TW200411963A - Electrolysis process and cell for use in same - Google Patents

Abstract

An electrolysis process for the recovery of metal from an aqueous solution is defined. On electrolysing the solution metal is caused to deposit on a deposition surface of a cathode. The process includes the step of inducing a non-uniform current density across the deposition surface so as to form areas of high current density interspaced by areas of low current density. The difference between the areas of high current density and low current density is sufficient to cause metal deposition to be concentrated on the areas of high current density so as to promote non-uniform deposition of metal across the deposition surface. An electrolysis cell for the electro-recovery of metal from an aqueous solution is also defined. The cell includes a cathode which includes a deposition surface on which metal is deposited on electrolysing of the aqueous solution. In operation of the cell, the deposition surface has a non-uniform electrical field having areas of strong electrical field interspaced by areas of weak electrical field. The difference between the areas of strong electrical field and weak electrical field is sufficient to cause metal deposition to be concentrated on the areas of high electrical field so as to promote non-uniform deposition of metal on the surface.

Description

200411963 玖, Description of invention:

[Minghu Jinshen " Lengbei J FIELD OF THE INVENTION The present invention relates generally to an electrolytic method for reducing metal from an aqueous solution, and an improved cathode which can be used in one of the methods. The main application of the present invention is related to the reduction of copper, but the present invention also has the same electric reduction function in other metals such as nickel, lead, zinc and the like. [Prior Art Background of the Invention] The method of leaching out alkali metals from ore and subsequently concentrating them by reduction of alkali metals in electrolytic cells is well known in the field of water-liquid metallurgy. One case was disclosed in Australian Patent Application No. 42999/93 (669906). The method is multi-stage, and after leaching the mineral in a gaseous medium, a solution stream is generated. The solvent stream is electrolyzed in an electrolytic cell to reduce the metal from the solution, which is deposited on the cathode of the battery. At the south current density, high-purity dendritic copper is generated on the cathode. In the past, it was necessary to regularly remove the cathodes to strip the metal-deposited plating, so that the current efficiency in the tank could be maintained. The ideal electro-metallurgical operation depends on the purity of the dissolving fluid flow and the general electrolytic cell parameters, such as current density and stripping cycle. Battery configuration and degree of agitation. It is therefore an object of the present invention to improve the efficiency of the electrometallurgical operation. In particular, an object is to provide an electrolytic method and an electrolytic cell structure that can better control the current slack 'through the deposition surface of the cathode to facilitate the formation and removal of the metal deposits. 5 200411963 [Summary of the Invention] Summary of the Invention A first aspect of the present invention provides an electrolytic method capable of reducing metal in an aqueous solution, and the solution is electrolyzed to cause metal to be deposited on a cathode 5 deposition surface. The steps of the method It includes causing a non-uniform current density to pass through the deposition surface such that areas with high current density are separated by areas with low current density. The difference between these high and low current densities is sufficient to make Metal deposits are concentrated on these areas of high current density, and can promote inconsistent metal deposition on the entire deposition surface. 10 In the context of the present invention, the deposition surface may be a single structure, or may be composed of multiple elements, which must be spaced apart or contact each other in one direction. Providing a non-uniform current density on the deposition surface will form a mechanism whereby the deposition of metal on the surface can be controlled. In particular, it enables metal deposition to be concentrated in certain areas (ie, high current density areas), thereby contributing to uneven deposition over the entire surface. The uneven deposition of the metal is advantageous because it can be easily removed from the cathode and facilitates the metal reduction process. Preferably, the metal deposition can be extremely severe at 20 locations in the high current density region, so that the metal deposition can be effectively intermittently distributed on the deposition surface. Preferably, the metal deposition concentration is higher than 80%, and more preferably higher than 95% at the high current density region when the battery is operated. Preferably, the high and low current density regions extend along the surface in one direction and alternately pass through the surface in an opposite direction. In this way, the 6 metals will be deposited in a series of straight strips, which is particularly ideally suited for removal with a wiping action, as described in detail. Preferably, the electrolysis method can cause a non-uniform current density across the entire deposition surface by providing a cathode. When the cathode is operated, the cathode will cause an uneven electric field with a strong electric field region and a weak electric field region. With this design, these strong electric field areas will form high current density areas, while weak electric field areas will form low current density areas. The non-uniform electric field can be formed by a variety of mechanisms, including the formation of the surface, and changing the resistance between the cathode and anode along the deposition surface, or a combination of the two mechanisms described above. The shape of the surface affects the electric field and is related to its surface curvature. The electric field is always parallel to the surface, so the sharp edges or peaks on the deposition surface will cause a higher electric field area than a flat or concave area. Its resistance can be changed by using different materials along the deposition surface (for example, forming sections with insulating material), or by changing the length of the current path between the cathode and anode. In a preferred form, the non-uniform electric field is generated on the deposition surface by the shape of the surface, and in particular, a series of alternate ridges and grooves are formed on the entire surface. Due to this shape, the battery will generate a higher electric field along the ridges compared to the grooves during operation. In addition, compared with the grooves, the current path length is shorter at the ridges, so a situation is caused that the resistance at the ridges is lower than at the grooves. The change in current density on the deposition surface can be set to have a sharp demarcation between high and low current density regions, or it can form a gentler and gradually change between high and 200411963 low current density regions. Conversion Department. Applicants have found that causing a gradual transition between these high and low current density regions will still provide a good deposition pattern and may promote discontinuous growth on the deposition surface. In particular, the applicant has found that if a cathode is used which contains 5 ridges and grooves on the deposition surface, but the ridges and grooves are not included in the-anxious transition section, then the highest current density and the lowest current density There will be relatively gentle changes, which can provide excellent results. This design will also cause a second effect 'to help metal deposition concentrate on the convex ridges, which will be detailed later' and also make it easier to remove the metal, compared to these convex 10 ridges and grooves The sharp transition between them may form inaccessible areas, which will allow easier valley access to the entire deposition surface. In the Chevrolet form, 'the battery is operable to remove copper from an aqueous solution', the current density range in the region of high current density is 500 to 2,500 A / m2, and more preferably i, 0.00 A / m2. The current density range of 15 in the low current density region is 0 to 2050 A / m2, and more preferably 0 to 500 A / m2. When transitioning between the highest current density region and the lowest current density region, the dividing line ® between the “high current density region,” and the “low current density region,” may be a little fuzzy. In this case, the transition region can be regarded as a medium current region, which is between the adjacent "high current density region" and "low current density region". 20 Preferably, the method further includes One step is to remove the deposited metal from the deposition surface by a component passing through the surface. Preferably, the high and low current density regions extend along the surface in one direction, and In the case where the opposite direction alternates across the surface, the element will move in the direction in which the high and low current density regions extend. 8 200411963 Preferably, the deposited metal, when removed by the element, The current is still maintained in the aqueous solution. In this way, the process can continue. In yet another aspect, the present invention relates to an electrolytic battery that can electrolytically reduce metal in an aqueous solution. The battery includes a cathode having a sinker. 5 surface, which can be used for metal deposition on the aqueous solution during electrolysis; and during the operation of the battery, the deposition surface has an uneven electric field, and a high electric field region is formed separated by a low electric field region. The difference between these high and low electric field regions is sufficient to allow metal deposits to concentrate on these high electric field regions, so that the metal is unevenly deposited on the surface. 10 Preferably, the high And the low electric field region will extend along the surface in one direction and alternately pass through the surface in the opposite direction. In a particularly preferred form, the deposition surface of the cathode includes a ridge and a groove arranged alternately. Array, where the ridges will form a high electric field area, and the grooves will form a low electric field area. 15 Set the deposition surface as an array of ridges and grooves in turns, which will intermittently deposit the forming metal on the cathode The operation has considerable benefits. Usually these designs will promote the deposition of metal such as dendritic growth on the ridges. Advantageously, the formed tree structure will be easier to remove (as described later). Provide the shape as above At the beginning of the operation of the battery, the appropriate non-uniform current density of 20 will not only cause metals such as trees to be concentrated on the ridges, but it will also help to maintain time while the process continues It should be understood that when the metal is deposited on the deposition surface, the deposited metal will form an extension of the deposition surface. One of the advantages of the ridge and groove design is that when the tree structure grows on the ridge When they are on, they will "shield" the grooves, this 9 can further prevent the metal from depositing in the grooves. Moreover, the aqueous solution will also tend to stagnate at the scales, which will further hinder the metal Deposited in the groove. In the test towel made by the applicant, using the alternating shape of ridges and grooves will allow more than 98.8% of the metal to be deposited on the ridges of the deposition surface. The ridges and grooves can achieve some advantageous effects, but the applicant has found that a regular shape can also have good results, in which the surface between the top of the convex ridge and the bottom of the groove is linear, and the phase There is an internal angle of about 60 ° between adjacent surfaces. It is also preferable that the pitch between adjacent ridges is about 10 ~ 40mm, and more preferably 15 ~ 25mm; and between the ridges and grooves. The depth of the gap is about 8 to 32 mm, and more preferably 12 to 20 mm. A deposition surface with these characteristics has been found to cause space-like metal deposition. Yet another advantage is that the shape enables the surface to be completely cleaned without causing "hot spots" of current density, which may result in impure metal deposition. When depositing, if the current density is too high in one place, the concentrate will be polarized (it will be generated around the generated deposit. When this happens, it will be deposited on the deposited metal (such as copper) Relatively high impurity content is generated in the reactor. Therefore, it is important to control the current density. The advantage of the above-mentioned shape is that the high current density areas for accumulated metal deposits will occupy the total area of the cathode. A large part (that is, about 25 to 35% of the total area of the deposition surface). With this design, the current will be able to maintain a fixed flow rate, regardless of whether the surface has no metal deposits or has begun to deposit. When starting the battery, it is not necessary to increase the current, because the shape itself does not tend to cause a strong "hot spot" of the current density, which is easy to cause problems when starting metal deposition in 200411963.-Especially preferred In the form, the cathode includes a thin sheet having at least a major surface capable of forming a deposition surface of the cathode, and the thin sheet is preformed without alternating ridges and grooves. Therefore, the thin The sheet may form a corrugated shape. Fortunately, 'the pre-forming operation is done by bending the sheet, but it is also known to use any other suitable manufacturing method, such as stamping, rolling, forging, prayer' or It is made by combination, etc. In a particularly preferred form, the sheet is made of titanium or similar antioxidant material. Although other antioxidant materials can also be used, such as Gu, stainless steel, age-resistant metal alloy Etc., but titanium is the best, @ has excellent-, oxidation resistance, and can form alloy chains with metals such as copper, and it is easier to obtain. Another advantage of using wave shape is that it helps Maintain the dimensional stability of the sheet. This design can help to overcome the shortcomings of the conventionally designed sheet cathode which is easy to bend f Zhao. Also, when metal deposits grow on the sheet in a tree or u-like shape, The dimensional stability of the sheet is available for the wiping method to easily remove deposits from the sheet. Applicants have found that a titanium sheet having a thickness of about 16 mm can provide sufficient dimensional stability for this process. Preferably, the sheet The sheet will be used to attach to a Conductive headstock. The headstock will support the cathode and supply electrons during use. In one example, the opposite major surface of the bent sheet will also be used as a deposition surface during the cathode operation. In a variation The cathode is formed by a composite structure, and the conductive element extends along the sheet. The conductive element is electrically connected to the sheet π 200411963, and is used to supply electrons to the deposition surface during the electrolysis process. One advantage of using a conductive element that extends along the sheet is to minimize resistive voltage drops, which occurs when electrons are supplied from only one edge of the sheet. A second advantage of using a conductive element is that It can have sufficient size to provide rigidity to the thin 5 sheets and help maintain the dimensional stability of the cathode. Therefore, the composite structure design will be able to use thinner sheet-like members as the deposition surface. In a preferred form, the cathode will include a second sheet connected to the first sheet, and a main surface will form a second deposition surface of the cathode; the second sheet will be formed in advance Alternate ridges and grooves are provided along the deposition surface. Preferably, the second sheet is connected to the first sheet of the cathode to form a plurality of cavities extending in the direction of the ridges and grooves. At least some of these cavities are capable of receiving conductive elements of the cathode. In a preferred form, the wiping device is operable to pass through the deposition surface of the cathode while removing the deposition material thereon. In a particularly preferred form 15, where the cathode contains convex ridges and groove shapes, the wiping device may include a plurality of convex portions that can protrude into corresponding grooves on the deposition surface. In a preferred form, the protrusions are made of a ceramic material, but they can also be made of any other resistant material. In a preferred form, the protrusions are movable between a first and a second position 20 and are operable to pass through the surface in the two positions. In the first position, the element will be in contact with or close to the deposition surface, and almost all of the deposited material will be removed from the surface. In the second position, preferably, the element can be separated from the deposition surface, and the deposition material protruding from the deposition surface by a predetermined distance can be removed. 12 5 5-A method for use in any one of the above, a method for use in any of the above, or a cathode in an electrolytic cell. In yet another aspect, the present invention relates to what form of wiping system in an electrolytic cell. The present invention relates to a kind of cathode for use in electric life = 2 = a cathode for reducing metal, the cathode contains 1 10

The shape is: two = most of the grooves are spaced apart, and they are put on the shoulders where the battery is known to concentrate the metal deposits, and a uniform metal deposit is formed on the surface. Brief description of the drawings Although many forms may be included in the scope of the present invention, the preferred embodiment of the present invention will be exemplified with reference to the following formula, where: Figure 1 is a schematic diagram of a process for processing and reducing copper Figure 2 is a cross-sectional view of an electrolytic cell according to the present invention, and the wiper group of the battery 15 is in a closed position; Figure 3 is a side cross-sectional view of the battery of Figure 2;

Figure 4 is a cross-sectional view of the battery of Figure 2, and the wiper is in the open position; Figure 5 is a detailed view of the connecting rod assembly of the battery of Figure 2; 20 Figure 6 is the battery of Figure 2 Fig. 7 is an enlarged schematic view showing the wiper group in the open position on the top of the cathode plate; Figure 8 is an enlarged view of the wiper group in the closed position; Figure 9 is used in the battery of Figure 2 The front view of the cathode plate of Figure 13; Figure 10 is an end view of the plate of Figure 9; _ Figure ^ is a three-dimensional schematic diagram of the cathode of the battery abutting against the battery of Figure 2;丨 丨 Cross-sectional view of the XII_XII cross-sectional view; FIG. 13 is a perspective view of a tab of a wiper used in the battery of FIG. 2; and FIGS. 14 and 15 are examples of modification of the tab structure shown in FIG. The third level is the three-dimensional intention of the cathode used in the battery of Figure 2; and

Fig. 17 shows the cathode of Guanguan along the χνιι_χνπ section line __. t Cold type; J Detailed description of the preferred embodiment In Figure 1, a block diagram of a combined process is shown, which includes metal and Hexian 1G4. In a preferred form of the process, copper sulfide_06 will be used to make M-rich metals, in which these metals will be dissolved by oxidation with an impurity. In a preferred form, the solution includes a complex compound, which will serve in the anode of the subsequent electrolysis stage and will be returned to the leaching stage as part of the electrolytic recovery. Metals dissolved in the desired oxidation state are removed from the leachate at various stages. The leachate is passed through peaks to remove unwanted solids, such as stone melon and iron oxide. The leaching ㈣ will in turn purify η to remove metals (such as silver and mercury) which may be dyeable for subsequent conversion. The dyed metal may be in the form of a metal oxide or carbonate. The purified leachate may be sent to an electrolysis stage 104, which may include a majority of electrolytic cells connected in series and / or in parallel with each other. In each group, different metals can be made. Typically, copper metal will be electrically reduced in a first battery pack while other metals such as silicon, lead, nickel, etc. will be reduced in subsequent or parallel gamma battery packs. The electrolysis process is typically operated such that a highly oxidizing / filtering agent (e.g., a complex compound) is generated on the anode. The used electrolytic shellfish (anolyte) plutonium will be recovered to the leaching stage and will contain the highly oxidizing agent 'which will participate in subsequent countercurrent leaching. As such, the process operates sustainably. The present invention is related to the optimization of the electroreduction of these metals, and related to major design improvements in the electrolysis process, including improvements in the design and shape of the cathode.凊 Referring to Figs. 2 to 5, the electrolytic cell 10 for the manufacturing process 100 is a series of cathode plates u and the like are set in the electrolytic cell tank 50 and separated by the anodes 2. The electrolyte fed into the battery will allow current to flow between the anode and cathode. The outer surfaces 13, 14 and the like of each cathode will form the deposition surface of the battery ' As will be described later, 'these cathode plates have a wave plate shape and have alternately arranged ridges and grooves, etc.', which can affect the pattern of metal deposition on each of the deposition surfaces 13 and 14. The battery 10 includes a wiping system 15 which contains a plurality of wiping groups 16 which are operatively inserted between each cathode and anode, so that the wiping members of each wiping group 16 can be operated to move through the cathodes. Deposition surfaces 13 and η are used to remove metal deposits. The erasing members 17 are set to be able to wipe down the deposition surfaces 13 and 14 at a predetermined period, so that the peeled metal drops to the bottom of the battery 10 and is transferred to a conveyor belt 18 It is removed by the battery 10. In order to achieve this wiping effect, the wiping system 15 includes two main movements. The first is a vertical movement that enables the wiping groups 16 to move between the top and bottom of each cathode ^, and the second The wiper 17 in each group 16 can be moved from an open position (as shown in FIG. 7) to a closed position (as shown in FIG. 8). The wiping groups 16 are provided on a frame 32, and the top end of the frame is fixed to four supporting rods 19, 20, 2 丨, 22, and the like. Each support rod includes a thread 23 and a worm wheel 24 is connected to the frame 32. In this way, the frame 32 can be moved relative to the poles 19-22. An electric motor 25 is provided on a cross beam 26 and is operable to drive the worm wheels 24 to cause the wipe groups 16 to move vertically relative to the deposition surfaces 13,14. Under this operation, the erasing members 17 can be moved between the lower position shown in FIG. 2 and the upper position shown in FIG. 4. Kou Xuan busy killing 32 broke a connecting rod assembly 27, which was connected to the wipe groups 16. The connecting rod assembly 27 includes a pair of connecting plates 28 provided at the two ends of the swab group and connected to the corresponding connecting walls 29. _Crankshaft Finance is pivoted to each pair of connecting plates 28 by pole turning points 31 and so on. The crankshaft arm office will extend from the crankshaft% to the rubbing tilts 16 to support the wiper ends. The link arms 29 can be moved vertically by the second actuator 41. In the illustrated YJ, the “Heidi One Actuator is in the form of a worm gear, and it will be matched with the screw, text, and text provided on each connection frame. The worm gears rotate to drive the connecting arm 29, so that the arms move vertically relative to the frame 18, and then the crankshaft% 200411963 moves the wiper between the open position and the closed position. The second actuator can be retarded to prevent the swabs from being overly tight and stuck on the cathode. The retarding effect can be provided by an elastic joint or using a pneumatic cylinder instead of the worm wheel. As shown in FIG. 6, each row of the cathodes in the battery 10 is formed by a plurality of cathode plates 11, which are connected to a rod 34 so that each plate is suspended from the groove pair. The contact rod 34 leads f and connects m so that money can be supplied to the cathode. The electrolyte is usually very aggressive, and it is typically made of metal ions of 5 moles or higher and 10 degrees. In order to enable these components to operate in this environment, the wiping system I5 will be made of a money-resistant material, and titanium is preferred. Other suitable materials include metal, stainless steel, metal alloys (e.g. Hasta UOyC22), or even some plastics. In addition, titanium is also most suitable as the cathode, because it has excellent resistance to recording, and can form an alloy chain with a metal such as copper, and it is relatively easy to obtain (thus cost-effective). Its ability to avoid the formation of alloy chains ' will improve the ability of the above-mentioned wiping system to wipe off deposits on the boards. 9 and 10 show the structure of each cathode plate 11. In the example shown, the cathode plate Η is made of -titanium foil, and its thickness is preferably about 6 mm. Thin films of this thickness have been found by the applicant to provide the cathode plate with appropriate rigidity and avoid deflection during use. The titanium sheet is bent to form a wavy shape, and alternate grooves and ridges 36 are formed on each of the deposition surfaces 13, 14 respectively. The waveforms extend the entire length of the cathode and are arranged between its top edge 37 and bottom edge 38. 17 200411963 In the example shown, the distance between adjacent ridges 36 is 20 mm, and the depth between the top of the ridge 36 and the bottom of the groove 35 is about 16 mm. The wall surface 43 and the like formed on the corrugated sheet are linear, and each has an internal angle of about 60 at the top of the ridge and the bottom of the groove. 5 The main purpose of providing ripples in the cathode is to affect the current density on the deposition surfaces 13, 14 during the operation of the battery. In other words, the ripples on the sunken surface will cause a uniform electricity on the surface during the operation of the battery. The wavy deposition surface on the cathode will cause high current density bands along the ridges, because These areas will correspond to high electric fields and lower current densities at the grooves. This will cause the metal deposition to be concentrated in the region of high current density, and cause uneven deposition over the entire surface. Therefore, most of the deposition will occur in the ridge 35 region of the deposition surface. Creating intermittent deposition will improve the ability of the wiping system 15 to be used to remove 15 reduced metal from the cathode. The deposition surface has the shape of grooves and ridges, which can cause the uneven electric field by two mechanisms. First, from the perspective of its shape, the electric field at the convex ridge is stronger than that at the groove, because its surface is curved. Normally, the electric field lines are always parallel to the surface. Therefore, there will be an electric field concentrated at each point along each ridge. Second, the current flow path will be shorter at each ridge than at the groove. As a result, the resistance is smaller at the convex ridge than at the groove. In addition, the use of a wavy cathode will allow better control at the main deposition locations (i.e. along the ridges). If the current density at one location is too high, it will result in polarization of the concentrate when it is deposited (it will be generated around the growing sediment 18 200411963). When this occurs' a relatively high impurity content will be produced in the deposited metal (e.g. copper). With this wavy shape, the main deposition location occupies approximately 25 to 34% of the total surface area of the cathode. For mass-produced work, the ideal current on the deposition surface should be around 1000 A / m2 or less. When growing like a tree on this surface, the actual deposition surface area will increase due to the continuous accumulation of metal on previously deposited metal. If the initial deposition position on the cathode-is too small, there will be a tendency that when tree-like deposits are removed from the cathode, the current density at that position will become too high. After testing by the applicant, using this wavy shape, it has been found that the current density at the 10th product of the Shen Lu area can be maintained at 1, no matter when the battery starts operation or after tree growth has occurred. 〇〇A / m2, so can provide high-quality metal deposition. Therefore, there is no need to change the current in this process. Another advantage of using a corrugated shape on the cathode is that it can improve the rigidity of the cathode plate, because the corrugated shape will be stiffer in the direction of the ridges and grooves than a 15 flat plate. In addition, this wave shape is ideally suitable for cleaning with a wiper, as described in detail later. Please refer to FIGS. 11 to 15. These erasing pieces 17 include convex fingers 39 and the like are fixed between a pair of holding bars 42. In the example shown, the fingers are made of a ceramic material and the rails are made of titanium. The protruding fingers 39 are arranged along the 20 rails 42 so that the erasing members 17 match the shape of the corrugated cathode plate 11, so that the protruding fingers can be swept in the grooves 35 on the deposition surface. Pass each corresponding ridge 36. As shown in FIG. 12, the wiping system 15 is designed such that when the wiping groups 16 are in their closed positions, the wiping members 17 will be inclined to the cathode plate 19 200411963 11, so that the fingers Phase 39, the route that the wiper 17 moves down from the cathode plate is at the tail end position. This design will be better, because the protruding finger can be prevented from getting stuck in the groove, which may occur if the protruding finger 39 is located at the front end position in the downward direction. 5 As mentioned above, due to the wave-like shape of the cathode plate 11, the metal reduced by the electrolytic cell Λ will be concentrated on the ridges of the deposition surfaces of the battery. Therefore, when the specialized wiper 17 moves through the deposition surface, the material peeled off by the ridges will move into the adjacent groove of the deposition surface. This will cause the metal to accumulate in the grooves, which will enclose the protruding fingers 34 and protect the Lu 10 ceramic protruding fingers 39 from abrasion. In addition, when a large amount of material is moved downward from the deposition surface, it will cause friction, which will help to remove the material, because the material will be dragged and scraped by the surface under this friction. It is not necessary for the raised fingers 39 to directly contact the deposition surface in order to actually clear the surface. Another advantage of the design of the wiping system 15 is that it can perform different levels of cleaning of the cathodes 15. In detail, as previously described, the wipers 17 can be manipulated to drag over the deposition surface in their closed position to remove a large amount of deposition material on the surfaces. The swabs can also be moved over the deposition surface in the open position. This system can not completely remove the deposition surface, and is only used to ensure that no protruding tree-shaped deposits grow on a part of the deposition surface. If it grows to an extended range, it may touch the anode and cause the electrolysis. Short circuit of battery *. In addition, this also allows more uniformly grown deposits to spread across the ridges of the cathodes, which helps control the current density along the deposition surface. Figures 14 and 15 show alternative designs of certain wipers 17. In the design of FIG. 13, each of the wiping members 17 includes a ceramic finger 39. However, if it is not 20 200411963, using the holding device 42 not shown in FIG. 13, the net finger 39 can also be connected to each other by an internal connecting rod 44. In the example of Fig. 14, the rod 44 is formed into a square section, and the connecting rod of Fig. 15 is composed of a solid cup 45. See Figures 16 and 17 for an alternative cathode structure. In this example, the cathode system is made into a composite structure, in which the outer deposition surfaces 13 and 14 are formed by two separate plates, which are fixed to each other along its side edges 60 and 61. Together, and may optionally be fixed together in the intermittent area 62 or the like. 10 In this embodiment, most of the conductive rods 63 will form part of the structure and extend downward from the head rod 34. The conductive rods are also typically made of titanium (or

-Copper-plated copper rods are made to further enhance conductivity). Generally, the conductive rods will pass through the channels formed between the two plates connected to each other, and extend the entire length of the plates 13 14. This design can provide enhanced through-the-assembly | electron distribution while minimizing resistive attribution. This is what can happen when the electronics are only on the edge of the plate. In addition, the composite design was found

Including, the conductive rod devices in these channels can strengthen the C 疋 f port of the plate. This thin plate structure (for example, as small as imm) or wide plate structure can be used; used as a 4 cathode. The operation principle of the cathode shown in Figs. 16 and I? Is as described above. Although this month has been described above with reference to some preferred embodiments, Ma understands other forms of this hair shirt to implement. … [Schematic description] Figure 1 is a schematic diagram of the process for processing and reducing copper; Figure 2 is a cross-sectional view of an electrolytic battery according to the embodiment of the present invention, the wipe group of the battery 21 200411963 is in the closed position; Figure 3 is a side cross-sectional view of the battery in Figure 2; Figure 4 is a cross-sectional view of the battery in Figure 2 with the wiper set in the open position; 5 Figure 5 is the battery rod assembly in Figure 2 Figure 6 is a sectional perspective view of the battery of Figure 2; Figure 7 is an enlarged schematic view of the open position of the wiper set on the top of the cathode plate;

Figure 8 is an enlarged view of the wiper group in the closed position; Figure 10 is a front view of the cathode plate used in the battery of Figure 2; Figure 10 is an end view of the plate of Figure 9; Figure 11 It is a three-dimensional view of the cathode of the battery abutting the battery in FIG. 2. FIG. 12 is a cross-sectional view taken along the line XII-XII in FIG. 11; FIG. 13 is a battery used in FIG. 2 Tab structure of the wiper

Perspective view; Figures 14 and 15 are modified examples of the tab structure shown in Figure 13; Figure 16 is a perspective view of another cathode for use in the battery of Figure 2, and Figure 20 is Figure 17 16 is a cross-sectional view of the cathode taken along the line XVII-XVII. [Representative symbols for main components of the figure] 10 ... electrolytic cells 13, 14 ... outer surface 11 ... cathode plate 15 ... wiping system 12 ... anode 16 ... wiping group 22 200411963 17 ... wiping member 18 ... conveyor belt 19 , 20,21,22—support rod 23… thread 24… worm gear 25… motor 26… cross beam 27… connecting rod assembly 28 ... connecting plate 29 ... connecting arm 30 ... crank 31 ... pivot point 32 ... frame 34 ... Head bar 35 ... groove 36 ... ridge 37 ... top edge 38 ... bottom edge 39 ... finger finger 40 ... brake arm 41 ... actuator 42 ... rail 43 ... wall 44 ... inner link 45 ... round rod 50 ... Electrolytic cell tanks 60, 61 ... Side edges 62 ... Intermittent areas 63 ... Conductive rods 100 ... Process method 102 ... Leaching 104 ... Electrolysis 106 ... Copper sulfide 108 ... Recovery 110 ... Filter 112 ... Purification

twenty three

Claims (1)

200411963 The scope of patent application: 1. An electrolytic method for reducing metal from an aqueous solution, in which the dissolved metal is deposited on a cathode deposition surface during electrolysis, and the method includes the following steps: 5 causing an unevenness The current density passes through the deposition surface to form a number of high current density regions separated by low current density regions. The difference between these high current density regions and low current density regions is sufficient for metal deposition to be concentrated in these high current density regions. This leads to inconsistent metal deposition over the entire deposition surface. 10 2. The method according to item 1 of the patent application range, wherein the high current density and low current density regions extend along the surface in one direction and alternately pass through the surface in an opposite direction. 3_ The method according to item 1 or 2 of the patent application scope, wherein the battery is operable to reduce copper from the aqueous solution, and the electric current density in these high current density regions is 500 ~ 2,500A / m2, More preferably, it is 100A / m2. 4. The method according to any one of the above patent applications, wherein the battery is operable to reduce copper from the aqueous solution, and the current density in these low current density regions is 0 to 1, 250 A / m2, and more It is 0 ~ 500A / m2. 5. The method according to any one of the above patent applications, further comprising a step of removing the deposited metal from the surface by passing a component through the surface. 6. If the method of the scope of patent application is applied to item 5, when attached to item 2, the element will move in the direction in which the high and low current density areas extend. 0 24 200411963 7-If the scope of patent application is 5 or A method according to item 6, wherein when the deposited metal is removed by the element, a current is maintained in the aqueous solution. 8. The method of claim 5 or 7, wherein the element is movable between the first and second positions and can be operated through the first and second 5 positions On the surface. 9. The method of claim 8 in which the element, when in the first position, contacts or approaches the deposition surface to remove almost all of the deposition metal from the surface. 10. The method of claim 7 or 8, wherein when in the second position 10, the element is separated from the deposition surface and is operable to touch and remove a predetermined distance from the deposition surface Of deposited metal. 11. An electrolytic cell capable of reducing metal by an aqueous solution, the battery comprising a cathode having a deposition surface on which metal can be deposited during electrolysis of the aqueous solution, and when the battery is operated, the deposition surface will have a non-uniform 15 There are many strong electric field regions that are separated by weak electric field regions. The difference between these strong and weak electric field regions is sufficient to allow metal deposition to concentrate on these high electric field regions, and cause inconsistencies on the surface. Metal deposition. 12. For a battery with the scope of patent application No. 11, in which the areas of the strong electric field and the weak electric field will extend along the surface in one direction and alternately pass through the surface in the opposite direction. 13- If the electrolytic cell of the scope of patent application No. 11 or 12, the deposition surface of the cathode includes an array of alternating ridges and grooves, and the ridges will form a strong electric field region, and the grooves will form a weak current Field area. 25 200411963 14. For an electrolytic cell in the thirteenth aspect of the patent application, wherein the cathode includes a plate having at least one major surface forming a deposition surface of the cathode, the plate is pre-formed and provided with the alternating projections. Ridges and grooves. 15. For an electrolytic cell in accordance with item 14 of the patent application, wherein the plate has two opposite major surfaces, each of which will form the deposition surface of the cathode. 16. For an electrolytic cell in the scope of application for patent No. 15, wherein the plate is bent to form grooves and ridges on the opposite deposition surfaces, the ridges on a deposition surface directly correspond to For grooves on the opposite surface, and vice versa. 10 17. The electrolytic cell according to item 13 or 14 of the patent application scope, wherein the plate is of uniform thickness. 18. The electrolytic cell according to any one of claims 14 to 17, wherein the plate is made of titanium. 19. The electrolytic cell according to item 14, including at least one conductive 15 element assembly It extends along the plate and is electrically connected to the plate, and electrons can be supplied to the deposition surface during electrolysis. 20. The electrolytic cell of claim 19, wherein the conductive element is of sufficient size to increase the rigidity of the plate. 21. For an electrolytic cell in the scope of claims 19 or 20, wherein the cathode package 20 contains a second plate which is connected to the first plate and has a second deposition surface whose main surface forms the cathode, The second plate is also pre-formed with alternating ridges and grooves along the deposition surface. 22. For example, the electrolytic cell of claim 21, wherein the second plate is connected to the first plate of the cathode, and a plurality of cavities are formed along the ridges and grooves of the alternating 26 200411963. Extending in the direction, the cavities can accommodate the conductive elements of the cathode. 23. The electrolytic cell according to any one of claims 11 to 21, further comprising a wiping device operable to pass through the deposition surface of the cathode, and to remove the deposition material from the deposition surface. 24. For an electrolytic cell with a scope of application for item 23, when attached to item 13, wherein the wiping device includes a plurality of protrusions and the like can be operated to protrude into each groove of the deposition surface. 25. A cathode for use in an electrolytic cell capable of reducing 10 metal by an aqueous solution, the cathode having an array having a deposition surface including alternating ridges and grooves and the like. 26. A mechanism for removing the metal deposited on the cathodic deposition surface of the scope of application for patent No. 25, the mechanism includes a plurality of elements arranged to protrude into the grooves, and can be moved along the The ridges and grooves come to 15 to strip the deposited metal. 27. In the case of an institution applying for item No. 26, the shape of the components corresponds to the grooves. 28. In the case of an institution applying for a patent scope No. 26 or 27, the components are made of a ceramic material. 20 29. The mechanism according to any one of claims 26 or 28, wherein the elements can be pivoted between a first position protruding into the groove and a second position not protruding so. operating. 30. An electrolysis method is shown in the attached drawings. 31. An electrolytic cell is shown in the attached drawings. 27 200411963 32. —A kind of cathode is shown in the attached drawing. 33. A mechanism for removing metal deposited on a cathode, as shown in the accompanying drawings. 28