Electrodeposition cell internal part assembly based on 3D printing

Abstract

The utility model discloses an electrodeposition cell internal part assembly based on 3D printing, which comprises a cell panel, and the cell panel is provided with a plurality of anode positioning strip-shaped holes and a plurality of cathode positioning strip-shaped holes which are uniformly and alternately distributed in parallel in the transverse direction. A circle of reinforcing rib is arranged on the edge of the vertical bottom surface of the groove panel, a cathode material distribution main channel is arranged in the reinforcing rib, and the discharging side of the cathode material distribution main channel is further communicated with a plurality of cathode material distribution branch channels arranged in the reinforcing rib. A circle of cathode coaming is arranged on the vertical bottom surface of the cell panel around each cathode positioning strip-shaped hole, and the vertical side wall, close to the cathode positioning strip-shaped holes, of the cathode coaming is provided with material distribution overflow grooves which are communicated with the cathode material distribution sub-channels in a one-to-one correspondence manner. And the vertical bottom surface of the cathode coaming is fixedly connected with a diaphragm frame. According to the utility model, the complex internal parts of the electrodeposition cell can be accurately printed into a whole by adopting the 3D printing technology, so that a series of problems that the positions of a cathode and an anode are not accurate and the like, which are not beneficial to later automatic operation, caused by dispersed processing and field assembly in the prior art are solved.

Description

Technical Field

[0001] This utility model belongs to the field of non-ferrous metal technology, and relates to insoluble anode metal electrodeposition, specifically to an electrodeposition cell internal assembly based on 3D printing. Background Technology

[0002] In recent years, with the continuous development of hydrometallurgy and the stringent environmental protection requirements of metallurgical processes, the development of sulfate-based hydrometallurgy has been very rapid, and the insoluble anode electrowinning process of sulfate systems has also gradually developed. The scale and materials of insoluble anode electrowinning cells have greatly expanded. However, with the increase in scale, the labor intensity of operators has also increased to varying degrees, which urgently requires mechanization and intelligent transformation and upgrading. The materials of electrowinning cells have also evolved from acid-resistant cement to fiberglass-based organic materials. Except for the cathode and anode, the internal components of the cell are mainly made of fiberglass and other organic materials. Fiberglass is currently the mainstream material for electrowinning cells, with little change. The most significant changes are in the internal components, including diaphragm frames, feeders, mist collectors, diaphragm bags, bag supports, and edge clamps. The diaphragm bags, bag supports, and edge clamps, like the anode and cathode, are independent and require disassembly. The diaphragm frames, feeders, mist collectors, and corresponding fasteners are all installed and positioned on-site, but they are manufactured independently by different companies. This results in significant spacing errors between the anode and cathode, which is very detrimental to the automated lifting of the cathode plates, affecting operational efficiency. Furthermore, these independent components are all handmade using organic resin, creating a poor on-site operating environment. The mist collectors, added in recent years due to environmental and occupational health requirements, are relatively crude in processing and installation, also affecting application effectiveness. Traditional drip feeders are difficult to control, leading to uneven material concentration distribution in the cathode area, ultimately resulting in uneven growth of the cathode electrowinning plates, significant differences in surface and internal properties, and even cracking and peeling of the generated plates. Chinese patents, including application number CN201520358200.4, have published parallel flow feeding technology, which has shown advantages over drip feeding methods and has been successfully applied in copper electrolysis production. However, many problems have been found in nickel and cobalt electrowinning production, preventing its widespread application. These problems stem from the fact that traditional cell components are manufactured individually and transported to the site for assembly. Furthermore, the limited space within the cell and the distance between the anode and cathode prevent full utilization of the limited space, hinder precise fixing of each component, and fail to effectively control the continuous and uniform replenishment of the feed solution, whether using unidirectional or bidirectional parallel flow. The addition of a mist collector further occupies space. All these factors affect the optimization of cell component layout, thus impacting overall electrowinning efficiency and quality, and hindering the automation and intelligentization of electrowinning production. Summary of the Invention

[0003] In view of the shortcomings of the existing technology, the purpose of this utility model is to provide an electrodeposition cell internal component assembly to solve the technical problem of inaccurate installation and positioning of anode and cathode plates in the existing technology.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] An electrodeposition cell internal assembly includes a cell panel, on which a plurality of anode positioning strip holes and a plurality of cathode positioning strip holes are arranged in a horizontally parallel and uniform alternating manner.

[0006] The vertical bottom edge of the groove panel is provided with a ring of reinforcing ribs, and a cathode feeding main channel is provided inside the reinforcing ribs. The discharge side of the cathode feeding main channel is also connected to multiple cathode feeding sub-channels provided inside the reinforcing ribs.

[0007] A cathode surround plate is provided on the vertical bottom surface of the groove panel around each cathode positioning strip hole. A material overflow groove is provided on the vertical side wall of the cathode surround plate near the cathode positioning strip hole. The material overflow groove is connected to the cathode material distribution channel in a one-to-one correspondence.

[0008] This utility model also has the following technical features:

[0009] The vertical top surface of the tank panel is provided with an anode exhaust port and an electrodeposition cell electrolyte inlet; the feed end of the cathode feeding channel is connected to the electrodeposition cell electrolyte inlet; the tank panel is also provided with an anode exhaust channel, which is connected to the anode exhaust port.

[0010] The length of the anode positioning strip holes and the cathode positioning strip holes are arranged longitudinally, and the width of the anode positioning strip holes and the cathode positioning strip holes is arranged transversely. The depth of the anode positioning strip holes and the cathode positioning strip holes is arranged vertically, and the anode positioning strip holes and the cathode positioning strip holes penetrate the vertical top and bottom surfaces of the groove panel.

[0011] The cathode enclosure is provided with a diaphragm bag hook on the vertical side wall below the fabric overflow trough, and a diaphragm frame is fixedly provided at the vertical bottom of the cathode enclosure; a diaphragm bag is placed inside the diaphragm frame, and the top of the diaphragm bag is hung on the diaphragm bag hook.

[0012] Compared with the prior art, this utility model has the following technical effects:

[0013] (I) This utility model uses 3D printing technology to accurately print complex electrodeposition cell internals into a whole, which avoids a series of problems that are not conducive to subsequent automated operation, such as inaccurate anode and cathode positions caused by the dispersed processing and on-site assembly of existing technologies. The accuracy of 3D printing can be controlled within 0.1mm, while the accuracy error of existing assembly is greater than 10mm.

[0014] (II) This utility model, by adopting 3D printing technology, avoids the disadvantages of the existing technology, such as high labor intensity and poor environmental hygiene caused by the manual production of fiberglass materials.

[0015] (III) The material selected in this utility model is thermoplastic resin, and the internal parts of the tank can be recycled and reused after they are scrapped, thus avoiding the problem that existing technologies cannot environmentally dispose of obsolete fiberglass products.

[0016] (IV) This utility model uses 3D printing technology to completely isolate the anode and cathode above the liquid surface, thus avoiding the drawback of existing technologies where acid (salt) mist overflows from the cathode due to poor sealing. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the overall structure of an insoluble anodic electrowinning system that can recycle byproducts.

[0018] Figure 2 This is a schematic diagram of the electrodeposition cell structure.

[0019] Figure 3 This is a schematic diagram of the oxygen collection and purification unit.

[0020] Figure 4 This is a schematic diagram of the structure of the electrolyte preparation and neutralization unit.

[0021] Figure 5 This is a schematic diagram of the homogeneous membrane electrodialysis concentration unit.

[0022] Figure 6 This is a schematic diagram of the resin purification unit.

[0023] Figure 7 This is a schematic diagram of the acid-base separation unit.

[0024] Figure 8 This is a front view structural diagram of the internal components assembly.

[0025] Figure 9 This is a schematic diagram of the grooved panel from below.

[0026] Figure 10 This is a schematic diagram showing the assembly relationship between the electrodeposition cell panel and the electrodeposition cell body.

[0027] Figure 11 This is a schematic diagram of the cathode enclosure structure viewed from below.

[0028] Figure 12 for Figure 11 A partially enlarged structural diagram.

[0029] Figure 13 This is a schematic diagram of the fabric overflow channel and the diaphragm bag hook.

[0030] Figure 14 This is a side view of the cathode surround and diaphragm frame.

[0031] Figure 15 This is a schematic diagram of the bag support frame.

[0032] The meanings of the labels in the diagram are as follows: 1-Electrolysis cell unit, 2-Oxygen collection and purification unit, 3-Electrolysis solution preparation and neutralization unit, 4-Homogeneous membrane electrodialysis concentration unit, 5-Resin purification unit, 6-Acid-base separation unit, 7-Pipeline, 8-Valve, 9-Feed pump, 10-Flow meter, 11-Level gauge, 12-Pressure gauge, 13-Pure water pipeline, 14-Anode area, 15-Cathode area.

[0033] 101-Electrodeionization cell body, 102-Cell internal components assembly, 103-Anode exhaust port, 104-Anode liquid overflow port, 105-Electrodeionization cell electrolyte inlet, 106-Electrodeionization electrolyte high-level tank.

[0034] 201-Condenser, 202-Oxygen storage tank, 203-Condensate storage tank, 204-Buffer tank, 205-Concentrated sulfuric acid drying tank, 206-Compressor.

[0035] 301 - Anode liquid storage tank; 302 - Electrolytic solution neutralization and preparation vessel; 303 - Filter press; 304 - Hydroxide preparation vessel; 305 - Filtrate storage tank; 306 - Second filter; 307 - First filter.

[0036] 401 - Homogeneous membrane electrodialysis feed tank; 402 - Homogeneous membrane electrodialysis unit; 403 - Homogeneous membrane electrodialysis concentrated brine storage tank; 404 - Homogeneous membrane electrodialysis dilute brine storage tank; 405 - Pure water preparation pipeline.

[0037] 501 - Resin exchange tower; 502 - Purified concentrated brine storage tank; 503 - Compressed air pipeline.

[0038] 601-Bipolar membrane electrodialysis unit, 602-Bipolar membrane electrodialysis saline temporary storage tank, 603-Dilute alkali circulation tank, 604-Dilute acid circulation tank, 605-Electro-water circulation tank, 606-Flame arrester.

[0039] 10201-Slot panel, 10202-Anode positioning strip hole, 10203-Cathode positioning strip hole, 10204-Reinforcing rib, 10205-Cathode material feeding main channel, 10206-Cathode material feeding sub-channel, 10207-Cathode enclosure plate, 10208-Material overflow trough, 10209-Diaphragm bag hook, 10210-Diaphragm frame, 10211-Anode exhaust channel, 10212-Bag support frame.

[0040] The specific content of this utility model will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0041] It should be noted that, unless otherwise specified, all raw materials and equipment used in this utility model are those known in the prior art.

[0042] Analysis of existing technologies in the background section reveals that they only focus on the main product, metal plates, from electrowinning. The generated byproduct, oxygen, is directly vented, and the byproduct, sulfuric acid, is neutralized directly with sodium carbonate without recovery. The lack of sulfuric acid recovery stems from a lack of feasible technology. The lack of oxygen recovery arises from focusing solely on the surface treatment of acid and salt mists while neglecting their underlying causes and the difficulty in oxygen recovery. Oxygen recovery is challenging because electrowinning cells are open, and currently, all internal components are manufactured separately by different companies and then manually installed and positioned on-site. This makes complete oxygen collection impossible due to the numerous and complex components. The current manual manufacturing and installation methods compromise installation accuracy and sealing effectiveness, hindering on-site automation upgrades. Therefore, standardizing the production of these complex internal components is crucial to solving the problem.

[0043] This invention proposes to directly print the internal components of the electrodeposition cell using thermoplastic polymer materials through 3D printing technology. The feeder, diaphragm frame, mist collector, sealing ring, diaphragm bag hook, and bag support column are integrated onto the overall panel of the electrodeposition cell. Fixing is achieved by embedding the overall panel into the electrodeposition cell along the groove. The groove has a concave structure and uses a non-volatile liquid as the sealing material to ensure that the processing accuracy and installation accuracy error of each component of the anode and cathode are less than 0.1mm.

[0044] In this invention, acid (salt) mist is collected through the gas collection channel in the tank internal assembly and is no longer exhausted by the traditional high-power exhaust fan. Instead, a condenser is installed on the exhaust pipe. When oxygen bubbles, acid mist, salt mist, and water vapor escaping from the anode liquid surface come into contact with the cold interface of the condenser, they will break and condense into liquid and be collected into the receiving tank. The released oxygen and liquid are separated.

[0045] In this invention, when oxygen bubbles and water vapor condense and contract upon cooling, a slight negative pressure is formed around the condenser (the water vapor pressure is 31.164 kPa at 70°C and 0.8731 kPa at 5°C; the pressure difference between the two is the resulting negative pressure of -30.29 kPa; currently, the pressure of forced exhaust fans used in factories is only 1.399–1.767 kPa). Thus, oxygen bubbles and water vapor escaping from the anode liquid surface without the need for negative pressure exhaust will automatically move towards the cold side of the condenser until they hit the wall and separate into gas and liquid. The exhaust gas discharged from the condenser can be dried with sulfuric acid and then compressed to recover high-quality oxygen.

[0046] In this invention, the direct separation and recovery of the byproduct sulfuric acid presents technical challenges. Successful technologies such as diffusion dialysis are only suitable for the metal pickling industry, and other technologies, such as resin exchange, are only suitable for hydrochloric acid systems. This invention addresses the shortcomings of existing technologies by proposing a roundabout approach of "electrodialysis + neutralization." First, sodium hydroxide reacts with the raw metal sulfate to generate metal hydroxide and sodium sulfate. The metal hydroxide neutralizes the anolyte to its equivalence point. The neutralized anolyte is then mixed and returned to the electrowinning process. Sodium sulfate is electrodialyzed to generate sulfuric acid and sodium hydroxide. The sodium hydroxide is recycled, and the sulfuric acid is essentially recovered acid. This not only recovers high-concentration acid but also ensures the quality of the returned anolyte.

[0047] Following the above technical solution, the following are specific embodiments of this utility model. It should be noted that this utility model is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solution of this application fall within the protection scope of this utility model.

[0048] Example 1:

[0049] This embodiment provides a 3D-printed electrodeposition cell internal component assembly, such as... Figure 8 As shown, it includes a tank panel 10201, and an anode exhaust port 103 and an electrowinning electrolyte inlet 105 are provided on the vertical top surface of the tank panel 10201.

[0050] like Figure 9 As shown, the groove panel 10201 has multiple anode positioning strip holes 10202 and multiple cathode positioning strip holes 10203 that are evenly and alternately arranged in a horizontal parallel direction. The length direction of the anode positioning strip holes 10202 and the cathode positioning strip holes 10203 is arranged along the longitudinal direction, and the width direction of the anode positioning strip holes 10202 and the cathode positioning strip holes 10203 is arranged along the horizontal direction. The depth direction of the anode positioning strip holes 10202 and the cathode positioning strip holes 10203 is arranged vertically, and the anode positioning strip holes 10202 and the cathode positioning strip holes 10203 penetrate the vertical top surface and bottom surface of the groove panel 10201.

[0051] like Figure 10 and Figure 11 As shown, a reinforcing rib 10204 is provided around the edge of the vertical bottom surface of the tank panel 10201. A cathode feeding main channel 10205 is provided inside the reinforcing rib 10204. The feed end of the cathode feeding main channel 10205 is connected to the electrodeposition tank electrolyte inlet 105. The discharge side of the cathode feeding main channel 10205 is also connected to multiple cathode feeding sub-channels 10206 provided inside the reinforcing rib 10204.

[0052] like Figure 11 , Figure 12 and Figure 13 As shown, a cathode surround plate 10207 is provided on the vertical bottom surface of the groove panel 10201 around each cathode positioning strip hole 10203. A material overflow groove 10208 is provided on the vertical side wall of the cathode surround plate 10207 near the cathode positioning strip hole 10203. The material overflow groove 10208 is connected to the cathode material distribution channel 10206 in a one-to-one correspondence.

[0053] like Figure 11 , Figure 12 and Figure 13 As shown, a diaphragm bag hook 10209 is provided on the vertical side wall of the cathode enclosure 10207 located below the fabric overflow trough 10208, and a diaphragm frame 10210 is fixedly provided at the vertical bottom of the cathode enclosure 10207; a diaphragm bag is placed inside the diaphragm frame 10210, and the top of the diaphragm bag is hung on the diaphragm bag hook 10209.

[0054] In this embodiment, as Figure 14 As shown, the diaphragm frame (10210) has the same length and width as the cathode baffle, and a height of 800~1200mm. The grid of the diaphragm frame is square, with the size of the square being (80mm~120mm)×(80mm~120mm) and the size of the edge strip of the square being (8mm~12mm)×(8mm~12mm).

[0055] like Figure 14 As shown, an anode exhaust channel 10211 is also provided on the tank panel 10201, and the anode exhaust channel 10211 is connected to the anode exhaust port 103.

[0056] As a preferred embodiment, the thickness of the groove panel 10201 is 10-30 mm.

[0057] As a preferred embodiment, the cathode positioning strip hole 10203 has a length of 600-900mm and a width of 60-80mm, the anode positioning strip hole 10202 has a length of 600-900mm and a width of 15-25mm, and a rubber sealing ring is also provided on the anode positioning strip hole 10202.

[0058] In this embodiment, the spacing between the same electrodes is determined according to the corresponding electrowinning metal and the electrowinning process, such as 140mm for nickel electrowinning.

[0059] As a preferred embodiment, the inner diameter of the cathode fabric channel 10205 is 15-32 mm.

[0060] As a preferred embodiment, the inner diameter of the anode exhaust channel 10211 is 50-100 mm.

[0061] As a preferred embodiment of this invention, such as Figure 15 As shown, a bag support frame 10212 is also installed inside the diaphragm bag.

[0062] In this embodiment, the area around the cathode inlet and outlet, from the tank panel 10201 to 50mm to 100mm below the electrolyte level, is closed.

[0063] In this embodiment, the fabric overflow channel 10208 is an annular channel with a horizontal outer edge to ensure that the added electrolytic electrolyte can overflow evenly. The drainage surface of the fabric overflow channel 10208 is inclined outward to ensure that the electrolytic electrolyte falls into the diaphragm bag.

[0064] In this embodiment, a diaphragm bag hook 10209 is also provided under the fabric overflow trough 10208, and the diaphragm bag hook 10209 is also one of the four support points of the bag support frame 10212.

[0065] In this embodiment, the vertical load-bearing capacity of the groove internal component assembly 102 is 350 kg.

[0066] In this embodiment, when installing the slot inlet assembly 102, simply place the slot inlet assembly 102 into the pre-made slot of the electrodeposition cell body 101 to complete the installation and fixation of the electrodeposition cell body 101.

[0067] In this embodiment, the groove internal component assembly 102 is manufactured using 3D printing technology; the 3D printing process includes the following steps:

[0068] Step S101, Cutting the groove panel:

[0069] The panel is cut from the plastic sheet using a CNC cutting tool of a CNC engraving machine. Then, cathode positioning strip holes 10203, anode positioning strip holes 10202, cathode material feeding main channel opening 10205, and anode exhaust channel opening 10211 are cut on the panel to obtain the groove panel 10201.

[0070] In this embodiment, the plastic is a thermoplastic organic polymer material, which is nylon, polyethylene (PE), polyvinyl chloride (PVC), polypropylene (PP), polystyrene (PS), or acrylonitrile-butadiene-styrene (ABS), preferably nylon. The selected plastic has a melting temperature range of 120 to 240°C, a heat distortion temperature greater than 100°C, and can be immersed in an acidic solution for a long time with a pH of 1.0 to 2.0 and a solution temperature of 50 to 85°C.

[0071] Step S102, one-time additive printing:

[0072] The robotic arm transfers the grooved panel 10201 cut in step S101 to the 3D printer platform. First, print the anode exhaust port 103 and the electrodeposition tank electrolyte inlet 105 on the vertical bottom surface of the grooved panel 10201, which can be printed in the form of a flange. Then, print the reinforcing rib 10204, the cathode feeding main channel 10205 and the cathode feeding sub-channel 10206 on the vertical top surface of the grooved panel 10201.

[0073] Step S103, secondary additive printing:

[0074] Printed cathode baffle 10207, fabric overflow trough 10208 and diaphragm bag hook 10209.

[0075] Step S104, three-stage additive printing:

[0076] Print diaphragm frame 10210.

[0077] Example 2:

[0078] This embodiment provides an insoluble anodic electrodeposition system that can recover byproducts, such as... Figure 1 As shown, the system includes an electrodeposition cell unit 1; as Figure 2 As shown, the electrodeposition cell unit 1 includes an electrodeposition cell body 101, which is divided into multiple alternating anode zones 14 and cathode zones 15. Each anode zone 14 is equipped with an anode and is connected to an anode vent 103 and an anode liquid overflow port 104, which is located on the electrodeposition cell body 101. Each cathode zone 15 has a diaphragm bag and a cathode plate extending into the diaphragm bag. The cathode zone 15 is connected to the electrodeposition liquid inlet 105 of the electrodeposition cell.

[0079] like Figure 1 As shown, the insoluble anodic electrodeposition system for recovering byproducts also includes an oxygen collection and purification unit 2, an electrodeposition solution preparation and neutralization unit 3, a homogeneous membrane electrodialysis concentration unit 4, a resin purification unit 5, and an acid-base separation unit 6.

[0080] like Figure 3As shown, the oxygen collection and purification unit 2 includes a condenser 201, and the condensed gas outlet at the top of the condenser 201 is connected to the oxygen storage tank 202.

[0081] like Figure 4 As shown, the electrolytic electrolyte preparation and neutralization unit 3 includes an anolyte storage tank 301, which is connected to an electrolytic electrolyte neutralization and preparation vessel 302. The hydroxide feed port of the electrolytic electrolyte neutralization and preparation vessel 302 is connected to the filter cake discharge chute of the filter press 303, and the feed port of the filter press 303 is connected to the hydroxide preparation vessel 304.

[0082] like Figure 5 As shown, the homogeneous membrane electrodialysis concentration unit 4 includes a homogeneous membrane electrodialysis raw brine feed tank 401, which is connected to the raw brine inlet of the homogeneous membrane electrodialysis unit 402, and the concentrated brine outlet of the homogeneous membrane electrodialysis unit 402 is connected to the homogeneous membrane electrodialysis concentrated brine temporary storage tank 403.

[0083] like Figure 6 As shown, the resin purification unit 5 includes multi-stage resin exchange towers 501, and the outlets of the multi-stage resin exchange towers 501 are all connected to the purified concentrated brine storage tank 502.

[0084] like Figure 7 As shown, the acid-base separation unit 6 includes a bipolar membrane electrodialysis unit 601. The brine outlet of the bipolar membrane electrodialysis unit 601 is connected to the brine storage tank 602. The dilute alkali circulation outlet of the bipolar membrane electrodialysis unit 601 is connected to the inlet of the dilute alkali circulation tank 603, and the outlet of the dilute alkali circulation tank 603 is connected to the dilute alkali circulation inlet of the bipolar membrane electrodialysis unit 601 to achieve dilute alkali circulation. The dilute acid circulation outlet of the bipolar membrane electrodialysis unit 601 is connected to the inlet of the dilute acid circulation tank 604, and the outlet of the dilute acid circulation tank 604 is connected to the dilute acid circulation inlet of the bipolar membrane electrodialysis unit 601 to achieve dilute acid circulation.

[0085] like Figure 1 and Figure 2 As shown, the outlet of the electrowinning solution neutralization and mixing vessel 302 is connected to the inlet of the electrowinning solution high-level tank 106, and the bottom outlet of the electrowinning solution high-level tank 106 is connected to the electrowinning solution inlet 105 of the electrowinning tank to provide electrowinning solution.

[0086] like Figure 1 and Figure 3 As shown, the anode exhaust port 103 is connected to the air inlet of the condenser 201.

[0087] like Figure 1 and Figure 4 As shown, the anolyte overflow port 104 is connected to the anolyte temporary storage tank 301; the dilute alkali circulation tank 603 is connected to the hydroxide preparation kettle 304.

[0088] like Figure 1 and Figure 5 As shown, the filtrate outlet of the filter press 303 is connected to the feed tank 401 of the homogeneous membrane electrodialysis raw brine; the dilute brine storage tank 602 of the bipolar membrane electrodialysis is connected to the feed inlet of the homogeneous membrane electrodialysis unit 402.

[0089] like Figure 1 and Figure 6 As shown, the homogeneous membrane electrodialysis concentrated brine storage tank 403 is connected to the inlet of the multi-stage resin exchange tower 501; the dilute acid circulation tank 604 is connected to the inlet of the multi-stage resin exchange tower 501.

[0090] like Figure 1 and Figure 7 As shown, the purified concentrated brine storage tank 502 is connected to the raw brine inlet of the bipolar membrane electrodialysis unit 601.

[0091] In this utility model, such as Figure 6 and Figure 7 As shown, the various devices are mainly connected by pipes 7. Each pipe 7 is equipped with a valve 8 and a feed pump 9 as needed. The valves 8 and feed pumps 9 are all commonly known in the art. The valves 8 and feed pumps 9 can be opened or closed according to process requirements. Each device and pipe 7 is equipped with a flow meter 10, a level gauge 11, and a pressure gauge 12 as needed. The flow meters 10, level gauges 11, and pressure gauges 12 are all commonly known in the art.

[0092] As a preferred embodiment of this invention, such as Figure 2 As shown, the top inlet of the high-level electrolytic electrolyte tank 106 is connected to the outlet of the first filter 307, and the inlet of the first filter 307 is connected to the outlet of the electrolytic electrolyte neutralization and mixing vessel 302 to achieve continuous feeding.

[0093] As one specific solution in this embodiment, such as Figure 3 As shown, in the oxygen collection and purification unit 2, the bottom condensate outlet of the condenser 201 is connected to the condensate storage tank 203, the top condensate outlet of the condenser 201 is connected to the buffer tank 204, the buffer tank 204 is connected to the concentrated sulfuric acid drying tank 205, the concentrated sulfuric acid drying tank 205 is connected to the compressor 206 through a check valve, and the compressor 206 is connected to the oxygen storage tank 202.

[0094] As one specific solution in this embodiment, such as Figure 4As shown, in the electrolytic liquid preparation and neutralization unit 3, the feed inlet of the filter press 303 is also connected to the pure water pipeline 13; the filtrate outlet of the filter press 303 is connected to the filtrate storage tank 305, the filtrate storage tank 305 is connected to the feed inlet of the second filter 306, and the discharge outlet of the second filter 306 is connected to the homogeneous membrane electrodialysis raw brine feed tank 401.

[0095] In this embodiment, both the second filter 306 and the first filter 307 are precision filters known in the art.

[0096] As one specific solution in this embodiment, such as Figure 5 As shown, in the homogeneous membrane electrodialysis concentration unit 4, the brine inlet of the homogeneous membrane electrodialysis unit 402 is connected to the homogeneous membrane electrodialysis brine temporary storage tank 404, and the homogeneous membrane electrodialysis brine temporary storage tank 404 is connected to the pure water preparation pipeline 405.

[0097] As one specific solution in this embodiment, such as Figure 6 As shown, in the resin purification unit 5, the inlets of the multi-stage resin exchange towers 501 are all connected to the compressed air pipeline 503; the outlet of the previous stage resin exchange tower 501 is also connected to the inlet of the next stage resin exchange tower 501.

[0098] In this embodiment, the multi-level, interconnected, and independently configured resin exchange towers 501 are configured to operate in a mode where a portion of the resin exchange towers 501 are in operation while the other portion is on standby or undergoing regeneration.

[0099] As one specific solution in this embodiment, such as Figure 7 As shown, in the acid-base separation unit 6, the outlet of the bipolar membrane electrodialysis unit 601 is connected to the inlet of the bipolar membrane electrodialysis tank 605, and the outlet of the bipolar membrane electrodialysis tank 605 is connected to the inlet of the bipolar membrane electrodialysis unit 601 to achieve bipolar water circulation; the bipolar membrane electrodialysis brine temporary storage tank 602 is also connected to the bipolar membrane electrodialysis brine temporary storage tank 602.

[0100] like Figure 7 As shown, the bipolar membrane electrodialysis unit 601's electrode water circulation outlet is also connected to the pure water pipeline 13 for water replenishment; the dilute alkali circulation tank 603 is also connected to the pure water pipeline 13 for water replenishment; and the dilute acid circulation tank 604 is also connected to the pure water pipeline 13 for water replenishment.

[0101] like Figure 7 As shown, the dilute alkali circulation tank 603 is connected to the hydroxide preparation vessel 304 via a check valve; the dilute acid circulation tank 604 is connected to the feed inlet of the multi-stage resin exchange tower 501 via a check valve.

[0102] like Figure 7 As shown, a flame arrester 606 is also installed on the top of the extreme water circulation tank 605.

[0103] As a preferred embodiment, an internal component assembly 102 is installed inside the electrodeposition cell body 101; the internal component assembly 102 is provided with an anode vent 103 and an electrodeposition cell electrolyte inlet 105.

[0104] More preferably, the in-cell assembly 102 adopts the 3D-printed electrodeposition cell in-cell assembly given in Example 1.

[0105] In this embodiment, as Figure 10 As shown, the tank panel 10201 is snapped onto the top opening of the electrodeposition tank body 101. The tank internals assembly 102 and the electrodeposition tank body 101 are sealed by a liquid; the liquid used is glycerol, ethylene glycol or polyethylene glycol; the polyethylene glycol used is a commonly known polyethylene glycol in the art.

[0106] In this embodiment, the anode positioning strip hole 10202 is used to position and install the anode, and the cathode positioning strip hole 10203 is used to position and install the cathode sheet.

[0107] This embodiment can recover byproducts from the insoluble anodic electrowinning process in the sulfate system, with good results and relatively low cost.

[0108] This embodiment utilizes cooling technology to effectively destroy and separate the acid and salt mist carried by oxygen, thus avoiding the high energy consumption problem of using high-power induced draft fans to treat acid and salt mist in existing technologies.

[0109] This embodiment effectively avoids the drawbacks of existing processes that consume large amounts of sodium carbonate by using homogeneous membrane concentration, bipolar membrane separation of acid and alkali, and then using alkali to prepare metal hydroxide to neutralize anolyte. It also recovers a high concentration of acid.

[0110] The material selected for the tank internals in this embodiment is thermoplastic resin. The internals can be recycled and reused after they are scrapped, avoiding the problem of existing technologies being unable to environmentally dispose of outdated fiberglass products.

[0111] Example 3:

[0112] This embodiment provides an insoluble anodic electrowinning process for recoverable byproducts, which uses the insoluble anodic electrowinning system for recoverable byproducts given in Example 2.

[0113] The process includes the following steps:

[0114] Step S1, Electrowinning:

[0115] like Figure 2As shown, the electrowinning solution is continuously added to the electrowinning tank electrowinning solution inlet 105 provided on the inlet assembly 102 through the electrowinning solution high-level tank 106, and the electrowinning solution is evenly added to the diaphragm bags of all cathode areas 15 of the electrowinning tank unit 1 through the material overflow channel 10208 of the inlet assembly 102. The electrowinning solution in the diaphragm bag seeps into the anode area 14 of the electrowinning tank unit 1 through the high level difference, and then the anode solution is introduced into the anode solution temporary storage tank 301 through the anode solution overflow port 104.

[0116] The anode is positioned and installed through the anode positioning strip hole 10202 provided on the tank internal component assembly 102, and the cathode starting plate is positioned and installed through the cathode positioning strip hole 10203 provided on the tank internal component assembly 102. The power is turned on, and the electrowinning process begins.

[0117] Step S2, Oxygen collection and purification:

[0118] like Figure 3 As shown, after electrodeposition begins, metal ions are reduced and deposited on the cathode starting plate in the cathode region 15. Oxygen and sulfuric acid are continuously generated at the anode. The sulfuric acid flows out with the anolyte, and the oxygen and acid mist accumulate in the top of the anode region 14 and enter the condenser 201 through the anode exhaust port 103. The discharged oxygen and acid mist are cooled by the condenser 201, and the condensate is collected in the condensate storage tank 203. The condensed oxygen is buffered by the buffer tank 204 and then dried with concentrated sulfuric acid in the concentrated sulfuric acid drying tank 205. Finally, it is compressed by the compressor 206 to obtain the recovered oxygen.

[0119] Step S3, electrolyte preparation and neutralization:

[0120] Step S301, as follows Figure 4 As shown, in hydroxide preparation vessel 304, metal sulfate is precipitated with the dilute alkali obtained in step S6, and then filtered in filter press 303 and washed with pure water to obtain metal hydroxide.

[0121] Step S302, as follows Figure 4 As shown, the sulfuric acid-containing anolyte in the anolyte temporary storage tank 301 is pumped into the electrolytic liquid neutralization and mixing vessel 302 by the feed pump 9, and then neutralized to the equivalence point by the metal hydroxide generated in step S301. The neutralized new electrolytic liquid is then pumped into the electrolytic liquid high-level tank 106 by the feed pump 9.

[0122] Step S4, homogeneous membrane electrodialysis concentration:

[0123] like Figure 5As shown, the sodium sulfate filtrate obtained by pressure filtration in step S301 is filtered through the second filter 306 and then concentrated by the homogeneous membrane electrodialysis unit 402 to the concentration that the bipolar membrane electrodialysis unit 601 in step S6 can produce for acid and alkali. The brine containing organic matter and insoluble silica suspension retained by the homogeneous membrane of the homogeneous membrane electrodialysis unit 402 is returned to the pure water preparation pipeline 405 and further purified by reverse osmosis or used as softened water.

[0124] Step S5, Resin purification:

[0125] like Figure 6 As shown, the concentrated sodium sulfate aqueous solution obtained in step S4 is added to resin exchange tower 501 for ion exchange to obtain the final purified sodium sulfate solution.

[0126] Step S6, acid-base separation:

[0127] like Figure 7 As shown, the sodium sulfate solution purified in step S5 is passed through a bipolar membrane electrodialysis unit 601 to produce acid and alkali. The resulting dilute alkali is used in step S301 to precipitate metal hydroxide, and the resulting dilute acid is the recovered acid. The resulting brine is returned to the feed water inlet of the homogeneous membrane electrodialysis unit 402 in step S4.

[0128] In step S2, the coolant in the condenser 201 is a coolant at 0 to 15°C, and the cooling area of ​​the condenser 201 is 3 to 5 times the total cross-sectional area of ​​the anodes in the electrodeposition cell unit 1.

[0129] In step S2, the mass concentration of concentrated sulfuric acid is 98 wt.% or 93 wt.%.

[0130] In step S4, the homogeneous membrane electrodialysis unit 402 undergoes superhydrophilic and oleophobic surface treatment. With the help of the electric drive of ions, sodium sulfate is replaced into pure water and the concentration is increased to the concentration required for bipolar membrane electrodialysis. Non-ionic organic matter, silicon-like substances, etc. are retained in the raw water.

[0131] In step S5, the resin used in resin exchange tower 501 is a chelating resin with an exchange capacity of Cu2+ ≥ 0.6 mmol / ml R-Na. The resin exchange tower 501 of this invention uses a known resin exchange tower. In this resin exchange tower, a cation exchange resin is used to further remove divalent and trivalent cations such as iron, calcium, magnesium, nickel, cobalt, manganese, and aluminum contained in the sodium sulfate aqueous solution, thus meeting the requirements of bipolar membrane electrodialysis.

[0132] Example 4:

[0133] This embodiment provides an insoluble anode nickel electrowinning process based on the recyclable byproducts of Embodiment 3 described above.

[0134] In this embodiment, the tank temperature is 75°C and the current density is 220A / m. 3 Electrode spacing 140mm, flow rate 3.0m³ / h 3 / (h.•tank), the electrowinning tank is 7.6 meters long, 1.2 meters wide, and 1.5 meters deep. The heat exchange area of ​​the condenser is 25m². 2 The coolant used is 7℃ water.

[0135] The initial composition (g / L) of the electrolyte is: Ni +2 (90), Na +1 (25) Co +2 (0.002), Cu +2 (0.002), Fe +3 (0.003), Pb +2 (0.000 3), Zn +2 (0.000 3), BO3 -3 (3) SO4 -2 (147.2).

[0136] The composition (g / L) of the anolyte is: Ni +2 (70), Na +1 (25) Co +2 (0.002), Cu +2 (0.002), Fe +3 (0.003), Pb +2 (0.000 3), Zn +2 (0.000 3), BO3 -3 (3) SO4 -2 (114.5), H2SO4 (33.4).

[0137] Contents of each component after concentration and ion exchange: Sodium sulfate content 294 g / L, Ca... +2 + Mg +2 0.016 / L (calculated as Ca), Sr +2 0.011 mg / L, Ba +2 0.006 mg / L, Fe +2 +Fe +3 0.022mg / L, Si0.012mg / L, Al +3 0.04 mg / L, Ni +2 +Co +2 +Mn +2 0.016 mg / L, total other cations 0.033 mg / L, total organic matter (TOC) 0.18 mg / L, oil content 0.02 mg / L.

[0138] The finished electrolytic nickel plate has dimensions of 850mm × 880mm × 8mm and a nickel content of 99.95%.

[0139] After stable operation, the acid mist concentration at a depth of 1 meter on the electrodeposition cell surface was measured to be less than 0.01 mg / m³. 3 After drying, the oxygen concentration was 97.0%.

[0140] The concentration of the saline solution discharged from both homogeneous membrane electrodialysis and bipolar membrane electrodialysis is less than 1%. The acid concentration discharged from the acid and alkali production unit is 98 g / L and the alkali concentration is 80 g / L.

[0141] Example 5:

[0142] This embodiment provides an insoluble anode cobalt electrowinning process based on the recyclable byproducts of Embodiment 3 described above.

[0143] In this embodiment, the tank temperature is 70°C and the current density is 200A / m. 3 Electrode spacing 140mm, flow rate 3.0m³ / h 3 / (h.•tank), the electrowinning tank is 5.8 meters long, 1.2 meters wide, and 1.5 meters deep. The heat exchange area of ​​the condenser is 18m². 2 The coolant used is 7℃ water.

[0144] The initial composition (g / L) of the electrolyte is: Co +2 (80), Na +1 (25) Ni +2 (0.002), Cu +2 (0.001), Fe +3 (0.002), Pb +2 (0.000 1), Zn +2 (0.000 1), BO3 -3 (3) SO4 -2 (130.3).

[0145] The composition (g / L) of the anolyte is: Co +2 (65), Na +1 (25) Ni +2 (0.002), Cu +2 (0.001), Fe +3 (0.003), Pb +2 (0.000 2), Zn +2 (0.000 2), BO3 -3 (3) SO4 -2 (105.9), H2SO4 (24.95).

[0146] Contents of each component after concentration and ion exchange: Sodium sulfate content 354 g / L, Ca... +2 + Mg +2 0.015 / L (calculated as Ca), Sr +2 0.012 mg / L, Ba +2 0.007 mg / L, Fe +2 +Fe +3 0.021mg / L, Si0.011mg / L, Al +3 0.03 mg / L, Ni +2 +Co +2 +Mn +2 0.015 mg / L, total other cations 0.029 mg / L, total organic matter (TOC) 0.16 mg / L, oil content 0.01 mg / L;

[0147] The finished electrolytic cobalt plate has dimensions of 800mm × 850mm × 6mm and a cobalt content of 99.95%.

[0148] After stable operation, the acid mist concentration at a depth of 1 meter on the electrodeposition cell surface was measured to be less than 0.01 mg / m³. 3 After drying, the oxygen concentration was 98.0%.

[0149] The concentration of the saline solution discharged from both homogeneous membrane electrodialysis and bipolar membrane electrodialysis is less than 1%. The acid concentration discharged from the acid and alkali production unit is 117.6 g / L and the alkali concentration is 96 g / L.

Claims

1. A 3D-printed electrodeposition cell internal component assembly, characterized in that, It includes a groove panel (10201), on which a plurality of anode positioning strip holes (10202) and a plurality of cathode positioning strip holes (10203) are evenly and alternately arranged in a horizontal parallel manner. The vertical bottom edge of the groove panel (10201) is provided with a ring of reinforcing ribs (10204), and a cathode feeding main channel (10205) is provided inside the reinforcing ribs (10204). The discharge side of the cathode feeding main channel (10205) is also connected to multiple cathode feeding sub-channels (10206) provided inside the reinforcing ribs (10204). A cathode surround plate (10207) is provided on the vertical bottom surface of the groove panel (10201) around each cathode positioning strip hole (10203). A fabric overflow groove (10208) is provided on the vertical side wall of the cathode surround plate (10207) near the cathode positioning strip hole (10203). The fabric overflow groove (10208) is connected to the cathode fabric distribution channel (10206) in a one-to-one correspondence.

2. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The vertical top surface of the tank panel (10201) is provided with an anode exhaust port (103) and an electrodeposition tank electrolyte inlet (105); the feed end of the cathode material distribution channel (10205) is connected to the electrodeposition tank electrolyte inlet (105); the tank panel (10201) is also provided with an anode exhaust channel (10211), which is connected to the anode exhaust port (103).

3. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The length direction of the anode positioning strip hole (10202) and the cathode positioning strip hole (10203) are both arranged longitudinally, and the width direction of the anode positioning strip hole (10202) and the cathode positioning strip hole (10203) is arranged transversely; the depth direction of the anode positioning strip hole (10202) and the cathode positioning strip hole (10203) is arranged vertically, and the anode positioning strip hole (10202) and the cathode positioning strip hole (10203) penetrate the vertical top and bottom surfaces of the groove panel (10201).

4. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The cathode enclosure (10207) is provided with a diaphragm bag hook (10209) on the vertical side wall below the fabric overflow trough (10208). A diaphragm frame (10210) is fixedly provided at the vertical bottom of the cathode enclosure (10207). A diaphragm bag is placed inside the diaphragm frame (10210), and the top of the diaphragm bag is hung on the diaphragm bag hook (10209).

5. The electrodeposition cell internal component assembly based on 3D printing as described in claim 4, characterized in that, The diaphragm frame (10210) has the same length and width as the cathode baffle, and a height of 800~1200mm. The grid of the diaphragm frame is square, with the size of the square being (80mm~120mm)×(80mm~120mm) and the size of the edge strip of the square being (8mm~12mm)×(8mm~12mm).

6. The electrodeposition cell internal component assembly based on 3D printing as described in claim 4, characterized in that, The diaphragm bag is also equipped with a bag support frame (10212).

7. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The thickness of the grooved panel (10201) is 10-30 mm.

8. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The cathode positioning strip hole (10203) has a length of 600-900 mm and a width of 60-80 mm; the anode positioning strip hole (10202) has a length of 600-900 mm and a width of 15-25 mm.

9. The electrodeposition cell internal component assembly based on 3D printing as described in claim 1, characterized in that, The inner diameter of the cathode fabric channel (10205) is 15-32 mm.

10. The electrodeposition cell internal component assembly based on 3D printing as described in claim 2, characterized in that, The inner diameter of the anode exhaust channel (10211) is 50-100 mm.

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