Regeneration cathode chamber and regeneration cathode system
By designing a regeneration cathode chamber including multi-layer covering, and using a proton membrane layer to isolate anions, the problems of useless electrolysis and fragility in the prior art are solved, and the effect of efficient regeneration and extended service life is achieved.
Patent Information
- Application Number
- CN202420373477.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-02-27
- Publication Date
- 2025-02-18
- Estimated Expiration
- 2034-02-27
AI Technical Summary
In the prior art, the flaky ceramic barrel, as an electrolytic cathode chamber, has problems such as useless electrolysis, fragility, chemical corrosion resistance and frequent replacement, resulting in low regeneration efficiency and high cost.
A regeneration cathode chamber is designed, including a cathode chamber body, a first cover layer, a second cover layer and a third cover layer. The cathode chamber body is provided with a through hole, the first cover layer covers the through hole, the second cover layer is a proton film layer for isolating anions, and the third cover layer is used to protect the second cover layer.
Through the design of the proton membrane layer, anions can be effectively isolated, avoid ineffective regeneration, and improve regeneration efficiency; at the same time, the design of the multi-layer cover layer extends the service life of the proton membrane and reduces the replacement frequency and cost.
Smart Images
Figure CN222499432U_ABST
Abstract
Description
Technical Field
[0001] The utility model belongs to the technical field of surface treatment technology, and in particular relates to a regenerative cathode chamber and a regenerative cathode system. Background Art
[0002] In the production of surface treatment industry, especially in plastic electroplating, steel oxidation coloring, PCB through-hole electroplating, aqueous solutions containing strong oxidants such as chromic acid and permanganate are often used. In continuous production, high-valent chromic acid, potassium permanganate and other oxidants need to be continuously consumed to generate low-valent substances, such as trivalent chromium salts and divalent manganese salts. When the substance accumulates to a certain concentration in the aqueous solution, the aqueous solution of the production line needs to be replaced or scrapped. This results in a large wastewater treatment burden, large waste, and serious environmental pollution.
[0003] To solve this problem, the market currently uses unglazed ceramic barrels as electrolytic cathode chambers to electrolytically oxidize trivalent chromium salts and divalent manganese salts, regenerating them into chromic acid and permanganic acid, respectively, and returning them to the original production line for use. However, this type of unglazed ceramic barrel has a series of disadvantages: 1. The unglazed ceramic diaphragm adopts the traditional electrolytic regeneration principle of large anode and small cathode. Because it cannot block the anions in the working solution from entering the cathode chamber, there is a huge problem of useless electrolysis, which seriously affects the efficiency of electrolytic regeneration; 2. The unglazed ceramic diaphragm is fragile and not resistant to strong corrosion by chemicals. The consumption and replacement frequency is too high, which makes the regeneration cost too high; 3. The installation and replacement are cumbersome. Utility Model Content
[0004] The utility model provides a regenerative cathode chamber and a regenerative cathode system, aiming to solve at least one problem existing in the above-mentioned prior art.
[0005] In a first aspect, the present application is implemented by providing a regenerative cathode chamber, comprising:
[0006] A cathode chamber body for placing an electrolytic solution, comprising a cathode electrode in contact with the electrolytic solution, wherein a target area of the cathode chamber body is provided with a plurality of through holes for conducting current to flow;
[0007] A first covering layer covering a target area of the cathode chamber body and used to cover all the through holes;
[0008] A second covering layer covering the first covering layer and used for isolating negative ions;
[0009] A third covering layer is covered on the second covering layer and is used to prevent external objects of the cathode chamber body from causing damage to the second covering layer.
[0010] In one embodiment, the cathode chamber body comprises:
[0011] cathode chamber;
[0012] A cathode chamber top cover and a cathode chamber bottom cover are respectively arranged at two ends of the cathode chamber cavity.
[0013] In one embodiment, the cathode electrode is disposed in the cathode chamber cavity and is electrically connected to a negative electrode of a power source.
[0014] In one embodiment, a cathode electrode hole is provided on the cathode chamber top cover, one end of the cathode electrode is provided in the cathode chamber cavity, and the other end passes through the cathode electrode hole to be electrically connected to the negative electrode of the power supply.
[0015] In one embodiment, when the cathode chamber cavity is made of stainless steel, the cathode chamber cavity is used as the cathode electrode and is electrically connected to the negative electrode of the power supply.
[0016] In one embodiment, the cathode chamber top cover is movably disposed on the cathode chamber cavity, and the cathode chamber bottom cover is sealed and engaged with the cathode chamber cavity.
[0017] In one embodiment, the first covering layer includes one or more layers, and is wrapped around a target area of the cathode chamber body to completely cover all the through holes.
[0018] In one embodiment, the third covering layer includes one or more layers and is wrapped around the second covering layer to prevent the second covering layer from being damaged by the external object.
[0019] In one embodiment, the second covering layer is formed by winding and covering a single-layer proton membrane, a double-layer proton membrane, or a plurality of proton membranes.
[0020] In a second aspect, an embodiment of the present application provides a regenerative cathode system, comprising:
[0021] A regeneration tank body, wherein a medicine solution is placed in the regeneration tank body;
[0022] At least one is disposed in the regeneration tank body, such as the regeneration cathode chamber described in the first aspect above, wherein an electrolytic solution is placed in the regeneration cathode chamber, and the regeneration cathode chamber is electrically connected to the cathode of the power supply; and
[0023] An anode electrode having one end disposed in the regeneration tank body and the other end electrically connected to the anode of a power source.
[0024] The utility model provides a regenerative cathode chamber and a regenerative cathode system, wherein the regenerative cathode chamber comprises: a cathode chamber body for placing an electrolytic solution, comprising a cathode electrode in contact with the electrolytic solution, a target area of the cathode chamber body being provided with a plurality of through holes for the flow of conductive current; a first covering layer covering the target area of the cathode chamber body and used for covering all the through holes; a second covering layer covering the first covering layer and used for isolating anions; and a third covering layer covering the second covering layer and used for preventing external objects of the cathode chamber body from damaging the second covering layer. In the embodiments of the present application, by utilizing the property of the proton membrane that only positively charged cations are allowed to pass through in the electrolytic solution, the negatively charged anions are isolated outside, and ineffective regeneration can be completely avoided, thereby greatly improving the regeneration efficiency; by wrapping the inner and outer layers of the cathode chamber proton membrane with a first covering layer and a second covering layer, slight physical collisions and frictions will not damage the relatively fragile proton membrane layer, thereby greatly extending the service life of the proton membrane; the effective surface of the proton membrane is fully and non-destructively utilized, so that the working current can efficiently pass through the diaphragm layer; and the cathode chamber adopts a simple and efficient sealing method, so that the solutions inside and outside the membrane layer cannot be physically mixed, but the current can pass efficiently; the entire cathode chamber is independently composed of components, easy to mass produce, easy to install, and can be conveniently applied to various production scenarios. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 This is a cross section of a regenerated cathode chamber provided by an embodiment of the utility model Figure 1 ;
[0026] Figure 2 This is a cross section of a regenerated cathode chamber provided by an embodiment of the utility model Figure 2 ;
[0027] Figure 3 It is a structural schematic diagram of a regeneration cathode chamber body provided by an embodiment of the utility model;
[0028] Figure 4 This is a schematic diagram of the structure of a regenerative cathode chamber system provided by an embodiment of the utility model. Figure 1 ;
[0029] Figure 5 This is a schematic diagram of the structure of a regenerative cathode chamber system provided by an embodiment of the utility model. Figure 2 ;
[0030] Among them, 100, regeneration cathode chamber, 200, regeneration tank body; 300, anode electrode; 1, cathode chamber body; 2, first covering layer; 3, second covering layer; 4, third covering layer; 11, cathode electrode; 12, through hole; 13, cathode chamber cavity; 14, cathode chamber top cover; 15, cathode chamber bottom cover. DETAILED DESCRIPTION
[0031] In order to make the purpose, technical solution and advantages of the utility model more clear, the utility model is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the utility model and are not used to limit the utility model.
[0032] In the description of the present invention, it should be understood that the terms "longitudinal", "radial", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In the description of the present invention, unless otherwise specified, "plurality" means two or more.
[0033] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
[0034] Embodiment 1
[0035] See also Figure 1-Figure 3 The utility model provides a regenerative cathode chamber 100, which comprises: a cathode chamber body 1 for placing an electrolytic solution, comprising a cathode electrode 11 in contact with the electrolytic solution, and a target area of the cathode chamber body 1 is provided with a plurality of through holes 12 for the flow of conductive current; a first covering layer 2 covering the target area of the cathode chamber body 1 for covering all the through holes; a second covering layer 3 covering the first covering layer 2 for isolating anions; and a third covering layer 4 covering the second covering layer 3 for preventing external objects of the cathode chamber body from damaging the second covering layer 3. The second covering layer is a proton membrane layer, and by wrapping the inner and outer layers of the cathode chamber proton membrane with the first covering layer and the second covering layer, slight physical collisions and frictions will not damage the relatively fragile proton membrane layer, thereby greatly extending the service life of the proton membrane.
[0036] The target area may be the area between the position of the side of the cathode chamber body 1 at 30-100 mm from the bottom and the position of the side of the cathode chamber body 1 at 30-100 mm below the liquid level of the top electrolytic solution, such as Figure 2 As shown, it can be the CD area, which can be understood as, the area between the position of 30-100mm from the bottom of the side of the cathode chamber body 1 and the bottom is not provided with a through hole, and the area between the position of 30-100mm below the liquid level line of the top electrolytic solution of the side of the cathode chamber body 1 and the top of the cathode chamber body 1 is not provided with the through hole.
[0037] The total area of the through holes 12 may be larger than a preset proportion of the area of the target region, for example, more than 40%.
[0038] The cathode chamber body 1 may be a cylindrical structure, or may be a cube, a rectangular parallelepiped structure, etc., and may be specifically configured according to actual conditions.
[0039] In one embodiment of the present application, the cathode chamber body 1 comprises: a cathode chamber cavity 13; a cathode chamber top cover 14 and a cathode chamber bottom cover 15 respectively arranged at both ends of the cathode chamber cavity 13. The cathode chamber cavity 13 is assembled by the cathode chamber top cover 13 and the cathode chamber bottom cover 14 to form a cathode chamber body for placing electrolytic dissolution. The through hole 12 is arranged on the target area of the cathode chamber cavity 13.
[0040] The cathode chamber 13 can be made of PTFE (polytetrafluoroethylene), PPS (polyphenylene sulfide), GF (glass fiber), or steel, copper, titanium and other metals sprayed with corrosion-resistant coatings. By using corrosion-resistant materials to prepare the cathode chamber, the cathode chamber will not be corroded by the solution in the working environment and can be used safely for a long time.
[0041] As an implementation of the present application, when the cathode chamber cavity 13 is made of stainless steel, the cathode chamber cavity 13 can be directly used as the cathode electrode 11 and electrically connected to the negative electrode of the power supply. It can be understood that if the cathode chamber cavity is made of stainless steel, it is not necessary to spray the insulating coating, and the stainless steel cavity can be directly used as the electrolysis chamber cathode electrode to directly connect to the negative electrode of the power supply, without the need to set up an electrolysis cathode electrode.
[0042] As another implementation of the present application, the cathode electrode 11 is disposed in the cathode chamber cavity 12 and is electrically connected to the negative electrode of the power supply. It can be understood that the cathode electrode is directly disposed in the accommodating cavity and connected to the negative electrode of the power supply to achieve the aggregation of cations. At this time, the cathode chamber cavity can be made of anti-corrosion materials or sprayed with insulating coatings to improve the corrosion resistance of the cathode chamber cavity.
[0043] The cathode electrode can be made of sheets or rods of copper and its alloy, stainless steel, platinum titanium mesh, etc.
[0044] Furthermore, a cathode electrode hole (not shown in the figure) is provided on the cathode chamber top cover 14, one end of the cathode electrode is provided in the cathode chamber cavity 13, and the other end passes through the cathode electrode hole to be electrically connected to the negative electrode of the power supply. By passing one end of the cathode electrode 11 through the cathode chamber top cover 14, it is possible to prevent the electrolytic solution from damaging the connection between the cathode electrode 11 and the cathode of the power supply.
[0045] Among them, the cathode electrode hole can be set in the middle position of the cathode chamber top cover 14. It can be understood that in order to adapt to different production scenarios, the position of the cathode electrode hole, the position of the cathode electrode, etc. can be adaptively adjusted.
[0046] The power supply may be a direct current power supply, and the cathode of the power supply is a negative electrode of the power supply.
[0047] In one embodiment of the present application, the cathode chamber top cover 14 is movably disposed on the cathode chamber cavity 13, and the cathode chamber bottom cover 15 is sealed and joined with the cathode chamber cavity 13. It can be understood that the edge joint portion of the cathode chamber bottom cover 15 and the cathode chamber cavity 13 is completely sealed to prevent the external solution from being mixed with the electrolytic solution inside the cathode chamber.
[0048] The sealing connection between the cathode chamber bottom cover 15 and the cathode chamber cavity 13 can be achieved by curing epoxy resin glue to seal, or by using a welded pipe head to seal.
[0049] In one embodiment of the present application, the first covering layer 2 may include one or more layers, which are wrapped and covered on the target area of the cathode chamber body 1 to completely cover all the through holes 12. This prevents sharp objects in the accommodating cavity of the cathode chamber body 1 from contacting, wearing or piercing the second covering layer 3, i.e., the proton membrane, thereby improving the service life of the proton membrane.
[0050] The first covering layer 2 can be a corrosion-resistant yarn or mesh wrapped with one to three layers, or multiple layers, to completely cover the location of the through hole 12. The corrosion-resistant yarn or mesh material preferably uses corrosion-resistant and wear-resistant materials such as PTFE (polytetrafluoroethylene), PPS (polyphenylene sulfide), GF (glass fiber), or stainless steel wrapped with PTFE fiber.
[0051] In one embodiment of the present application, the third covering layer 4 may include one or more layers, which are wrapped and covered on the second covering layer 3 to prevent the second covering layer 3 from being damaged. By covering the third covering layer 4 on the outer surface of the second covering layer 3, it is possible to prevent external sharp objects from contacting, wearing or piercing the second covering layer 3, i.e., the proton membrane, thereby improving the service life of the proton membrane. By arranging the proton membrane between the first covering layer 2 and the third covering layer 3, double protection is achieved for both the inside and outside of the proton membrane, and slight physical collisions and frictions will not damage the relatively fragile proton membrane, greatly extending the service life of the proton membrane.
[0052] The third covering layer 4 can be a corrosion-resistant yarn or mesh wrapped with one to three layers, or multiple layers, which can completely cover the second covering layer 3. The corrosion-resistant yarn or mesh material preferably uses PTFE (polytetrafluoroethylene), PPS (polyphenylene sulfide), GF (glass fiber), or stainless steel wrapped with PTFE fiber and other corrosion-resistant and wear-resistant materials.
[0053] In one embodiment of the present application, the second covering layer 3 may be a single-layer proton membrane, a double-layer proton membrane, or a multi-layer proton membrane wound and covered. The covering area of the second covering layer 3 may be greater than the covering area of the first covering layer 2.
[0054] See also Figure 2 In one embodiment of the present application, the regenerative cathode chamber may be a potassium chromate permanganate regenerative cathode chamber. Taking the regenerative cathode chamber as a cylinder as an example, the specific preparation process may include:
[0055] 1. Production of cathode chamber cavity:
[0056] a Cutting: Use PPS (polyphenylene sulfide) pipe with a diameter of 110mm to make a cylindrical cavity, the pipe wall thickness is 3mm, and the pipe length (length AE in the figure) is 550mm;
[0057] b Draw a circular line around the cavity (such as Figure 2 Cross-sectional view): AB=150mm, AC=200mm, AD=500mm, DE=50mm;
[0058] c Opening: Side of cylinder (such as Figure 2 Cross-sectional diagram (part CD) Circular holes are opened every 2 mm, with a diameter of 8 mm, and a total of 34 groups of holes, 30 holes in each group, for a total of 1020 holes;
[0059] d Bottom cover and top cover: The bottom cover of the cylinder is made of a PPS round plate with a diameter of 110mm and a thickness of 8mm, which is cured and sealed with epoxy resin glue; the cylinder is equipped with a movable top cover of the same size, and a 6*90mm rectangular cathode rod hole is reserved in the middle of the top cover;
[0060] 2. The first covering layer (inner layer) on the side of the outer cylindrical body of the cathode chamber cavity:
[0061] Use PPS (polyphenylene sulfide) yarn to wrap two layers, the yarn tension can be 0.8-1.2 kg, and completely cover the circular hole CD of the cathode chamber cavity;
[0062] 3. The second covering layer (middle layer) on the side of the outer cylindrical body of the cathode chamber cavity:
[0063] A 400*700mm perfluorinated proton membrane can be used to wrap 2 layers of the cathode chamber cavity (BE part);
[0064] 4. The third covering layer (outer layer) on the side of the outer cylinder of the cathode chamber cavity:
[0065] PPS (polyphenylene sulfide) yarn can be used to wrap five layers, and the yarn tension can be 1.2-1.8 kg, completely covering the proton membrane (i.e., the BE part);
[0066] 5. Electrolysis cathode rod part:
[0067] The cathode electrode of the electrolysis chamber can be made of a rolled copper strip with a size of 3*88*650mm, which can be fixed in the middle of the top cover.
[0068] Among them, the distance between A and E is the height of the cathode chamber body 1, the CD is the height of the target area, BE can be the second covering layer, that is, the height of the proton membrane, the height of the third covering layer can also be BE or greater than the height of BE, the height of the first covering layer can also be BE, or less than the BE and greater than the height of the CD, or greater than the height of the BE, so that all the through holes 12 are covered.
[0069] In the embodiments of the present application, the property of the proton membrane that only positively charged cations are allowed to pass through in the electrolytic solution is utilized to isolate negatively charged anions, which can completely avoid ineffective regeneration and greatly improve the regeneration efficiency; the inner and outer layers of the cathode chamber proton membrane are wrapped with a first covering layer and a second covering layer, thereby blocking sharp objects inside and outside the cavity, and slight physical collisions and frictions will not damage the relatively fragile proton membrane layer, thereby greatly extending the service life of the proton membrane; the effective surface of the proton membrane is fully and non-destructively utilized, so that the working current can efficiently pass through the diaphragm layer; and the cathode chamber adopts a simple and efficient sealing method, so that the solutions inside and outside the membrane layer cannot be physically mixed, but the current can pass efficiently; the entire cathode chamber is independently formed into components, which is easy to mass produce and install, and can be conveniently applied to various production scenarios.
[0070] Embodiment 2
[0071] See also Figure 4 , Figure 5The utility model also provides a regenerative cathode system, including: a regeneration tank body 200, in which a medicine solution is placed; at least one regeneration cathode chamber 100 arranged in the regeneration tank body 200, such as the one described in the first embodiment, in which an electrolytic solution is placed, and the regeneration cathode chamber 100 is electrically connected to the cathode of a power supply; an anode electrode 300, one end of which is arranged in the regeneration tank body 100 and the other end is electrically connected to the anode of a power supply. In the present application, by placing a medicine solution in the regeneration tank body 100 and an electrolytic solution in the regeneration cathode chamber, and then transmitting a positive current and a cathode current to the anode electrode and the cathode electrode respectively, anions are blocked outside the proton membrane and cannot pass through the proton membrane to enter the cathode chamber, thereby greatly improving the electrolysis efficiency.
[0072] The anode electrodes 300 may include two, which are respectively disposed on both sides of the regeneration cathode chamber 100 .
[0073] Among them, Figure 5 As shown, the regeneration cathode chamber 100 may include multiple regeneration cathode chambers 100, which may be connected in series and arranged side by side in the regeneration tank body 200. An anode electrode 300 is arranged on both sides of each cathode chamber 100. It can be understood that the regeneration cathode chamber 100 may include 2, 3, 4, etc., which may be arranged according to actual conditions, and the present application does not limit it here.
[0074] In an implementation scenario of the present application, when the regeneration cathode chamber is used in the regeneration cathode system of chromic acid in the roughening solution of plastic electroplating, that is, a plurality of the regeneration cathode chambers 100, for example, 3, can be placed side by side in the regeneration tank body 200, and the tops of the cathode rods of the cathode chambers are all connected to the negative pole of the DC power supply. The internal dimensions of the regeneration tank body 200 are: 500*500*500mm, and the liquid level control depth is 400mm. Then, the solution is placed in the regeneration tank body 200. For example, 100 liters of the roughening tank solution of the plastic electroplating production line can be placed in the above-mentioned regeneration tank body 200 for testing to analyze the roughening solution. The initial contents of the chemical bath components are as follows: 313 g / L chromic acid, 321 g / L sulfuric acid, and 72 g / L trivalent chromium; 3 cathode chambers are regenerated using chromic acid potassium permanganate in the middle of the regeneration tank body 200, and the electrolyte in the cathode chamber is 300 g / L sulfuric acid; the anode electrodes 300 on both sides of the regeneration tank body 200 can use lead-tin alloy anode plates with a size of 12*120*650 mm, with a total of three pairs and six strips, connected to the positive pole of a DC power supply; power is turned on to electrolyze and oxidize trivalent chromium to regenerate chromic acid; voltage: 5 volts, current: 500 amps, at this time, the electrochemical reaction near the anode electrode 300 is as follows:
[0075] Cr 3+ -3e+4H2O=H2CrO4+6H +
[0076] 2OH - -2e=O2↑+2H +
[0077] The electrochemical reaction near the cathode electrode 11 is as follows:
[0078] 2H + +2e=H2↑
[0079] The trivalent chromium and chromic anhydride content is tested every 8 hours, and the data are as follows:
[0080] Electrolysis time (hours) Trivalent chromium (g / L) Chromic anhydride (g / L) 0 72 313 8 48.35 357.11 16 27.13 395.71 24 9.71 427.17
[0081] From the above data analysis, it can be seen that since hexavalent chromium exists in anion CrO4 - It only exists outside the cathode chamber and cannot pass through the proton membrane to enter the cathode chamber and cannot obtain electrons at the cathode. Therefore, the system using the cathode chamber can efficiently oxidize the trivalent chromium in the bath solution to generate hexavalent chromium compound chromic acid, and the generated chromic acid only exists outside the cathode chamber, thereby greatly improving the electrolysis efficiency.
[0082] In an implementation scenario of the present application, when the regeneration cathode chamber is used in a regeneration cathode system of chromic acid using stainless steel oxidation solution, that is, multiple regeneration cathode chambers 100, for example, 3, can be placed side by side in the regeneration tank body 200, and the tops of the cathode rods of the cathode chambers are all connected to the negative pole of the DC power supply. The internal dimensions of the regeneration tank body 200 are: 500*500*500mm, and the liquid level control depth is 400mm. Then, the solution is placed in the regeneration tank body 200. For example, 100 liters of the oxidation tank solution of the stainless steel oxidation blackening production line is taken and placed in the above regeneration tank body 200. The test was conducted in the regeneration tank 200, and the initial contents of the components of the oxidation tank solution were analyzed as follows: 91 g / L of chromic acid, 410 g / L of sulfuric acid, and 89 g / L of trivalent chromium; 3 cathode chambers were regenerated using chromic acid potassium permanganate in the middle of the regeneration tank 200, and the electrolyte in the cathode chambers was 300 g / L of sulfuric acid; the anode electrodes 300 on both sides of the regeneration tank 200 used lead-tin alloy anode plates, which could be 12*120*650 mm in size, with three pairs of six strips in total, connected to the positive pole of a DC power supply; the trivalent chromium was electrolytically oxidized to regenerate chromic acid; the voltage was 5 volts, and the current was 500 amps. The electrochemical reaction near the anode electrode 300 is as follows:
[0083] Cr 3+ -3e+4H2O=H2CrO4+6H +
[0084] 2OH - -2e=O2↑+2H +
[0085] The electrochemical reaction near the cathode electrode 11 is as follows:
[0086] 2H + +2e=H2↑
[0087] The trivalent chromium and chromic anhydride content is tested every 8 hours, and the data are as follows:
[0088] Electrolysis time (hours) Trivalent chromium (g / L) Chromic anhydride (g / L) 0 89 91 8 64.53 137.35 16 41.58 181.66 24 22.65 221.03
[0089] From the above data analysis, it can be seen that since hexavalent chromium exists in the anion (CrO4)2-, it is outside the cathode chamber and cannot pass through the proton membrane to enter the cathode chamber and cannot obtain electrons at the cathode; therefore, the system using this cathode chamber can efficiently oxidize the trivalent chromium in the bath solution to generate a hexavalent chromium compound, chromic acid, and the generated chromic acid only exists outside the cathode chamber, thereby greatly improving the electrolysis efficiency.
[0090] In an implementation scenario of the present application, when the regeneration cathode chamber is used in the regeneration system of potassium permanganate for PCB through-hole electroplating desmear solution, that is, multiple regeneration cathode chambers 100, for example, 3, can be placed side by side in the regeneration tank body 200, and the tops of the cathode rods of the cathode chambers are all connected to the negative pole of the DC power supply. The internal dimensions of the regeneration tank body 200 are: 500*500*500mm, and the liquid level control depth is 400mm. Then, the solution is placed in the regeneration tank body 200. For example, 100 liters of the desmear tank solution of the PCB through-hole electroplating production line is taken and placed in the above regeneration tank body 200. The tank body 200 is tested and analyzed to have the following initial contents of the components of the desmear tank solution: 47 g / L potassium permanganate, 53 g / L sodium hydroxide, and 63 g / L divalent manganese; three regeneration cathode chambers of the present invention are used in the middle of the regeneration tank body 200, and the electrolyte in the cathode chamber is 70 g / L sodium hydroxide; the anode electrodes 300 on both sides of the regeneration tank body 200 use 316 stainless steel plates as anodes, and the size can be 2*450*550 mm, with a total of 2 plates, connected to the positive pole of a DC power supply; power is turned on to electrolyze and oxidize divalent manganese to regenerate potassium permanganate; voltage: 7 volts, current: 400 amps. The electrochemical reaction near the anode electrode 300 is as follows:
[0091] Mn 2+ -4e+4H2O=(MnO4) 2- +8H +
[0092] (MnO4) 2- -e=(MnO4) -
[0093] The electrochemical reaction near the cathode electrode 11 is as follows:
[0094] 2H + +2e=2(OH) - +H2↑
[0095]
[0096]
[0097] From the above data analysis, it can be seen that hexavalent manganese and heptavalent manganese exist in anions (MnO4) 2- , (MnO4) - In the process, outside the cathode chamber, the protons cannot penetrate the proton membrane into the cathode chamber and cannot obtain electrons at the cathode; therefore, the system using the cathode chamber can efficiently oxidize the divalent manganese in the bath solution to generate potassium permanganate.
[0098] It can be seen from the above implementation scenarios that the regenerated cathode chamber can be applied to the trivalent chromium and divalent manganese solution regeneration cathode system with good effect, and can be widely used in plastic electroplating production lines, steel oxidation production lines, PCB through-hole electroplating production lines, chromium slag and manganese slag recovery production lines, etc., in various production regeneration processes that convert low-valent anions into high-valent anions (or the opposite electrochemical reaction), and its application scenarios are extremely wide.
[0099] In the embodiments of the present application, by utilizing the property of the proton membrane that only positively charged cations are allowed to pass through in the electrolytic solution, the negatively charged anions are isolated outside, and ineffective regeneration can be completely avoided, thereby greatly improving the regeneration efficiency; by wrapping the inner and outer layers of the cathode chamber proton membrane with a first covering layer and a second covering layer, sharp objects inside and outside the cavity are blocked, and slight physical collisions and frictions will not damage the relatively fragile proton membrane layer, thereby greatly extending the service life of the proton membrane; the effective surface of the proton membrane is fully and non-destructively utilized, so that the working current can efficiently pass through the diaphragm layer; and the cathode chamber adopts a simple and efficient sealing method, so that the solutions inside and outside the membrane layer cannot be physically mixed, but the current can pass efficiently; the entire cathode chamber is independently composed of components, easy to mass produce, easy to install, and can be conveniently applied to various production scenarios.
[0100] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A regenerative cathode chamber, characterized in that: The regenerated cathode chamber comprises: A cathode chamber body for placing an electrolytic solution, comprising a cathode electrode in contact with the electrolytic solution, wherein a target area of the cathode chamber body is provided with a plurality of through holes for conducting current to flow; A first covering layer covering a target area of the cathode chamber body and used to cover all the through holes; A second covering layer covering the first covering layer and used for isolating anions; A third covering layer is covered on the second covering layer and is used to prevent external objects of the cathode chamber body from causing damage to the second covering layer.
2. The regenerated cathode chamber according to claim 1, characterized in that: The cathode chamber body comprises: cathode chamber; A cathode chamber top cover and a cathode chamber bottom cover are respectively arranged at two ends of the cathode chamber cavity.
3. The regenerated cathode chamber according to claim 2, characterized in that: The cathode electrode is disposed in the cathode chamber and is electrically connected to the negative electrode of the power supply.
4. The regenerated cathode chamber according to claim 3, characterized in that: A cathode electrode hole is arranged on the cathode chamber top cover, one end of the cathode electrode is arranged in the cathode chamber cavity, and the other end passes through the cathode electrode hole and is electrically connected to the negative electrode of the power supply.
5. The regenerated cathode chamber according to claim 2, characterized in that: When the cathode chamber cavity is made of stainless steel, the cathode chamber cavity is used as the cathode electrode and is electrically connected to the negative electrode of the power supply.
6. The regenerated cathode chamber according to claim 2, characterized in that: The cathode chamber top cover is movably arranged on the cathode chamber cavity, and the cathode chamber bottom cover is sealed and connected with the cathode chamber cavity.
7. The regenerated cathode chamber according to claim 1, characterized in that: The first covering layer includes one or more layers and is wrapped around a target area of the cathode chamber body to completely cover all the through holes.
8. The regenerated cathode chamber according to claim 1, characterized in that: The third covering layer includes one or more layers and is wound around the second covering layer to prevent the second covering layer from being damaged by the external object.
9. The regenerated cathode chamber according to claim 1, characterized in that: The second covering layer is formed by winding and covering a single-layer proton membrane, a double-layer proton membrane, or a multi-layer proton membrane.
10. A regenerative cathode system, characterized in that: The regenerative cathode system comprises: A regeneration tank body, wherein a medicine solution is placed in the regeneration tank body; At least one regeneration cathode chamber according to any one of claims 1 to 9 is disposed in the regeneration tank body, wherein an electrolytic solution is placed in the regeneration cathode chamber, and the regeneration cathode chamber is electrically connected to a power supply cathode; and An anode electrode having one end disposed in the regeneration tank body and the other end electrically connected to the anode of a power source.