plating solution contains 350 g / L of lead methanesulfonate, 100 g / L of methanesulfonic acid, 30 g / L of SrTiO3-SiO2-Ag composite ceramic powder, and 50 g / L of sodium tungstate; the electroplating temperature is 100℃, the anode current density is 20 A / dm 2 , the electroplating time is 180 min, and the plating solution circulation amount is 20 L / min; The preparation method of the SrTiO3-SiO2-Ag composite ceramic powder comprises the following steps: SrTiO3 powder, nano-SiO2 powder, and flaky Ag powder are added into an ethanol-water mixed solvent (in a volume ratio of 1:1) in a proportion, ultrasonic dispersion treatment is performed for 30 min, SrTiO3 / SiO2 / Ag mixed powder is obtained through centrifugal separation, the SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1600℃ for 20 h, the furnace is cooled to room temperature, grinding is performed until the particle size is less than 10 μm, and the SrTiO3-SiO2-Ag composite ceramic powder is obtained; The titanium-based lead dioxide composite anode plate prepared in the embodiment has the following advantages: compared with a traditional titanium-based lead dioxide, the anode life is prolonged by 1.5 times, the cell voltage is reduced by more than 17%, the current efficiency is increased by more than 3%, the lead dioxide plating layer is not easy to fall off, the oxygen evolution potential is low, the service life is long, and the electric efficiency is high. 2+ 2 The titanium-based lead dioxide composite anode plate prepared in the embodiment has the following advantages: compared with a traditional titanium-based lead dioxide, the anode life is prolonged by 1.5 times, the cell voltage is reduced by more than 17%, the current efficiency is increased by more than 3%, the lead dioxide plating layer is not easy to fall off, the oxygen evolution potential is low, the service life is long, and the electric efficiency is high.

[0029] Example 3: The titanium-based lead dioxide composite anode plate for hydrometallurgy in the embodiment is basically the same as the titanium-based lead dioxide composite anode plate for hydrometallurgy in Example 1, and the difference lies in that: The Ti-Cu-stainless steel conductive beam 1 comprises, from inside to outside, a stainless steel rod core 11, a copper layer 12, and a titanium layer 13; the height of the Ti-Cu-stainless steel conductive beam 1 is 60 mm, the thickness is 30 mm, the thickness of the copper layer 12 is 5 mm, and the thickness of the titanium layer 13 is 2.5 mm; The Cu-stainless steel conductive head 10 is integrally formed with the Ti-Cu-stainless steel conductive beam 1, and the Cu-stainless steel conductive head 10 comprises, from inside to outside, a stainless steel rod core 11 and a copper layer 12; the thickness of the copper layer 12 is 5 mm; The γ-MnO2-CaO is doped with cobalt-coated glass fiber powder / nano-Al2O3 particles x ​The cobalt-coated glass fiber powder content in the composite oxide bottom layer 92 is 0.4 wt.%, the nano-Al2O3 particle content is 5 wt.%, the Ca content is 1.4 wt.%, and the balance is γ-MnO2; the cobalt-coated glass fiber powder has a length diameter of 5 μm and a short diameter of 15 nm, and the nano-Al2O3 particle has a particle size of 80 nm; The Pb-Co-Zr-SbO x The total molar amount of Pb, Co, Zr, and Sb in the oxide intermediate layer 93 is 100%, of which Pb accounts for 42%, Co accounts for 30%, Zr accounts for 15%, and Sb accounts for 13%; The β-PbO2-WO x The SrTiO3-SiO2-Ag composite ceramic powder content in the composite oxide active layer 94 is 4 wt.%, the W content is 3 wt.%, and the balance is β-PbO2; The SrTiO3-SiO2-Ag composite ceramic powder contains 75 wt.% of SrTiO3, 15 wt.% of SiO2, and 10 wt.% of Ag; the SrTiO3 has a particle size of 3 μm, the SiO2 has a particle size of 50 nm, and the Ag has a particle size of 3 μm; The titanium mesh substrate 91 of the titanium-based lead dioxide composite mesh plate 9 has a mesh hole long axis of 12 mm, a short axis of 6 mm, a cross-sectional thickness of 3.0 mm, and a γ-MnO2-CaO x The composite oxide bottom layer 92 has a thickness of 7 μm, and the Pb-Co-Zr-SbO x The oxide intermediate layer 93 has a thickness of 12 μm, and the β-PbO2-WO x The composite oxide active layer 94 has a thickness of 1.2 mm; The titanium transition plate 2 has a height of 250 mm, a thickness of 5 mm, a vertical height of the rectangular through hole of 200 mm, and a horizontal width of 125 mm; The titanium substrate of the longitudinal conductive reinforcing rib I 4 and the horizontal conductive reinforcing rib I 5 has a cross-sectional width of 35 mm and a thickness of 12 mm, and the Pb-Co-Zr-SbO x The oxide intermediate layer has a thickness of 13 μm, and the β-PbO2-WO x The composite oxide active layer has a thickness of 1.2 mm; The titanium substrate of the longitudinal conductive reinforcing rib II 6, the horizontal conductive reinforcing rib II 7, and the annular conductive reinforcing rib 8 has a cross-sectional width of 12 mm and a thickness of 12 mm, and the Pb-Co-Zr-SbOx The thickness of the oxide intermediate layer is 13 μm, and the thickness of the composite oxide active layer is 1.2 mm. x The thickness of the oxide intermediate layer is 13 μm, and the thickness of the composite oxide active layer is 1.2 mm. The preparation method of the titanium-based lead dioxide composite anode plate for hydrometallurgy comprises the following specific steps: 1) titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x Preparation of the composite oxide bottom layer: the titanium mesh substrate is subjected to sand blasting, leveling, oil removal, and phosphoric acid activation treatment in sequence to obtain a pretreated titanium mesh substrate, and the pretreated titanium mesh substrate is placed in a manganese nitrate composite plating solution to obtain a titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO by electroplating x The composite oxide bottom layer; the manganese nitrate composite plating solution contains 125 g / L of manganese nitrate, 45 g / L of calcium nitrate, 30 g / L of nitric acid, 5 g / L of cobalt-coated glass fiber powder, and 12 g / L of nano-Al2O3; the electroplating temperature is 90°C, the mechanical stirring speed is 300 rpm, the anode current density is 2.5 A / dm 2 , and the electroplating time is 30 min. The sand blasting is performed by using silicon carbide sand with a particle size of 60 mesh, the oil removal method is to place the titanium mesh substrate in a sodium hydroxide-sodium carbonate mixed solution at a temperature of 70°C for oil removal treatment for 20 min, the sodium hydroxide-sodium carbonate mixed solution contains 8 g / L of sodium hydroxide and 30 g / L of sodium carbonate, the phosphoric acid activation treatment method is to polarize the titanium mesh substrate subjected to the oil removal treatment as a cathode and graphite as an anode in a sodium phosphate solution (the cathode current density is 8 A / dm 2 , the temperature is 90°C, and the time is 40 min), and the sodium phosphate solution contains 30 g / L of sodium phosphate, 10 g / L of sodium hydroxide, and 0.1 g / L of sodium dodecyl sulfate; The preparation method of the cobalt-coated glass fiber powder: the glass fiber powder is placed in an ammonium fluoride solution with a concentration of 30 g / L, ultrasonic roughening is performed at a temperature of 35°C for 8 min, after washing with deionized water, the glass fiber powder is placed in a stannous chloride / hydrochloric acid mixed solution (stannous chloride concentration of 8 g / L and hydrochloric acid concentration of 7 ml / L) for sensitization for 8 min, after washing with deionized water, the glass fiber powder is placed in a silver nitrate solution with a concentration of 4 g / L for ultrasonic activation for 20 min, and after washing with deionized water, activated glass fiber powder is obtained; the activated glass fiber powder is placed in a chemical plating cobalt solution, chemical plating is performed at a temperature of 65°C for 80 min to obtain cobalt-coated glass fiber powder; the chemical plating cobalt solution contains 30 g / L of cobalt sulfate, 25 g / L of sodium hypophosphite, 8 g / L of ethylenediaminetetraacetic acid disodium, 60 g / L of trisodium citrate, and 0.05 g / L of polyvinylpyrrolidone. 2) titanium mesh-based Pb-Co-Zr-SbO xPreparation of oxide intermediate layer: Pb-Co-Zr-SbO x The precursor solution is evenly coated on the surface of the titanium mesh substrate, dried at a temperature of 110 ℃, and then sintered at a temperature of 550 ℃ for 8 min, and the coating of Pb-Co-Zr-SbO is repeated 12 times x Preparation of oxide intermediate layer: Pb-Co-Zr-SbO x The precursor solution and sintering process are repeated 15 times, and finally sintered at a temperature of 550 ℃ for 1.5 h to obtain the titanium mesh substrate based Pb-Co-Zr-SbO x Oxide intermediate layer; the Pb-Co-Zr-SbO x Preparation method of the precursor solution: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate, and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a certain proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 3) Titanium-based Pb-Co-Zr-SbO of the conductive support x Preparation of oxide intermediate layer: the titanium base of the longitudinal conductive reinforcing rib I, the longitudinal conductive reinforcing rib II, the transverse conductive reinforcing rib I, the transverse conductive reinforcing rib II, and the annular conductive reinforcing rib is sequentially subjected to annealing and flattening, sandblasting, oil removal, and oxalic acid treatment (mass concentration of 10%) to obtain a pretreated titanium base, and Pb-Co-Zr-SbO x The precursor solution is evenly coated on the surface of the pretreated titanium base, dried at a temperature of 110 ℃, and then sintered at a temperature of 550 ℃ for 13 min, and the coating of Pb-Co-Zr-SbO is repeated 15 times x The precursor solution and sintering process are repeated 15 times, and finally sintered at a temperature of 550 ℃ for 1.5 h to obtain the titanium-based Pb-Co-Zr-SbO of the conductive support x Oxide intermediate layer; the Pb-Co-Zr-SbO x Preparation method of the precursor solution: under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate, and antimony trichloride are dissolved in an ethanol-n-butanol mixed solvent in a certain proportion to obtain Pb-Co-Zr-SbO x The precursor solution; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; 4) Assembly of titanium mesh based Pb-Co-Zr-SbO x Oxide intermediate layer electrode plate: a clean stainless steel rod is placed in a copper pipe and extruded and drawn to form a copper-coated stainless steel rod; then the copper-coated stainless steel rod is placed in a titanium pipe subjected to oil removal pretreatment, and is extruded and drawn to be combined, and is oil-cooled at a temperature of 250 ℃ to obtain a Ti-Cu-stainless steel conductive beam; the Ti-Cu-stainless steel conductive beam is milled by a milling machine to mill off the surface Ti layer to obtain a Cu-stainless steel conductive head; and the titanium mesh based Pb-Co-Zr-SbOx The oxide interlayer is cut and treated, and the titanium transition plate and the titanium-based Pb-Co-Zr-SbO of the conductive support are welded x The oxide interlayer is assembled and welded to form a titanium mesh base plate substrate, and the titanium transition plate of the titanium mesh base plate substrate is welded at the bottom end of the Ti-Cu-stainless steel conductive beam to obtain the titanium mesh base Pb-Co-Zr-SbO x The oxide interlayer plate; 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x Preparation of the composite oxide active layer: titanium mesh base Pb-Co-Zr-SbO x The oxide interlayer plate is an anode, and the stainless steel mesh plate is a cathode. The β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder is formed by electroplating in a lead methanesulfonate plating solution x The composite oxide active layer is obtained, and the titanium-based lead dioxide composite anode plate is obtained; the lead methanesulfonate plating solution contains 200 g / L lead methanesulfonate, 55 g / L methanesulfonic acid, 18 g / L SrTiO3-SiO2-Ag composite ceramic powder, and 30 g / L sodium tungstate; the electroplating temperature is 80°C, the anode current density is 15 A / dm 2 , the electroplating time is 120 min, and the plating solution circulation amount is 15 L / min; The preparation method of the SrTiO3-SiO2-Ag composite ceramic powder is as follows: SrTiO3 powder, nano-SiO2 powder, and flaky Ag powder are added to an ethanol-water mixed solvent (volume ratio of 1:1) in a proportion, ultrasonic dispersion treatment is performed for 20 min, centrifugal separation is performed to obtain SrTiO3 / SiO2 / Ag mixed powder, the SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1300°C for 15 h, the furnace is cooled to room temperature, and grinding is performed to a particle size of less than 10 μm to obtain SrTiO3-SiO2-Ag composite ceramic powder; The titanium-based lead dioxide composite anode plate prepared in this embodiment is used in hydrometallurgy, and the electrolysis conditions are as follows: the electrolyte is 50 g / L Zn 2+ and 150 g / L sulfuric acid, the solution temperature is 40°C, the anode current density is 500 A / m 2 Compared with the traditional titanium-based lead dioxide, the anode life is prolonged by 1.5 times, the cell voltage is reduced by more than 20%, the current efficiency is increased by more than 5%, the lead dioxide coating is not easy to fall off, the oxygen evolution potential is low, the service life is long, and the electric efficiency is high.

[0030] The above detailed description of the present application is made with reference to specific embodiments thereof, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present application.

Claims

1. A titanium-based lead dioxide composite anode plate for hydrometallurgy, characterized by: It includes a Ti-Cu-stainless steel conductive beam (1), a titanium transition plate (2), and a titanium mesh-based lead dioxide composite gradient plate (3). The Ti-Cu-stainless steel conductive beam (1) is fixedly provided with Cu-stainless steel conductive heads (10) at both ends, and a titanium transition plate (2) is welded to the bottom end of the Ti-Cu-stainless steel conductive beam (1). A rectangular through hole is opened symmetrically with respect to the central axis on the top of the titanium transition plate (2). A titanium mesh-based lead dioxide composite gradient plate (3) is welded to the bottom end of the titanium transition plate (2). The titanium mesh-based lead dioxide composite gradient plate (3) includes a longitudinal conductive reinforcement rib I (4), a longitudinal conductive reinforcement rib II (6), a transverse conductive reinforcement rib I (5), a transverse conductive reinforcement rib II (7), an annular conductive reinforcement rib (8), and a titanium-based lead dioxide composite mesh plate (9). The longitudinal conductive reinforcement rib I (4) is provided on both sides of the titanium-based lead dioxide composite mesh plate (9), the longitudinal conductive reinforcement rib II (6) is vertically provided in the middle of the titanium-based lead dioxide composite mesh plate (9), and the transverse conductive reinforcement rib I (5) is provided on the titanium-based lead dioxide composite mesh plate (9). At the bottom end, the transverse conductive reinforcement rib II (7) is horizontally arranged in the middle of the titanium-based lead dioxide composite mesh plate (9), and the annular conductive reinforcement rib (8) is arranged on the titanium-based lead dioxide composite mesh plate (9). The intersection of the longitudinal conductive reinforcement rib II (6) and the transverse conductive reinforcement rib II (7) is the center of the annular conductive reinforcement rib (8), and the end points of the longitudinal conductive reinforcement rib II (6) and the transverse conductive reinforcement rib II (7) are both connected to the annular conductive reinforcement rib (8); the longitudinal conductive reinforcement rib I (4), the longitudinal conductive reinforcement rib II (6), the transverse conductive reinforcement rib I (5), the transverse conductive reinforcement rib II (7) and the annular conductive reinforcement rib (8) constitute a conductive bracket, and the titanium-based lead dioxide composite mesh plate (9) is welded in the area formed by the longitudinal conductive reinforcement rib I (4), the longitudinal conductive reinforcement rib II (6), the transverse conductive reinforcement rib I (5), the transverse conductive reinforcement rib II (7) and the annular conductive reinforcement rib (8) in the conductive bracket; The titanium-based lead dioxide composite mesh plate (9) comprises, from the inside to the outside, a titanium mesh matrix (91), a cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x (x is 1~2) composite oxide bottom layer (92), Pb-Co-Zr-SbO x (x is 1~3) oxide intermediate layer (93) and β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x (x is 1 to 3) composite oxide active layer (94); The conductive support comprises a titanium matrix, a Pb-Co-Zr-SbO x (x is 1~3) oxide intermediate layer and SrTiO3-SiO2-Ag doped composite ceramic powder β-PbO2-WO x (x is 1~3) composite oxide active layer.

2. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 1, characterized in that: The Ti-Cu-stainless steel conductive beam (1) comprises, from the inside to the outside, a stainless steel rod core (11), a copper layer (12) and a titanium layer (13); The Cu-stainless steel conductive head (10) and the Ti-Cu-stainless steel conductive beam (1) are integrally formed, and the Cu-stainless steel conductive head (10) comprises a stainless steel rod core (11) and a copper layer (12) in sequence from the inside to the outside.

3. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 2, characterized in that: The Ti-Cu-stainless steel conductive beam (1) has a length of 40 to 80 mm and a thickness of 20 to 40 mm, a thickness of the copper layer (12) of 2 to 8 mm, and a thickness of the titanium layer (13) of 1 to 4 mm.

4. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 1, characterized in that: The cobalt-doped γ-MnO2-CaO coated glass fiber powder / nano-Al2O3 particles x (x is 1-2) The content of cobalt-coated glass fiber powder in the composite oxide bottom layer (92) is 0.1-0.8 wt.%, the content of nano-Al2O3 particles is 1-8 wt.%, the content of Ca is 0.8-2.0 wt.%, and the balance is γ-MnO2; the particle size of the cobalt-coated glass fiber powder is 1-10 μm in long diameter and 5-30 nm in short diameter, and the particle size of the nano-Al2O3 particles is 50-100 nm; The Pb-Co-Zr-SbO x (x is 1 to 3) the total molar amount of Pb, Co, Zr, and Sb in the oxide intermediate layer (93) is 100%, Pb accounts for 25 to 60%, Co accounts for 20 to 40%, Zr accounts for 10 to 20%, and Sb accounts for 10 to 15%; The β-PbO2-WO doped SrTiO3-SiO2-Ag composite ceramic powder x (x is 1~3) composite oxide active layer (94) SrTiO3-SiO2-Ag composite ceramic powder content is 0.5~8wt.%, W content is 1~5wt.%, and the balance is β-PbO2; The SrTiO3-SiO2-Ag composite ceramic powder has a SrTiO3 content of 60-85wt.%, a SiO2 content of 10-20wt.%, and an Ag content of 5-20wt.%; the SrTiO3 particle size is 0.5-5μm, the SiO2 particle size is 20-80nm, and the Ag particle size is 1-5μm.

5. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 4, characterized in that: The titanium mesh matrix (91) of the titanium-based lead dioxide composite mesh plate (9) has a mesh length of 6 to 16 mm, a short axis of 3 to 10 mm, a cross-sectional thickness of 1.0 to 5.0 mm, and a cobalt-doped γ-MnO2-CaO coated with glass fiber powder / nano-Al2O3 particles. x The thickness of the composite oxide bottom layer (92) is 5~10μm, Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer (93) is 5~20μm, and the β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x The thickness of the composite oxide active layer (94) is 0.4 to 1.8 mm.

6. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 1, characterized in that: The height of the titanium transition plate (2) is 100-400 mm, the thickness is 3-7 mm, the vertical height of the rectangular through hole is 100-300 mm, and the horizontal width is 50-200 mm.

7. The titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 1, characterized in that: The titanium matrix cross-section width of the longitudinal conductive reinforcing ribs Ⅰ (4) and the transverse conductive reinforcing ribs Ⅰ (5) is 15-50 mm, the thickness is 5-20 mm, and the Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer is 5~20μm, and the SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x The thickness of the composite oxide active layer is 0.4~1.8mm; The cross-sectional width of the titanium matrix of the longitudinal conductive reinforcement rib II (6), the transverse conductive reinforcement rib II (7), and the annular conductive reinforcement rib (8) is 5~20 mm, the thickness is 5~20 mm, and the Pb-Co-Zr-SbO x The thickness of the oxide intermediate layer is 5~20μm, and the SrTiO3-SiO2-Ag composite ceramic powder β-PbO2-WO x The thickness of the composite oxide active layer is 0.4~1.8mm.

8. The method for preparing a titanium-based lead dioxide composite anode plate for hydrometallurgy according to any one of claims 1 to 7, characterized in that: The specific steps are as follows: 1) Titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particles γ-MnO2-CaO x Preparation of composite oxide bottom layer: The titanium mesh substrate is sequentially sandblasted, leveled, degreased, and activated with phosphoric acid to obtain a pretreated titanium mesh substrate. The pretreated titanium mesh substrate is then electroplated in a manganese nitrate composite plating solution to obtain a titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particle γ-MnO2-CaO x Composite oxide bottom layer; the manganese nitrate composite plating solution contains 50-200 g / L manganese nitrate, 10-80 g / L calcium nitrate, 10-60 g / L nitric acid, 2-8 g / L cobalt-coated glass fiber powder, and 5-20 g / L nano-Al2O3; 2) Titanium mesh-based Pb-Co-Zr-SbO x Preparation of oxide intermediate layer: Pb-Co-Zr-SbO x The precursor liquid is evenly coated on the titanium mesh-based cobalt-doped glass fiber powder / nano-Al2O3 particles of γ-MnO2-CaO x The surface of the composite oxide bottom layer is dried at a temperature of 100~120℃, and then sintered at a temperature of 450~650℃ for 5~10min. Repeat this process 5~20 times to coat Pb-Co-Zr-SbO x The precursor liquid and sintering process are finally placed at a temperature of 450~650℃ for 1.0~2.0h to obtain titanium network-based Pb-Co-Zr-SbO x oxide intermediate layer; 3) Titanium-based Pb-Co-Zr-SbO conductive support x Preparation of oxide intermediate layer: The titanium substrate of longitudinal conductive reinforcement rib I, longitudinal conductive reinforcement rib II, transverse conductive reinforcement rib I, transverse conductive reinforcement rib II and annular conductive reinforcement rib is subjected to annealing, leveling, sandblasting, degreasing and oxalic acid treatment in sequence to obtain pretreated titanium substrate. x The precursor liquid is evenly coated on the surface of the pretreated titanium substrate, dried at a temperature of 100-120 ° C, and then sintered at a temperature of 450-650 ° C for 5-10 minutes. Repeat 10-20 times to coat the Pb-Co-Zr-SbO x The precursor liquid and sintering process are finally placed at a temperature of 450~650℃ for 1.0~2.0h to obtain the titanium-based Pb-Co-Zr-SbO conductive support. x oxide intermediate layer; 4) Assembling titanium mesh-based Pb-Co-Zr-SbO x Oxide intermediate layer plate: The Ti layer is milled off at both ends of the Ti-Cu-stainless steel conductive beam to obtain a Cu-stainless steel conductive head; Titanium mesh-based Pb-Co-Zr-SbO x The oxide intermediate layer is cut and then connected to the titanium transition plate and the titanium-based Pb-Co-Zr-SbO conductive support. x The oxide intermediate layer is assembled and welded to form a titanium mesh base plate substrate, and the titanium transition plate of the titanium mesh base plate substrate is welded to the bottom end of the Ti-Cu-stainless steel conductive beam to obtain a titanium mesh base Pb-Co-Zr-SbO x Oxide intermediate layer plate; 5) β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder x Preparation of composite oxide active layer: Pb-Co-Zr-SbO based on titanium network x The oxide intermediate layer plate is the anode, the stainless steel mesh plate is the cathode, and β-PbO2-WO doped with SrTiO3-SiO2-Ag composite ceramic powder is electroplated in a lead methanesulfonate plating solution. x A composite oxide active layer is prepared to obtain a titanium-based lead dioxide composite anode plate; the lead methanesulfonate plating solution contains 50-350 g / L lead methanesulfonate, 10-100 g / L methanesulfonic acid, 5-30 g / L SrTiO3-SiO2-Ag composite ceramic powder, and 10-50 g / L sodium tungstate.

9. The method for preparing a titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 8, characterized in that: Step 1) Electroplating temperature is 80~100℃, mechanical stirring speed is 100~600 rpm, and anode current density is 1.0~4.0A / dm 2 and electroplating time is 10~60min; Pb-Co-Zr-SbO in step 2) and step 3) x Preparation method of precursor solution: Under ultrasonic and magnetic stirring, lead nitrate, cobalt nitrate, zirconium oxychloride octahydrate and antimony trichloride are dissolved in ethanol-n-butanol mixed solvent in proportion to obtain Pb-Co-Zr-SbO x Precursor liquid; the volume ratio of ethanol to n-butanol in the ethanol-n-butanol mixed solvent is 1:1; Step 3) The mass concentration of oxalic acid is 8% to 12%; Step 5) The electroplating temperature is 60~100℃ and the anode current density is 5~20A / dm 2 The electroplating time is 60~180min, and the plating solution circulation volume is 5~20 L / min.

10. The method for preparing a titanium-based lead dioxide composite anode plate for hydrometallurgy according to claim 8, characterized in that: Step 1) sandblasting is to blast silicon carbide sand with a particle size of 40-80 mesh. The degreasing method is to place the mixture in a sodium hydroxide-sodium carbonate mixed solution at a temperature of 60-80°C for degreasing for 10-30 minutes. The sodium hydroxide-sodium carbonate mixed solution contains 5-10g / L sodium hydroxide and 10-50g / L sodium carbonate. The phosphoric acid activation method is to use the degreasing titanium mesh substrate as the cathode and graphite as the anode, and polarize the mixture in a sodium phosphate solution. The sodium phosphate solution contains 10-40g / L sodium phosphate, 5-20g / L sodium hydroxide, and 0.01-0.2g / L sodium lauryl sulfate. The cathode current density of the polarization treatment is 5-10 A / dm 2 , temperature is 80~100℃, time is 20~60min; Step 1) Preparation of cobalt-coated glass fiber powder: placing the glass fiber powder in an ammonium fluoride solution, ultrasonically roughening it at a temperature of 20-50°C for 5-10 minutes, washing it with deionized water, sensitizing it in a stannous chloride / hydrochloric acid mixed solution for 5-10 minutes, washing it with deionized water, ultrasonically activating it in a silver nitrate solution for 10-30 minutes, and washing it with deionized water to obtain activated glass fiber powder; placing the activated glass fiber powder in an electroless cobalt plating solution, and electrolessly plating it at a temperature of 50-80°C for 30-120 minutes n obtain cobalt-coated glass fiber powder; the concentration of the ammonium fluoride solution is 10-50 g / L, the concentration of stannous chloride in the stannous chloride / hydrochloric acid mixed solution is 5-10 g / L, the concentration of hydrochloric acid is 5-10 ml / L, the concentration of the silver nitrate solution is 3-5 g / L, and the chemical cobalt plating solution contains 20-40 g / L cobalt sulfate, 10-40 g / L sodium hypophosphite, 5-20 g / L disodium edetate, 40-80 g / L trisodium citrate, and 0.01-0.1 g / L polyvinyl pyrrolidone; Step 5) The preparation method of SrTiO3-SiO2-Ag composite ceramic powder is as follows: SrTiO3 powder, nano-SiO2 powder, and flaky Ag powder are added to an ethanol-water mixed solvent in proportion, ultrasonically dispersed for 10 to 30 minutes, and centrifuged to obtain a SrTiO3 / SiO2 / Ag mixed powder. The SrTiO3 / SiO2 / Ag mixed powder is sintered at a temperature of 1000 to 1600°C for 10 to 20 hours, cooled to room temperature in the furnace, and ground to obtain a SrTiO3-SiO2-Ag composite ceramic powder.

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