Electrolytic chlorate electrode assembly and preparation process

Abstract

The invention discloses an electrolytic chlorate electrode group and a preparation process thereof, and particularly relates to structural design and installation of a bipolar chlorate electrolytic bath and preparation and application of a titanium anode electrode coating liquid. The electrolytic cell structure adopts a bipolar design, adopts a plastic screw, a gasket and a snap fastener which are good in insulation and corrosion resistance, and adopts a modular design, so that the electrolytic cell can effectively reduce current, reduce conductive connection and line loss, and can realize customization of different series stages according to parameters such as yield and power supply. In addition, a formed titanium plate serves as a base material, oil removal, sand blasting, acid pickling, water washing and drying treatment are sequentially carried out, and then ruthenium-containing coating liquid is sequentially coated and high-temperature oxidation is carried out. The titanium anode coating takes ruthenium as a main material, tin and other easily available and cheap metal elements are added, and a small amount of platinum is added to improve the electrode stability. The chlorine evolution performance of the optimized titanium anode is enhanced, the durability of the anode and the cathode can be effectively improved by acting with a cathode material during electrolysis, and the cost is remarkably reduced.

Description

Technical Field

[0001] The invention relates to the technical field of chlorate electrolysis equipment, and in particular to a chlorate electrolysis electrode group and a preparation process thereof. Background Art

[0002] As one of the three major electrolytic industries in the world, the industrial manufacturing of sodium chlorate can be traced back to the 19th century. Products such as potassium chlorate, ammonium chlorate, hypochlorous acid and chlorine dioxide processed from sodium chlorate are widely used as water disinfectants, medical disinfectants, pesticides and herbicides, paper fiber bleaching agents, rocket fuel components, uranium ore processing additives, etc. In recent years, it has also been used to treat inorganic or organic pollutants, such as cyanide, nitrite, phenol and organic phosphide.

[0003] At present, the electrochemical production of chlorate mainly uses a diaphragmless electrolytic cell for electrolyzing saturated sodium chloride as the production unit. However, this type of electrolytic cell still has some problems, such as low efficiency of chlorine evolution at the anode, poor stability of hydrogen evolution at the cathode, complex installation and maintenance, and high cost.

[0004] Based on the above problems, it is necessary to make technical improvements to the existing electrolytic chlorate equipment and electrode preparation process. Summary of the invention

[0005] In order to solve the above problems, the present invention proposes an electrolytic chlorate electrode group and a preparation process, aiming to improve the current efficiency, enhance the electrode stability, simplify the installation process and reduce the cost of the electrolytic cell by optimizing the electrolytic cell structure, titanium anode coating components, cathode materials, etc.; by adopting a bipolar design, the cathode and anode use materials and coatings with good electrocatalytic activity to achieve the purpose of energy saving and consumption reduction. The specific technical scheme is as follows: A chlorate electrolysis electrode group comprises an anode assembly, a bipolar assembly and a cathode assembly arranged in sequence; wherein the anode assembly comprises an anode end flange and a number of anodes arranged at intervals on one side of the anode end flange, the cathode assembly comprises a cathode end flange and a number of cathodes arranged at intervals on one side of the cathode end flange, the bipolar assembly comprises a bipolar connector, a number of anodes arranged at intervals on one side of the bipolar connector, and a number of cathodes arranged at intervals on the other side of the bipolar connector; a number of anodes in the anode assembly and a number of cathodes in the bipolar assembly are arranged alternately and plugged in, a number of anodes in the bipolar assembly and a number of cathodes in the cathode assembly are arranged alternately and plugged in, and a gap is provided between adjacent anodes and cathodes after the alternate plugging arrangement; wherein the anode is a titanium-based precious metal oxide coating electrode, and the precious metal oxide in the titanium-based precious metal oxide coating electrode is composed of one or more of ruthenium oxide, titanium oxide, platinum oxide, tin oxide, bismuth oxide, and indium oxide.

[0006] The number of the above-mentioned bipolar components can be one or more.

[0007] Preferably, there are multiple bipolar components and they are arranged adjacent to each other in sequence from beginning to end, a number of anodes and a number of cathodes in the adjacent bipolar components are arranged alternately, and a gap is provided between adjacent anodes and cathodes after the alternate arrangement; a number of anodes in the anode component and a number of cathodes in the first bipolar component in the bipolar component are arranged alternately, and a number of anodes in the last bipolar component in the bipolar component and a number of cathodes in the cathode component are arranged alternately.

[0008] Preferably, the bipolar assembly comprises bipolar assembly 1 and bipolar assembly 2 which are arranged alternately in sequence from the beginning to the end, wherein the first bipolar assembly and the last bipolar assembly are both bipolar assembly 1; the number of anodes on the anode assembly is N, the number of cathodes on the cathode assembly is N, the number of anodes and the number of cathodes of the bipolar assembly 1 are both N+1, and the number of anodes and the number of cathodes of the bipolar assembly 2 are both N; the anodes and the cathodes of the bipolar assembly are respectively provided with a plurality of mounting connection holes, and are also provided with insulating screws for connecting and fixing adjacent bipolar assemblies in the plurality of bipolar assemblies, insulating female buckles for connecting and fixing the anode assembly and the bipolar assembly, and insulating female buckles for connecting the bipolar assembly and the cathode. An insulator female buckle is used to connect and fix components; after the anodes and cathodes between adjacent bipolar components are alternately inserted into each other, the connection and fixation between adjacent bipolar components are achieved by insulating screws passing through the installation connection holes; female buckles in the insulator female buckle are respectively installed in the installation connection holes on the cathode of the bipolar component connected to the anode component and the installation connection holes on the anode of the bipolar component connected to the cathode component, and sub-buckles in the insulator female buckle are respectively fixed on the anode of the anode component and the cathode of the cathode component, and the anode component and the bipolar component, as well as the bipolar component and the cathode component, are connected and fixed by combining the corresponding female buckles and sub-buckles in the insulator female buckle.

[0009] In the present invention, the insulating screw is also covered with an insulating gasket and the insulating gasket is arranged at a position between adjacent anodes and cathodes that are alternately inserted into each other on the bipolar assembly, and nuts are connected to both ends of the insulating screw; a flange mounting hole 1 is provided on the anode end flange, and a flange mounting hole 2 is provided on the cathode end flange; the anode assembly is an anode assembly made of titanium material, the cathode assembly is a cathode assembly made of stainless steel or carbon steel material, the bipolar assembly is a bipolar assembly of a titanium-steel composite structure, the insulator buckle is an insulator buckle made of PVDF or PTFE material, the insulating screw is an insulating screw made of PVDF or PTFE material, and the insulating gasket is an insulating gasket made of PVDF or PTFE material.

[0010] Preferably, the bipolar connector is a titanium-steel composite plate.

[0011] Preferably, the anode in the anode assembly is used as anode one, and the anode one is welded on the anode end flange with a fixed spacing; the cathode in the cathode assembly is used as cathode one, and the cathode one is welded on the cathode end flange with a fixed spacing; the bipolar connector in the bipolar assembly one is used as bipolar connector one, the anode in the bipolar assembly one is used as anode two, and the anode two is welded on one side of the bipolar connector one with a fixed spacing, and the cathode in the bipolar assembly one is used as cathode two, and the cathode two is welded on the other side of the bipolar connector one with a fixed spacing; the bipolar connector in the bipolar assembly two is used as bipolar connector two, the anode in the bipolar assembly two is used as anode three, and the anode three is welded on one side of the bipolar connector two with a fixed spacing, and the cathode in the bipolar assembly two is used as cathode three, and the cathode three is welded on the other side of the bipolar connector two with a fixed spacing.

[0012] In the present invention, the anode assembly, bipolar assembly and cathode assembly are arranged in sequence along the longitudinal direction of the electrolytic cell body in the electrolytic cell, and a number of anodes and a number of cathodes are arranged opposite to each other along the longitudinal direction of the electrolytic cell body.

[0013] Preferably, the anode is a titanium-based ruthenium oxide coated electrode, the cathode is a stainless steel, carbon steel or Hastelloy electrode, the bipolar connector is a bipolar connector of a titanium-steel composite structure, and the two ends of the bipolar connector are respectively welded with a titanium-based ruthenium oxide coated electrode as an anode and a stainless steel, carbon steel or Hastelloy electrode as a cathode; the bipolar assembly is installed inside the tank body, and the anode assembly and cathode assembly are then installed at both ends of the tank body; the inner sides of the flange mounting hole one and the flange mounting hole two are respectively connected to the anode side and the cathode side of the tank body, and the outer sides are connected to the positive and negative input terminals of the DC power supply through cables or copper bars.

[0014] A preparation process for an electrolytic chlorate electrode group includes the preparation of an anode, wherein the preparation of the anode includes the following steps: (I) Titanium forming: Titanium is processed into a titanium anode forming substrate of a certain shape; (ii) Pretreatment of titanium anode forming substrate: the formed titanium anode substrate is successively subjected to degreasing, sandblasting, pickling, water washing and drying; (III) Preparation of titanium anode coating, including the following steps: (1) Preparation of coating liquid: one or more raw materials selected from ruthenium trichloride, butyl titanate, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, bismuth nitrate, indium trichloride, hydrochloric acid, acetylacetone, and n-butanol are dissolved in a solvent containing n-butanol in different molar ratios to prepare a coating liquid; (2) Coating and oxidation sintering: Apply the prepared coating liquid to the surface of the titanium anode forming substrate several times, and dry and oxidize it in turn after each coating. The last coating and drying is followed by sintering.

[0015] Preferably, in the coating solution preparation step of step (iii) for preparing the titanium anode coating, one or more of the following coating solutions are prepared: Ruthenium titanium coating liquid: a ruthenium titanium coating liquid prepared from ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:(2-4):(8-12):(100-150); Ruthenium coating liquid: a ruthenium coating liquid prepared from ruthenium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:100; Ruthenium platinum tin coating liquid: a ruthenium platinum tin coating liquid prepared from ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol in the ruthenium platinum tin coating liquid is (6-8):1:(0.5-1.5):1:(80-100); Ruthenium bismuth indium coating liquid: a ruthenium bismuth indium coating liquid prepared from ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol in the ruthenium bismuth indium coating liquid is 10:(1~2):(1~2):10:120.

[0016] Preferably, in the coating and oxidation sintering process of the anode coating preparation in step (iii), the coating and oxidation sintering are performed according to the following method: coating the surface of the titanium anode forming substrate with a ruthenium titanium coating solution several times, a ruthenium coating solution several times, a ruthenium platinum tin coating solution several times, and a ruthenium bismuth indium coating solution several times, and drying and oxidation treatment are performed in sequence after each coating, and the last coating and drying are followed by sintering.

[0017] Preferably, in the coating and oxidation sintering process of preparing the anode coating in step (iii), the coating and oxidation sintering are performed according to the following method: First, apply ruthenium titanium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium platinum tin coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 470℃ for 10 min; finally, apply ruthenium bismuth indium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 480℃ for 10 min. After each coating, dry and oxidize it in turn. After the last coating and drying, sinter it for 20 minutes.

[0018] The beneficial effects of the present invention are: First, the present invention discloses an electrolytic chlorate electrode group and a preparation process, wherein anodes and cathodes of different materials are compounded, wherein the anode adopts a chlorine-evolving titanium anode with high chlorine-evolving catalytic activity, which can efficiently and stably evolve chlorine for a long time, and the cathode adopts a high hydrogen-evolving material, which can steadily evolve hydrogen for a long time and has good resistance to "hydrogen embrittlement".

[0019] Second, the electrolytic chlorate electrode group and preparation process of the present invention adopts a bipolar design, which effectively reduces the current, reduces the conductive connection and line loss, and improves the current efficiency.

[0020] Third, the electrolytic chlorate electrode group and preparation process of the present invention adopts plastic screws, gaskets and snap fasteners with good insulation and corrosion resistance, which are easy to install and maintain.

[0021] Fourthly, the present invention provides an electrolytic chlorate electrode group and a preparation process, by arranging a plurality of anodes and a plurality of cathodes mutually interlaced along the longitudinal direction of the electrolytic cell body, which can greatly increase the total effective area of ​​the anodes and cathodes, thereby improving the electrolysis efficiency per unit cell volume; by adopting a modular design, customization of different series connection levels can be achieved according to parameters such as output and power supply, which is conducive to reducing costs.

[0022] Fifth, in the present invention, an electrolytic chlorate electrode group and preparation process, the titanium anode coating is mainly ruthenium, and tin and other easily available and inexpensive metal elements are added, and a small amount of platinum is added to improve the electrode stability. The optimized titanium anode has enhanced chlorine evolution performance, and the interaction with the cathode material during electrolysis can effectively improve the durability of the anode and cathode, and significantly reduce costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a structural schematic diagram of a chlorate electrolysis electrode group of the present invention; Figure 2 yes Figure 1 Schematic diagram of the explosion of the chlorate electrolysis electrode group.

[0024] Figure 3 It is an assembly diagram of the anode assembly, cathode assembly, bipolar assembly 1 and bipolar assembly 2 in the chlorate electrolysis electrode group.

[0025] Figure 4 is the surface SEM image of the anode sample prepared in Example 1.3.

[0026] Figure 5 is a cross-sectional SEM image of the anode sample prepared in Example 1.3.

[0027] In the figure: 1, anode assembly, 2, cathode assembly, 3, bipolar assembly one, 4, bipolar assembly two, 5, insulator buckle, 6, insulating screw, 7, mounting hole, 11, anode one, 12, anode end flange, 121, flange mounting hole one, 21, cathode one, 22, cathode end flange, 221, flange mounting hole two, 31, anode two, 32, cathode two, 33, bipolar connector one, 41, anode three, 42, cathode three, 43, bipolar connector two. DETAILED DESCRIPTION

[0028] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and cannot be used to limit the protection scope of the present invention.

[0029] Example 1.1: like Figures 1 to 5 The present invention shows an embodiment of an electrolytic chlorate electrode group, comprising an anode assembly 1, a bipolar assembly and a cathode assembly 2 arranged in sequence; wherein the anode assembly 1 comprises an anode end flange 12 and a plurality of anodes arranged at intervals on one side of the anode end flange 12, the cathode assembly 2 comprises a cathode end flange 22 and a plurality of cathodes arranged at intervals on one side of the cathode end flange 22, the bipolar assembly comprises a bipolar connector, a plurality of anodes arranged at intervals on one side of the bipolar connector, and a plurality of cathodes arranged at intervals on the other side of the bipolar connector; a plurality of anodes in the anode assembly 1 and a plurality of cathodes in the bipolar assembly are arranged alternately, a plurality of anodes in the bipolar assembly and a plurality of cathodes in the cathode assembly 2 are arranged alternately, and a gap is provided between adjacent anodes and cathodes arranged alternately; wherein the anode is a titanium-based precious metal oxide coated electrode, and the precious metal oxide in the titanium-based precious metal oxide coated electrode is composed of one or more of ruthenium oxide, titanium oxide, platinum oxide, tin oxide, bismuth oxide and indium oxide.

[0030] The number of the above-mentioned bipolar components can be one or more.

[0031] Preferably, there are multiple bipolar components and they are arranged adjacent to each other in sequence from beginning to end, a number of anodes and a number of cathodes in the adjacent bipolar components are arranged alternately, and a gap is provided between adjacent anodes and cathodes after the alternate arrangement; a number of anodes in the anode component and a number of cathodes in the first bipolar component in the bipolar component are arranged alternately, and a number of anodes in the last bipolar component in the bipolar component and a number of cathodes in the cathode component are arranged alternately.

[0032] Preferably, the bipolar assembly comprises bipolar assembly one 3 and bipolar assembly two 4 which are arranged alternately in sequence from the beginning to the end, wherein the first bipolar assembly and the last bipolar assembly are both bipolar assembly one; the number of anodes on the anode assembly 1 is N, the number of cathodes on the cathode assembly 2 is N, the number of anodes and the number of cathodes of the bipolar assembly one 3 are both N+1, and the number of anodes and the number of cathodes of the bipolar assembly two 4 are both N; a plurality of mounting connection holes 7 are respectively provided on the anode and the cathode of the bipolar assembly, and an insulating screw 6 for connecting and fixing adjacent bipolar assemblies in the plurality of bipolar assemblies, an insulating female buckle 5 for connecting and fixing the anode assembly 1 and the bipolar assembly, and a female buckle 5 for connecting and fixing the bipolar assembly and the cathode assembly 2; the anodes and cathodes between adjacent bipolar components are alternately inserted and arranged to achieve connection and fixation between adjacent bipolar components through insulating screws 6 passing through the mounting connection holes 7; the mounting connection holes 7 on the cathode of the bipolar component connected to the anode component 1 and the mounting connection holes 7 on the anode of the bipolar component connected to the cathode component 2 are respectively installed with female buckles in the insulator female buckle 5, and the anode of the anode component 1 and the cathode of the cathode component 2 are respectively fixed with corresponding sub-buckles in the insulator female buckle 5, and the anode component 1 and the bipolar component, and the bipolar component and the cathode component 2 are connected and fixed by combining the corresponding female buckles and sub-buckles in the insulator female buckle 5.

[0033] In the present invention, the insulating screw 6 is also covered with an insulating gasket and the insulating gasket is arranged at a position between adjacent anodes and cathodes that are alternately inserted into each other on the bipolar assembly, and nuts are connected to both ends of the insulating screw; the anode end flange 12 is provided with a flange mounting hole 121, and the cathode end flange 22 is provided with a flange mounting hole 221; the anode assembly 1 is an anode assembly made of titanium material, the cathode assembly 2 is a cathode assembly made of stainless steel or carbon steel, the bipolar assembly is a bipolar assembly of a titanium-steel composite structure, the insulator buckle 5 is an insulator buckle made of PVDF or PTFE material, the insulating screw 6 is an insulating screw made of PVDF or PTFE material, and the insulating gasket is an insulating gasket made of PVDF or PTFE material.

[0034] Preferably, the bipolar connector is a titanium-steel composite plate.

[0035] Preferably, the anode in the anode assembly 1 is used as anode 11, and the anode 11 is controlled to be welded on the anode end flange 12 at a fixed interval; the cathode in the cathode assembly 2 is used as cathode 21, and the cathode 21 is controlled to be welded on the cathode end flange 22 at a fixed interval; the bipolar connector in the bipolar assembly 3 is used as bipolar connector 33, and the anode in the bipolar assembly 3 is used as anode 2 31, and the anode 2 31 is controlled to be welded on one side of the bipolar connector 33 at a fixed interval, and the bipolar assembly The cathode in component 1 3 is used as cathode 2 32, and the cathode 2 32 is controlled to be welded at the other side of the bipolar connector 1 33 at a fixed interval; the bipolar connector in the bipolar component 2 4 is used as bipolar connector 2 43, and the anode in the bipolar component 2 4 is used as anode 3 41, and the anode 3 41 is controlled to be welded at one side of the bipolar connector 2 43 at a fixed interval; the cathode in the bipolar component 2 4 is used as cathode 3 42, and the cathode 3 42 is controlled to be welded at the other side of the bipolar connector 2 43 at a fixed interval.

[0036] In the present invention, the anode assembly 1, bipolar assembly and cathode assembly 2 are arranged in sequence along the longitudinal direction of the electrolytic cell, and a number of anodes and a number of cathodes are arranged opposite to each other along the longitudinal direction of the electrolytic cell.

[0037] Preferably, the anode is a titanium-based ruthenium oxide coated electrode, the cathode is a stainless steel, carbon steel or Hastelloy electrode, the bipolar connector is a bipolar connector of a titanium-steel composite structure, and the two ends of the bipolar connector are respectively welded with a titanium-based ruthenium oxide coated electrode as an anode and a stainless steel, carbon steel or Hastelloy electrode as a cathode; the bipolar assembly is installed inside the tank body, and the anode assembly and cathode assembly are then installed at both ends of the tank body; the inner sides of the flange mounting hole 121 and the flange mounting hole 221 are respectively connected to the anode side and the cathode side of the tank body, and the outer sides are connected to the positive and negative input terminals of the DC power supply through cables or copper bars.

[0038] Example 1.2: A preparation process for an electrolytic chlorate electrode group includes the preparation of an anode, wherein the preparation of the anode includes the following steps: (I) Titanium forming: Titanium is processed into a titanium anode forming substrate of a certain shape; (ii) Pretreatment of titanium anode forming substrate: the formed titanium anode substrate is successively subjected to degreasing, sandblasting, pickling, water washing and drying; (III) Preparation of titanium anode coating, including the following steps: (1) Preparation of coating liquid: one or more raw materials selected from ruthenium trichloride, butyl titanate, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, bismuth nitrate, indium trichloride, hydrochloric acid, acetylacetone, and n-butanol are dissolved in a solvent containing n-butanol in different molar ratios to prepare a coating liquid; (2) Coating and oxidation sintering: Apply the prepared coating liquid to the surface of the titanium anode forming substrate several times, and dry and oxidize it in turn after each coating. The last coating and drying is followed by sintering.

[0039] Preferably, in the coating solution preparation step of step (iii) for preparing the titanium anode coating, one or more of the following coating solutions are prepared: Ruthenium titanium coating liquid: a ruthenium titanium coating liquid prepared from ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:(2-4):(8-12):(100-150); Ruthenium coating liquid: a ruthenium coating liquid prepared from ruthenium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:100; Ruthenium platinum tin coating liquid: a ruthenium platinum tin coating liquid prepared from ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol in the ruthenium platinum tin coating liquid is (6-8):1:(0.5-1.5):1:(80-100); Ruthenium bismuth indium coating liquid: a ruthenium bismuth indium coating liquid prepared from ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol in the ruthenium bismuth indium coating liquid is 10:(1~2):(1~2):10:120.

[0040] Preferably, in the coating and oxidation sintering process of the anode coating preparation in step (iii), the coating and oxidation sintering are performed according to the following method: coating the surface of the titanium anode forming substrate with a ruthenium titanium coating solution several times, a ruthenium coating solution several times, a ruthenium platinum tin coating solution several times, and a ruthenium bismuth indium coating solution several times, and drying and oxidation treatment are performed in sequence after each coating, and the last coating and drying are followed by sintering.

[0041] Preferably, in the coating and oxidation sintering process of preparing the anode coating in step (iii), the coating and oxidation sintering are performed according to the following method: First, apply ruthenium titanium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium platinum tin coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 470℃ for 10 min; finally, apply ruthenium bismuth indium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 480℃ for 10 min. After each coating, dry and oxidize it in turn. After the last coating and drying, sinter it for 20 minutes. Example 1.3:

[0042] Based on the preparation process of a chlorate electrolysis electrode group in Example 1.2, a titanium-based noble metal oxide coating anode used in the chlorate electrolysis electrode group in Example 1.1 was prepared. The coating preparation process was as follows: 1. Preparation of 300 g / L NaCl solution: Ultrasonic disperse 30 g of NaCl solid in 70 ml of ultrapure water, and then transfer to a 100 ml volumetric flask to make up the volume.

[0043] 2. Preparation of 1 mol / L H2SO4 solution: Slowly add 54.3 ml of 98%wt H2SO4 into 900 ml of pure water along the wall of the beaker using a glass rod and stir continuously. After the solution cools, transfer it to a 1000 ml volumetric flask and make up the volume.

[0044] 3. Titanium substrate processing, coating preparation and coating oxidation: (I) Titanium forming: Titanium is processed into a titanium anode forming substrate of a certain shape; (ii) Pretreatment of titanium anode forming substrate: the formed titanium anode substrate is successively subjected to degreasing, sandblasting, pickling, water washing and drying; (III) Preparation of titanium anode coating, including the following steps: (1) Preparation of coating liquid: one or more raw materials selected from ruthenium trichloride, butyl titanate, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, bismuth nitrate, indium trichloride, hydrochloric acid, acetylacetone, and n-butanol are dissolved in a solvent containing n-butanol in different molar ratios to prepare a coating liquid; (2) Coating and oxidation sintering: The prepared coating liquid is coated on the surface of the titanium anode forming substrate several times, and each coating is followed by drying and oxidation treatment, and the last coating, drying and sintering treatment is performed; 4. Preparation of coating liquid: one or more raw materials selected from ruthenium trichloride, butyl titanate, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, bismuth nitrate, indium trichloride, hydrochloric acid, acetylacetone, and n-butanol are dissolved in a solvent containing n-butanol in different molar ratios to prepare a coating liquid; The proportions of each layer of electrode coating are as follows: Ruthenium titanium coating liquid: a ruthenium titanium coating liquid prepared from ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid, and n-butanol, wherein the molar ratio of ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid, and n-butanol in the ruthenium coating liquid is 10:10:3:10:120; Ruthenium coating liquid: a ruthenium coating liquid prepared from ruthenium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:100; Ruthenium platinum tin coating liquid: a ruthenium platinum tin coating liquid prepared from ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol in the ruthenium platinum tin coating liquid is 7:1:1:1:90; Ruthenium bismuth indium coating liquid: a ruthenium bismuth indium coating liquid prepared with ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol in the ruthenium bismuth indium coating liquid is 10:1.5:1.5:10:120.

[0045] 5. In the coating and oxidation sintering process of the titanium anode forming substrate coating treatment in step (iii), the coating and oxidation sintering are carried out according to the following method: First, apply ruthenium titanium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium platinum tin coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 470℃ for 10 min; finally, apply ruthenium bismuth indium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 480℃ for 10 min. After each coating, dry and oxidize it in turn. After the last coating and drying, sinter it for 20 minutes.

[0046] 6. Application (1) Polarization curve test of titanium anode electrode A three-electrode system was used, the working electrode was the titanium anode coating electrode in the preparation process of the electrolytic chlorate electrode, the auxiliary electrode was a platinum sheet, the reference electrode was a calomel electrode of a saturated potassium chloride solution, the electrolyte was a 300 g / L NaCl solution, the temperature was 25±2°C, the electrochemical workstation used a linear sweep voltammetry (LSV) program, the test interval was 0.5-1.5 V Vs.SCE, the scan rate was 10 mV / s, the electrode polarization curve was collected and compared with the standard hydrogen electrode potential. The experimental results are shown in Table 1.

[0047] (2) Titanium anode strengthening life test The titanium anode coating electrode in the preparation process of the electrolytic chlorate electrode is connected to a constant current DC power supply with a current density of 10000 A / m 2 The solution system is 1 mol / L H2SO4, the distance between the cathode and the anode is 20 mm, the temperature is 40±2℃, and the time for the test voltage to rise to 10 V is 167 h. The experimental results are shown in Table 2.

[0048] VII. Surface and cross-sectional SEM images of the preparation in Example 1 are shown in Figure 4 , 5 As shown, the synthesized composite coating electrode has a regular morphology.

[0049] Embodiment 2: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum and tin in the ruthenium-platinum-tin coating solution is 6:1:1, and the other preparation methods are the same as those in Example 1.3.

[0050] Embodiment 3: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum and tin in the ruthenium-platinum-tin coating solution is 8:1:1, and the other preparation methods are the same as those in Example 1.3.

[0051] Embodiment 4: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum and tin in the ruthenium-platinum-tin coating solution is 7:1:0.5, and the other preparation methods are the same as those in Example 1.3.

[0052] Embodiment 5: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum and tin in the ruthenium-platinum-tin coating solution is 7:1:1.5, and the other preparation methods are the same as those in Example 1.3.

[0053] Embodiment 6: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, bismuth and indium in the ruthenium bismuth indium coating solution is 10:1:1.5, and the other preparation methods are the same as those in Example 1.3.

[0054] Embodiment 7: Compared with Example 1.3, the difference is that the molar ratio of ruthenium, bismuth and indium in the ruthenium bismuth indium coating solution is 10:1.5:1, and the other preparation methods are the same as those in Example 1.3.

[0055] Comparative Example 1:

[0056] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:2:10:120, and the other preparation methods are the same as those in Example 1.3.

[0057] Comparative Example 2:

[0058] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:4:10:120, and the other preparation methods are the same as those in Example 1.3.

[0059] Comparative Example 3:

[0060] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:3:8:120, and the other preparation methods are the same as those in Example 1.3.

[0061] Comparative Example 4:

[0062] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:3:12:120, and the other preparation methods are the same as those in Example 1.3.

[0063] Comparative Example 5:

[0064] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:3:10:120, and the other preparation methods are the same as those in Example 1.3.

[0065] Comparative Example 6:

[0066] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:3:12:100, and the other preparation methods are the same as those in Example 1.3.

[0067] Comparative Example 7:

[0068] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, titanium, acetylacetone, hydrochloric acid and n-butanol in the ruthenium-titanium coating liquid is 10:10:3:12:150, and the other preparation methods are the same as those in Example 1.3.

[0069] Comparative Example 8:

[0070] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum, tin, hydrochloric acid and n-butanol in the ruthenium-platinum-tin coating solution is 7:1:1:1:80, and the other preparation methods are the same as those in Example 1.3.

[0071] Comparative Example 9:

[0072] Compared with Example 1.3, the difference is that the molar ratio of ruthenium, platinum, tin, hydrochloric acid and n-butanol in the ruthenium-platinum-tin coating solution is 7:1:1:1:120, and the other preparation methods are the same as those in Example 1.3. Example 8

[0073] (1) Chlorine evolution potential detection The oxygen evolution potential was tested using a three-electrode system: the working electrode was the titanium anode prepared in Example 1.3 and Example 2 to Example 7, the auxiliary electrode was titanium, the reference electrode was a saturated calomel electrode, and the current density was 3000 A / m 2 , 300 g / L sodium chloride solution.

[0074] Table 1: Chlorine evolution potential test data

[0075] (2) Enhanced lifespan The anode is the titanium anode prepared in Example 1.3, Example 2 to Example 7, the cathode is titanium, and the current density is 10000A / m 2 , solution system 1 mol / L H2SO4 solution, time for the voltage to rise by 5 V from the initial voltage.

[0076] The experimental results show that Example 1.3 has the best strengthening life.

[0077] Table 2: Enhanced life test data

[0078] (3) Morphology test The surface and cross-sectional morphology of the titanium anode prepared in Example 1.3 were scanned using a German ZEISS-Ultra Plus field emission scanning electron microscope and an American FEI- Quanta 250FEG field emission scanning electron microscope, which were consistent with the morphological characteristics of a chlorine-evolving titanium anode.

[0079] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the technical principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A chlorate electrolysis electrode assembly, characterized in that: The invention comprises an anode assembly, a bipolar assembly and a cathode assembly arranged in sequence; wherein the anode assembly comprises an anode end flange and a number of anodes arranged at intervals on one side of the anode end flange, the cathode assembly comprises a cathode end flange and a number of cathodes arranged at intervals on one side of the cathode end flange, the bipolar assembly comprises a bipolar connector, a number of anodes arranged at intervals on one side of the bipolar connector, and a number of cathodes arranged at intervals on the other side of the bipolar connector; a number of anodes in the anode assembly and a number of cathodes in the bipolar assembly are arranged alternately, a number of anodes in the bipolar assembly and a number of cathodes in the cathode assembly are arranged alternately, and a gap is provided between adjacent anodes and cathodes arranged alternately; wherein the anode is a titanium-based precious metal oxide coated electrode, and the precious metal oxide in the titanium-based precious metal oxide coated electrode is composed of one or more of ruthenium oxide, titanium oxide, platinum oxide, tin oxide, bismuth oxide, and indium oxide.

2. The chlorate electrolysis electrode assembly according to claim 1, characterized in that: There are multiple bipolar components and they are arranged adjacent to each other in sequence from the beginning to the end. A number of anodes and a number of cathodes in the adjacent bipolar components are arranged alternately, and a gap is provided between adjacent anodes and cathodes after the alternate arrangement. A number of anodes in the anode component and a number of cathodes in the first bipolar component in the bipolar component are arranged alternately, and a number of anodes in the last bipolar component in the bipolar component and a number of cathodes in the cathode component are arranged alternately.

3. The chlorate electrolysis electrode assembly according to claim 1, characterized in that: The bipolar assembly comprises bipolar assembly 1 and bipolar assembly 2 which are arranged alternately in sequence from the beginning to the end, wherein the first bipolar assembly and the last bipolar assembly are both bipolar assembly 1; the number of anodes on the anode assembly is N, the number of cathodes on the cathode assembly is N, the number of anodes and the number of cathodes of the bipolar assembly 1 are both N+1, and the number of anodes and the number of cathodes of the bipolar assembly 2 are both N; a plurality of mounting connection holes are respectively provided on the anode and the cathode of the bipolar assembly, and insulating screws for connecting and fixing adjacent bipolar assemblies in the plurality of bipolar assemblies, insulating female buckles for connecting and fixing the anode assembly and the bipolar assembly, and insulating female buckles for connecting the bipolar assembly and the cathode assembly An insulator female buckle is used to connect and fix the two components; after the anodes and cathodes between adjacent bipolar components are alternately inserted into each other, the connection and fixation between adjacent bipolar components are achieved by insulating screws passing through the installation connection holes; female buckles in the insulator female buckle are respectively installed in the installation connection holes on the cathode of the bipolar component connected to the anode component and in the installation connection holes on the anode of the bipolar component connected to the cathode component, and sub-buckles in the insulator female buckle are respectively fixed on the anode of the anode component and the cathode of the cathode component, and the anode component and the bipolar component, as well as the bipolar component and the cathode component, are connected and fixed by combining the corresponding female buckles and sub-buckles in the insulator female buckle.

4. The chlorate electrolysis electrode assembly according to claim 3, characterized in that: The insulating screw is also covered with an insulating gasket and the insulating gasket is arranged between adjacent anodes and cathodes that are alternately inserted into each other on the bipolar assembly, and nuts are connected to both ends of the insulating screw; a flange mounting hole 1 is provided on the anode end flange, and a flange mounting hole 2 is provided on the cathode end flange; the anode assembly is an anode assembly made of titanium material, the cathode assembly is a cathode assembly made of stainless steel or carbon steel material, the bipolar assembly is a bipolar assembly of a titanium-steel composite structure, the insulator buckle is an insulator buckle made of PVDF or PTFE material, the insulating screw is an insulating screw made of PVDF or PTFE material, and the insulating gasket is an insulating gasket made of PVDF or PTFE material.

5. The chlorate electrolysis electrode assembly according to claim 3, characterized in that: The anode in the anode assembly is used as anode one, and the anode one is controlled to be welded on the anode end flange at a fixed interval; the cathode in the cathode assembly is used as cathode one, and the cathode one is controlled to be welded on the cathode end flange at a fixed interval; the bipolar connector in the bipolar assembly one is used as bipolar connector one, the anode in the bipolar assembly one is used as anode two, and the anode two is controlled to be welded on one side of the bipolar connector one at a fixed interval, and the cathode in the bipolar assembly one is used as cathode two, and the cathode two is controlled to be welded on the other side of the bipolar connector one at a fixed interval; the bipolar connector in the bipolar assembly two is used as bipolar connector two, the anode in the bipolar assembly two is used as anode three, and the anode three is controlled to be welded on one side of the bipolar connector two at a fixed interval, and the cathode in the bipolar assembly two is used as cathode three, and the cathode three is controlled to be welded on the other side of the bipolar connector two at a fixed interval.

6. The chlorate electrolysis electrode assembly according to claim 4, characterized in that: The anode is a titanium-based ruthenium oxide coated electrode, the cathode is a stainless steel, carbon steel or Hastelloy electrode, the bipolar connector is a titanium-steel composite structure bipolar connector, and the two ends of the bipolar connector are respectively welded with a titanium-based ruthenium oxide coated electrode as an anode and a stainless steel, carbon steel or Hastelloy electrode as a cathode; the bipolar assembly is installed inside the tank body, and the anode assembly and cathode assembly are then installed at both ends of the tank body; the inner sides of the flange mounting hole 1 and the flange mounting hole 2 are respectively connected to the anode side and the cathode side of the tank body, and the outer sides are connected to the positive and negative input terminals of the DC power supply through cables or copper bars.

7. A process for preparing an electrolytic chlorate electrode assembly, characterized in that: The method comprises the steps of preparing an anode, wherein the preparation of the anode comprises the following steps: (I) Titanium forming: Titanium is processed into a titanium anode forming substrate of a certain shape; (ii) Pretreatment of titanium anode forming substrate: the formed titanium anode substrate is successively subjected to degreasing, sandblasting, pickling, water washing and drying; (III) Preparation of titanium anode coating, including the following steps: (1) Preparation of coating liquid: one or more raw materials selected from ruthenium trichloride, butyl titanate, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, bismuth nitrate, indium trichloride, hydrochloric acid, acetylacetone, and n-butanol are dissolved in a solvent containing n-butanol in different molar ratios to prepare a coating liquid; (2) Coating and oxidation sintering: Apply the prepared coating liquid to the surface of the titanium anode forming substrate several times, and dry and oxidize it in turn after each coating. The last coating and drying is followed by sintering.

8. The process for preparing a chlorate electrolytic electrode assembly according to claim 7, characterized in that: In the step (iii) of preparing the coating solution for the titanium anode coating, one or more of the following coating solutions are prepared: Ruthenium titanium coating liquid: a ruthenium titanium coating liquid prepared from ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, butyl titanate, acetylacetone, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:(2-4):(8-12):(100-150); Ruthenium coating liquid: a ruthenium coating liquid prepared from ruthenium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, hydrochloric acid and n-butanol in the ruthenium coating liquid is 10:10:100; Ruthenium platinum tin coating liquid: a ruthenium platinum tin coating liquid prepared from ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, chloroplatinic acid or hydroxylamine platinum, tin tetrachloride, hydrochloric acid and n-butanol in the ruthenium platinum tin coating liquid is (6-8):1:(0.5-1.5):1:(80-100); Ruthenium bismuth indium coating liquid: a ruthenium bismuth indium coating liquid prepared from ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol, wherein the molar ratio of ruthenium trichloride, bismuth nitrate, indium trichloride, hydrochloric acid and n-butanol in the ruthenium bismuth indium coating liquid is 10:(1~2):(1~2):10:

120.

9. The process for preparing a chlorate electrolytic electrode assembly according to claim 7, characterized in that: In the coating and oxidation sintering process of the anode coating preparation in step (iii), coating and oxidation sintering are performed in the following manner: coating the surface of the titanium anode forming substrate with ruthenium titanium coating solution several times, ruthenium coating solution several times, ruthenium platinum tin coating solution several times, and ruthenium bismuth indium coating solution several times, and drying and oxidation treatment are performed in sequence after each coating, and sintering is performed after the last coating and drying.

10. The process for preparing a chlorate electrolytic electrode assembly according to claim 7, characterized in that: In the coating and oxidation sintering process of the anode coating preparation in step (iii), the coating and oxidation sintering are performed according to the following method: First, apply ruthenium titanium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 450℃ for 10 min; then apply ruthenium platinum tin coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 470℃ for 10 min; finally, apply ruthenium bismuth indium coating liquid twice, dry it at 120℃, and then transfer it to a high-temperature oxidation furnace at 480℃ for 10 min. After each coating, dry and oxidize it in turn. After the last coating and drying, sinter it for 20 minutes.

Images