CN104404575A - Metallic electrolytic cell and metal electrolysis process - Google Patents
Metallic electrolytic cell and metal electrolysis process Download PDFInfo
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- CN104404575A CN104404575A CN201410713935.4A CN201410713935A CN104404575A CN 104404575 A CN104404575 A CN 104404575A CN 201410713935 A CN201410713935 A CN 201410713935A CN 104404575 A CN104404575 A CN 104404575A
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Abstract
The invention discloses a metallic electrolytic cell which comprises a cell body, anode plates, cathode plates and arc-shaped drainage bulges, wherein the arc-shaped drainage bulges are mounted at the two opposite ends of the cell body; the anode plates and the cathode plates are alternatively arranged in the cell body, and liquid inlets and overflow openings are formed in the cell body; the liquid inlets in the two sides of each cathode plate are positioned in the same end of the cathode plate, and the liquid inlets in the two sides of each anode plate are respectively positioned in the two ends of the anode plate; the two ends of each cathode plate are respectively butted with the convex ends of the arc-shaped drainage bulges, and a liquid drainage cavity is formed between the cathode plates and the arc-shaped drainage bulges. Two adjacent cathode plates and one anode plate between the cathode plates form a similar closed space, electrolyte is fast ejected to enter the space through the liquid inlets in one end of one cathode plate and the other end of the adjacent cathode plate, and then the electrolyte flows clockwise and anticlockwise. The kinetic energy of electrolyte is utilized, the concentration difference of metal ions between the two pole plates is greatly reduced, and the concentration polarization is effectively reduced. The invention further discloses a metal electrolysis process.
Description
Technical field
The present invention relates to material extractive technique field, particularly a kind of electrolytic etching of metal groove.The invention still further relates to a kind of electrolytic etching of metal technique.
Background technology
Electrolytic etching of metal groove is mainly used in the electrolysis of metal and the purifications of electrolytic solution such as copper, lead, nickel.The smelting of such as traditional copper is that mineral raw material copper ore concentrates is obtained anode copper after melting, blowing, fire refining step.Anode copper obtains electrolytic copper after the electrolytic refining of electrolytic etching of metal groove, and the purity of copper improves.
Electrorefining is the Main Means of refining of metal in nonferrous metallurgical process, is also a final link of non-ferrous metal metallurgy, and whether the advanced person of its technology and support equipment directly has influence on quality and the production capacity height of metal.In non-ferrous metal, the electrolysis of the metal such as copper, lead and nickel or electrolyte purification process are all based on electrochemical principle, negative electrode and anode are placed in the groove of the solution filling metal ion, on electrode, electrochemical reaction is there is after energising, on anode, elemental metals loses electronics and becomes metal ion, is moved to cathode direction by diffusion; On negative electrode, metal ion is constantly separated out, is deposited.Electropotential due to metal ion species each in solution determines the order that they react on negative electrode and anode, on negative electrode, preferential precipitation is the metal that electropotential is higher, and the electropotential of each metal is determined by the concentration of standard potential and this metal ion.
Copper is in aqueous electrolysis process, and the amount that its electrolysis goes out observes Faraday's law, can be expressed as with following formula (1):
m
Cu＝1.1852×i×A×t (1)
In formula: m
cufor the quality (g) of the metal of precipitation, i is current density (A/m
2), t is the time (s).
As can be seen from (1) formula, under the prerequisite of existing processing unit and technology, to improve production capacity, unique approach improves current density exactly.
But in production practice, only improve current density if simple, on negative electrode, the speed of precipitating metal is accelerated, and this often causes the Ni metal near negative electrode
2+concentration reduces, and namely creates concentration polarization, thus causes the reduction of electropotential, main metal preferentially can not be separated out on negative electrode, cause the precipitation of foreign metal, affect quality product.The raising of current density on anode, impels anode dissolution too fast, makes the Cu that anode dissolution produces
2+anode-the solution interface that can not speed away spreads to cathodic area, equally also causes concentration polarization, by positive column Cu
2+concentration arrives saturated or supersaturation, by producing the salt sedimentation of the oxide compound of copper or insoluble in anode surface, will block anodic reaction, anode potential raises, cause the dissolving of a large amount of foreign ion to enter in electrolytic solution and pollute electrolytic solution, even cause anode passivation time serious, increase energy consumption.Therefore, concentration polarization causes copper, lead, nickel current density in electrolysis or electrolytic deposition process to improve the major cause be restricted.
In actual production, the concentration polarization between two-plate can be reduced by the internal circulating load improving electrolytic solution in electrolytic process, thus improve electrolytic current density, improve production capacity.But in the production practice of nearly 200 years, although cupric electrolysis technique has had significant progress, current density is also by original 250A/m
2bring up to 420A/m
2, but due to by its circulation of elecrolyte mode, still not can solve the impact that concentration polarization problem is brought, current density again without larger breakthrough, with theoretical electrolytic current density 1000A/m
2differ greatly.As depicted in figs. 1 and 2, existing electrolytic etching of metal groove comprises cell body 01, positive plate 03, negative plate 04 and busbar 06, and wherein positive plate 03 and negative plate 04 staggered arrangement are in cell body 01, and positive plate 03 and negative plate 04 two ends are all placed on busbar 06.Cell body 01 top-side is provided with overflow port 05, and cell body 01 bottom is provided with fluid inlet 02, and wherein fluid inlet 02 is positioned at cell body 01 the same side.
Electrolytic etching of metal groove operationally, it is inner that electrolytic solution enters cell body 01 by fluid inlet 02, electrolytic solution is sprayed along being parallel to negative plate 04 direction by the fluid inlet near negative plate 04 both sides, then, the electrolytic solution of ejection to cell body two end motion, turns back to electrolyte circulation system by the overflow port at cell body two ends by the gap between pole plate and offside cell body 01 wall afterwards.Electrolytic solution moves from the bottom to top, discharge eventually through overflow port 05, wherein electrolytic solution is in the process of moving upward, and negative electrode and anode are placed in the groove of the solution filling metal ion, on electrode, there is electrochemical reaction after energising, negative electrode has metal constantly separate out, deposit.
But because fluid inlet 02 is positioned at the same side of cell body, namely electrolytic etching of metal groove is one-sided feed liquor, when electrolytic solution is moved to opposite side by cell body 01 side, the electrolyte flow speed of side relative to fluid inlet 02 and upper part of the electrolytic cell is slower.When current density raises, metal ion enhanced dissolution rate on anode, on negative electrode, metal ion speed of separating out is accelerated, because circulation of elecrolyte speed is excessively slow, the concentration difference of metal ion between two-plate can not be reduced in time, cause negative plate Quality Down, bath voltage to raise, seriously can cause the series of problems such as anode passivation, not only have impact on normal production, the rising of bath voltage also substantially increases production energy consumption.
Simultaneously, prior art adopts bottom in and top out Recycle design, make circulation of elecrolyte direction contrary with anode slime direction, if improve circulation of elecrolyte amount, anode slime will certainly be affected, electrolytic solution can be caused time serious muddy, and what make a large amount of anode sludge machinery is attached on negative plate, causes quality product to decline.
Therefore, how reducing concentration polarization, is those skilled in the art's technical problems urgently to be resolved hurrily.
Summary of the invention
The object of this invention is to provide a kind of electrolytic etching of metal groove, the concentration polarization in this electrolytic etching of metal groove reduces.Another object of the present invention is to provide a kind of electrolytic etching of metal technique.
For achieving the above object, the invention provides a kind of electrolytic etching of metal groove, comprise cell body, positive plate and negative plate, described positive plate and described negative plate staggered arrangement are in described cell body, described cell body is provided with fluid inlet and overflow port, also comprise the arc drain being arranged on described cell body opposite end protruding, the described fluid inlet of described negative plate both sides is positioned at the same one end of described negative plate, the described fluid inlet of described positive plate both sides lays respectively at described positive plate two ends, described negative plate two ends abut with the protruding end of described arc drain projection respectively, liquid guide flow cavity is provided with between described positive plate and described arc drain projection.
Preferably, described fluid inlet is positioned at described cell body top.
Preferably, the radian of described arc drain projection is 60 ° to 180 °.
Preferably, the angle that described fluid inlet is downward-sloping is 0 ° to 20 °.
Preferably, also comprise the liquid guide flow plate be arranged on described cell body, described liquid guide flow plate and described cell body side seal, described liquid guide flow plate and described cell body side form overflow ducts, and described overflow ducts two ends are communicated with described overflow port with described cell body internal cavity respectively.
Preferably, described cell body bottom is inclined guide surface, and the bottom of described cell body is provided with leakage fluid dram and desilting mouth, and the height of described desilting mouth is lower than the height of described leakage fluid dram.
A kind of electrolytic etching of metal technique, comprises step:
1) electrolytic solution enters between negative plate and positive plate by the fluid inlet on cell body top, and wherein, the described fluid inlet of described negative plate both sides is positioned at the same one end of described negative plate, and the described fluid inlet of described positive plate both sides lays respectively at described positive plate two ends;
2) arc drain is set at described cell body opposite end protruding, described negative plate two ends abut with the protruding end of described arc drain projection respectively, be provided with liquid guide flow cavity between described positive plate and described arc drain projection, electrolytic solution around positive plate clockwise or be rotated counterclockwise;
3) in the overflow ducts that electrolytic solution is extremely formed by the flow deflector be arranged in cell body and described cell body sidewall by described cell body flows, then discharged by the overflow port on described cell body.
Preferably, the one-sided flow of electrolyte of described negative plate is 1.0L/min-3.0L/min, and electrolyte pressure is at 0.2MPa-0.5MPa.
Preferably, current density is 500A/m
2~ 700A/m
2.
In technique scheme, electrolytic etching of metal groove provided by the invention comprises cell body, positive plate, negative plate and is arranged on the arc drain projection of cell body opposite end, positive plate and negative plate staggered arrangement are in cell body, cell body is provided with fluid inlet and overflow port, the fluid inlet of negative plate both sides is positioned at the same one end of negative plate, the fluid inlet of positive plate both sides lays respectively at positive plate two ends, negative plate two ends abut with the protruding end of arc drain projection respectively, are provided with liquid guide flow cavity between positive plate and arc drain projection.Known by foregoing description, the two ends of positive plate are equipped with fluid inlet, electrolytic solution around positive plate clockwise and rotate counterclockwise, by electrolytic solution convection current, enhance the velocity of flow of electrolytic solution around positive plate and negative plate, electrolytic solution flows downward in enclosed space, and flowing respectively to cell body two ends in the space bottom pole plate and cell body, is come back in electrolyte circulation system afterwards by overflow port.Two adjacent cathode plate form a similar closed space with the positive plate in the middle of it, after electrolytic solution is sprayed fast entered this space by the fluid inlet of negative plate one end and the adjacent cathode plate the other end, by flowing clockwise or counterclockwise, merit make use of electrolytic solution self exist kinetic energy, reduce the concentration difference of metal ion between two-plate well, significantly reduce concentration polarization.
Accompanying drawing explanation
Fig. 1 is the structural representation of existing electrolytic etching of metal groove;
Fig. 2 is the vertical view of existing electrolytic etching of metal groove;
The structural representation of the electrolytic etching of metal groove that Fig. 3 provides for the specific embodiment of the invention;
The cell body that Fig. 4 provides for the specific embodiment of the invention and arc drain is protruding and the structural representation of liquid guide flow plate;
The vertical view of the electrolytic etching of metal groove that Fig. 5 provides for the specific embodiment of the invention;
The installation site figure of the cell body that Fig. 6 provides for the specific embodiment of the invention and guiding fluid plate.
Wherein in Fig. 1-6: 01-cell body, 02-fluid inlet, 03-positive plate, 04-negative plate, 05-overflow port, 06-busbar;
1-cell body, 2-fluid inlet, 3-positive plate, 4-negative plate, 5-overflow port, 6-busbar, 7-liquid guide flow plate, 8-desilting mouth, 9-leakage fluid dram, 10-inclined guide surface, 11-arc drain are protruding, 12-overflow ducts.
Embodiment
Core of the present invention is to provide a kind of electrolytic etching of metal groove, and the concentration polarization of this electrolytic etching of metal groove reduces.Another core of the present invention is to provide a kind of electrolytic etching of metal technique.
In order to make those skilled in the art understand technical scheme of the present invention better, below in conjunction with drawings and embodiments, the present invention is described in further detail.
Please refer to Fig. 3 to Fig. 6, in a kind of embodiment, electrolytic etching of metal groove provided by the invention comprises cell body 1, busbar 6, positive plate 3, negative plate 4 and is arranged on the arc drain projection 11 of cell body 1 opposite end, concrete, preferably, the radian of arc drain projection 11 be 60 ° to 180 °, concrete, the radian of arc drain projection 11 is 75 °.Negative plate 4 two ends abut with the protruding end of arc drain projection 11 respectively, are provided with liquid guide flow cavity between positive plate 3 and arc drain projection 11.Positive plate 3 and negative plate 4 staggered arrangement are in cell body 1, and positive plate 3 and negative plate 4 are installed on busbar 6.Negative plate 4 can be stainless steel, and the concrete quantity of positive plate 3 and negative plate 4 is determined according to the actual requirements.For the ease of circulation of elecrolyte, preferably, positive plate 3 is than negative plate more than 4 one pieces.The bottom of cell body 1 is provided with desilting mouth 8 and leakage fluid dram 9, concrete, and cell body 1 inner bottom surface can be horizontal plane.Cell body 1 is provided with fluid inlet 2 and overflow port 5, and fluid inlet 2 can be positioned at bottom cell body 1, in order to consistent with anode slime direction, be conducive to the sedimentation of the anode sludge, avoid the anode sludge to pollute the situation of the metal that cathodic electricity solves, preferably, fluid inlet 2 is positioned at the top of cell body 1.As shown in Figure 5, the fluid inlet 2 of negative plate 4 both sides is positioned at the same one end of negative plate 4, and the fluid inlet 2 of positive plate 3 both sides lays respectively at positive plate 3 two ends.Wherein fluid inlet 2 can be the vertical gap of one fixed width and length, also can be circular hole.
The fluid inlet 2 of the every side of negative plate 4 can be multiple, multiple fluid inlet 2 can laterally be arranged, also can longitudinally arrange, because the transverse distance between negative plate 4 and positive plate 3 is shorter, preferably, fluid inlet 2 is arrangement longitudinally, processes fluid inlet 2 for the ease of staff, preferably, fluid inlet 2 is the circular hole of equal diameters.The width of fluid inlet 2, vertical height or number, diameter need to determine according to concrete liquid inlet volume and feed liquor speed.Cell body 1 can adopt the cast molding of corrosion resistant material disposable integral, material selection resin slurry, any one in resin material in preferred epoxy, unsaturated polyester resin or furane resin, improves the performances such as anticorrosive, the insulation of cell body 1, anti-leakage effectively, and safety and environmental protection.For the ease of anode sludge rapid subsidence, and be convenient to electrolytic solution and react, preferably, the downward-sloping angle of fluid inlet 2 is 0 ° to 20 °, and specifically, the downward-sloping angle of fluid inlet 2 is 10 °.
Known by foregoing description, in the electrolytic etching of metal groove that the specific embodiment of the invention provides, the two ends of positive plate 3 are equipped with fluid inlet 2, and electrolytic solution around positive plate 3 clockwise and rotate counterclockwise, by electrolytic solution convection current, enhance the velocity of flow of positive plate 3 and negative plate 4 surrounding electrolytic solution.Flowing clockwise or counterclockwise in the similar enclosed space formed by adjacent cathode plate 4 and intake chute by arranging electrolytic solution, by electrolytic solution convection current, enhancing the velocity of flow of positive plate 3 and negative plate 4 surrounding electrolytic solution, reducing concentration polarization.Electrolytic solution flows downward in enclosed space, flows respectively to cell body 1 two ends in the space bottom pole plate and cell body 1, enters overflow port 5 afterwards come back in electrolyte circulation system by overflow ducts 12.The position of fluid inlet 2 is closer in negative plate 4 both sides.Two adjacent cathode plate 4 form a similar closed space with the positive plate 3 in the middle of it, after electrolytic solution after can being pressurizeed by variable frequency pump is sprayed fast entered this space by the fluid inlet 2 of negative plate 4 one end and adjacent cathode plate 4 the other end, by flowing clockwise or counterclockwise, merit make use of electrolytic solution self exist kinetic energy, also the concentration difference of metal ion between two-plate can well be reduced, enhance the diffusion of positive plate and negative plate two ends ion, reduce concentration polarization, improve current density, add production capacity, reduce energy consumption.Due to, fluid inlet 2 is positioned at the top of cell body 1, consistent with the sedimentation direction of the anode sludge, is conducive to the sedimentation of the anode sludge, better reduces the possibility that the anode sludge pollutes electrolytic solution.Meanwhile, in the situation that the cathodic metal electrolysis amount with traditional is identical, the circulation of elecrolyte amount at fluid inlet 2 place is effectively reduced.Due to by electrolytic solution convection current, enhance the velocity of flow of positive plate 3 and negative plate 4 surrounding electrolytic solution, can current density be improved, and then improve the production efficiency of electrolytic etching of metal groove.
Further, this electrolytic etching of metal groove also comprises the liquid guide flow plate 7 be arranged on cell body 1, liquid guide flow plate 7 and cell body 1 side seal, liquid guide flow plate 7 and cell body 1 side form overflow ducts 12, and overflow ducts 12 two ends are communicated with overflow port 5 with cell body 1 internal cavity respectively.Electrolytic solution is by downwards and after transverse flow, after the anode slime that carries is bottom cell body 1, logical by overflow at cell body 1 two ends, again flows into electrolyte circulation system after entering overflow port 5.
On the basis of above-mentioned each scheme, preferably, cell body 1 bottom is inclined guide surface 10, and the bottom of cell body 1 is provided with leakage fluid dram 9 and desilting mouth 8, and the height of desilting mouth 8 is lower than the height of leakage fluid dram 9.Because the height of desilting mouth 8 is lower than the height of leakage fluid dram 9, be convenient to the collection of the anode sludge, and when avoiding liquid in discharge cell body 1, the situation that the anode sludge is also discharged, avoids energy dissipation.
A kind of electrolytic etching of metal technique that the application provides, comprises step:
1) electrolytic solution enters between negative plate 4 and positive plate 3 by the fluid inlet 2 on cell body 1 top, and the fluid inlet 2 of negative plate 4 both sides is positioned at the same one end of negative plate 4, and the fluid inlet 2 of positive plate 3 both sides lays respectively at positive plate 3 two ends.Wherein the one-sided flow of electrolyte of negative plate 4 is 1.0L/min-3.0L/min, and preferably, the one-sided liquid inlet volume of negative plate 4 controls at 2.0L/min, and in electrolytic solution, copper ion concentration controls between 48g/L-50g/L, and electrolyte pressure is at 0.2MPa-0.5MPa.Current density is 500A/m
2~ 700A/m
2, specifically, current density can control at 570A/m
2.In cell body 1, temperature is 60 DEG C ~ about 65 DEG C.
2) arc drain is set at cell body 1 opposite end protruding, negative plate 4 two ends abut with the protruding end of arc drain projection 11 respectively, be provided with liquid guide flow cavity between positive plate 3 and arc drain projection 11, electrolytic solution around positive plate 3 clockwise or be rotated counterclockwise; Preferably, the radian of arc drain projection 11 be 60 ° to 180 °, concrete, the radian of arc drain projection 11 is 75 °.Negative plate 4 two ends are connected with the protruding end of arc drain projection 11 respectively, are provided with liquid guide flow cavity between positive plate 3 and arc drain projection 11.Flowing clockwise or counterclockwise in the similar enclosed space formed by adjacent cathode plate 4 and intake chute by arranging electrolytic solution, by electrolytic solution convection current, enhancing the velocity of flow of positive plate 3 and negative plate 4 surrounding electrolytic solution, reducing concentration polarization.
3) in the overflow ducts 12 that electrolytic solution is extremely formed by the flow deflector 7 be arranged in cell body and cell body 1 sidewall by cell body 1 flows, then discharged by the overflow port 5 on cell body 1.Namely cell body 1 is provided with liquid guide flow plate 7, liquid guide flow plate 7 and cell body 1 side seal, liquid guide flow plate 7 and cell body 1 side form overflow ducts 12, and overflow ducts 12 two ends are communicated with overflow port 5 with cell body 1 internal cavity respectively.Electrolytic solution, by downwards and after transverse flow, after the anode slime that carries is bottom cell body 1, passes through overflow ducts 12 at cell body 1 two ends, again flows into electrolyte circulation system after entering overflow port 5.
By this electrolytic etching of metal technique, because electrolytic solution enters cell body 1 inside by cell body 1 top, consistent with anode slime direction, be conducive to the sedimentation of the anode sludge, avoid the anode sludge to pollute the situation of the metal that cathodic electricity solves, this electrolytic etching of metal technique can improve the electrolysis precision of cathodic metal.
In this specification sheets, each embodiment adopts the mode of going forward one by one to describe, and what each embodiment stressed is the difference with other embodiments, between each embodiment identical similar portion mutually see.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (9)
1. an electrolytic etching of metal groove, comprise cell body (1), positive plate (3) and negative plate (4), described positive plate (3) and described negative plate (4) staggered arrangement are in described cell body (1), described cell body (1) is provided with fluid inlet (2) and overflow port (5), it is characterized in that, also comprise the arc drain projection (11) being arranged on described cell body (1) opposite end, the described fluid inlet (2) of described negative plate (4) both sides is positioned at described negative plate (4) same to one end, the described fluid inlet (2) of described positive plate (3) both sides lays respectively at described positive plate (3) two ends, described negative plate (4) two ends abut with the protruding end of described arc drain projection (11) respectively, liquid guide flow cavity is provided with between described positive plate (3) and described arc drain projection (11).
2. electrolytic etching of metal groove according to claim 1, is characterized in that, described fluid inlet (2) is positioned at described cell body (1) top.
3. electrolytic etching of metal groove according to claim 1, is characterized in that, the radian of described arc drain projection (11) is 60 ° to 180 °.
4. electrolytic etching of metal groove according to claim 1, is characterized in that, the downward-sloping angle of described fluid inlet (2) is 0 ° to 20 °.
5. electrolytic etching of metal groove according to claim 1, it is characterized in that, also comprise the liquid guide flow plate (7) be arranged on described cell body (1), described liquid guide flow plate (7) and described cell body (1) side seal, described liquid guide flow plate (7) and described cell body (1) side form overflow ducts (12), and described overflow ducts (12) two ends are communicated with described overflow port (5) with described cell body (1) internal cavity respectively.
6. the electrolytic etching of metal groove according to any one of claim 1-5, it is characterized in that, described cell body (1) bottom is inclined guide surface (10), the bottom of described cell body (1) is provided with leakage fluid dram (9) and desilting mouth (8), and the height of described desilting mouth (8) is lower than the height of described leakage fluid dram (9).
7. an electrolytic etching of metal technique, is characterized in that, comprises step:
1) electrolytic solution enters between negative plate (4) and positive plate (3) by the fluid inlet (2) on cell body (1) top, wherein, the described fluid inlet (2) of described negative plate (4) both sides is positioned at described negative plate (4) same to one end, and the described fluid inlet (2) of described positive plate (3) both sides lays respectively at described positive plate (3) two ends;
2) arc drain is set at described cell body (1) opposite end protruding, described negative plate (4) two ends abut with the protruding end of described arc drain projection (11) respectively, be provided with liquid guide flow cavity between described positive plate (3) and described arc drain projection (11), electrolytic solution around described positive plate (3) clockwise or be rotated counterclockwise;
3) in the overflow ducts (12) that electrolytic solution is extremely formed by the flow deflector be arranged in cell body (7) and described cell body (1) sidewall by described cell body (1) flows, then discharged by the overflow port (5) on described cell body (1).
8. electrolytic etching of metal technique according to claim 7, is characterized in that, described negative plate (4) one-sided flow of electrolyte is 1.0L/min-3.0L/min, and electrolyte pressure is at 0.2MPa-0.5MPa.
9. electrolytic etching of metal technique according to claim 7, is characterized in that, current density is 500A/m
2~ 700A/m
2.
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