WO2012069701A2 - Equipment and method for electrolytic recovery of metal - Google Patents
Equipment and method for electrolytic recovery of metal Download PDFInfo
- Publication number
- WO2012069701A2 WO2012069701A2 PCT/FI2011/051027 FI2011051027W WO2012069701A2 WO 2012069701 A2 WO2012069701 A2 WO 2012069701A2 FI 2011051027 W FI2011051027 W FI 2011051027W WO 2012069701 A2 WO2012069701 A2 WO 2012069701A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- gas ducts
- ducts
- equipment
- cathodes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
Definitions
- the invention concerns a gas duct system as well as equipment and a method for electrolytic recovery of metal, such as copper, as defined in the independent claims.
- Electrolytic recovery for example, is used as a hydro-metallurgic method when production of pure metal, such as copper, is the objective.
- copper is reduced directly from the electrolytic solution, which is a copper sulphate solution.
- copper is precipitated on to the surface of cathodes made of, for example, acid-proof steel, whereupon the copper is removed mechanically from the plate surface.
- the anodes are insoluble metal plates in the process.
- the precipitation rate of the metal, such as copper depends on the current density, but this can not be increased indefinitely without lowering the quality of the precipitate.
- the highest possible current density is determined by the so-called critical maximum current density, that is, the highest current density, when the precipitate is still of a sufficiently high quality, which is proportional, for example, to the content of metal to be precipitated and inversely proportional to the thickness of the so-called diffusion layer.
- a method and equipment for bubbling in electrolytic recovery are known from the US 2007/0251828 publication. According to this method, the process produced air bubbles with a diameter of 0.5 - 3 millimetres, and a pipe system of a porous material is used for supplying bubbling gas into the basin. It is also known that the use of very small air bubbles is more advantageous for the recovery process as it promotes the production of a thinner diffusion layer on the cathode surface, which will for its part allow the use of a higher current density without resulting in a poorer precipitate quality.
- the purpose of the invention is to present a new and more efficient way of electrolytic production of metal, such as copper.
- a particular purpose of the invention is to bring about a new kind of equipment and method for electrolytic recovery of metal, such as copper, in a manner wherein the production of gas bubbles on the electrolyte and further on the cathode surfaces is controlled by equipment according to the invention.
- the formation of bubbles in the basin preferably takes place in such a way that the joining together of bubbles and the formation of large bubbles are prevented.
- Figure 1 is an overall view of the invention
- FIG 2 shows equipment in accordance with an embodiment of the invention
- Figure 3a shows an embodiment of the invention
- FIG. 3b shows an embodiment of the invention
- FIG. 4 shows an embodiment of the invention.
- FIG. 1 shows an electrolytic recovery process
- Figure 2 showing a related piece of electrolysis equipment 1 according to an embodiment of the invention.
- a basin 2 in which there is an electrolyte 3 containing metal, such as copper to be reduced, a suitable number of cathodes 4 are suspended, so that the direction of suspension is the lengthwise direction of the basin.
- anodes 9 between the cathodes in the basin.
- a suitable number of gas supply holes 7 are arranged in a system of gas ducts 6, such as a piping, in a wall 19 limiting the system of gas ducts for transporting gas into the equipment 1 for electrolytic recovery of metal, that is, into electrolysis equipment.
- the invention concerns a method for electrolytic recovery of metal, such as copper, whereby anodes 9 and cathodes 4 are placed in turns in the basin 2 into an electrolytic solution 3 containing metal ions, whereby gas bubbles 8 are spread out into the electrolytic solution, whereby gas bubbles are spread out on to the surfaces of cathodes 4 from the system of gas ducts, in which the passage of gas through wall 19 of the system of gas ducts is prevented in part.
- the bubbling device 13 belonging to the equipment 1 contains a piping 6, which has gas supply holes 7 for supplying gas into the electrolytic solution 3.
- the bubbling device 13 contains means for producing gas bubbles and for controlling the volume of air supplied for their production, such as a pump.
- Electrolyte is removed from the basin, for example, as an overflow 15 or by pumping it into a separate container.
- a hood 16 from which the acid fog formed in the process is recovered by a treating device 17,
- a current source 18 is connected to the basin to produce a current for the process.
- the system of gas ducts 6 of the equipment 1 there is a sufficient number of gas supply holes 7, from which gas bubbles are spread out under the effect of a pressure into the electrolyte 3 and further on to the surfaces of cathodes 4, where they will affect the thickness of the diffusion layer.
- the system of gas ducts consists of a piping 6 and of a porous material, whereby the diameter of the supply holes 7 therein is less than 3 millimetres.
- the piping of the bubbling device is placed in the basin 2 at least partly in a perpendicular position in relation to the suspension direction B of the cathodes 4.
- the piping 6 of the gas supply device consists, for example, of pipes, which are placed in a perpendicular position in relation to the suspension direction of the cathodes and which are connected to each other in such a way that gas is allowed to pass between the pipes.
- the gas supply holes 7 of the piping are located in such a way in the piping 6 that the bubbles are allowed to discharge directly upwards in basin 2 without colliding with each other as the gas 8 is discharging from the supply hole 7. In passing through the holes formed in the piping wall, the gas will form bubbles, which will end up on the cathode surfaces.
- the access of gas through the piping wall is prevented in part.
- the gas is guided to be carried through wall 19 of piping 6 in the part located on the side of cathode 4.
- the gas penetrates the wall at the wall on the side of the cathodes of the piping, from which the bubbles are free to ascend directly on to the cathode surfaces.
- the diameter of the piping is preferably within a range of 4 - 40 millimetres.
- the piping for supplying gas can be implemented in different ways.
- the piping is of a porous gas-permeable material, whereby the gas supply holes preferably have a diameter of less than 3 millimetres.
- a separate part 11 impermeable to gas is placed when required as a replacement into the wall 19 of piping 6 to prevent gas from passing through the wall.
- That part of the piping, which is on the side of the basin bottom, can hereby be coated at least in part with a gas -impermeable material 11, which can be exchanged easily, such as paint, lacquer or glue.
- the piping can advantageously be implemented in such a way that the walls of the piping are impermeable to gas in a place, such as the part on the side of the basin bottom, where passage of gas will cause a harmful effect to the process.
- Figure 3b shows an example of a way of embodying the invention, in accordance with which there are gas supply holes in the pipe wall on that side only, where the gas penetrates the pipe. That part of the piping, which is gas-permeable, is coated with a material promoting the disintegration of gas bubbles. According to the example, the gas supply holes 7 of piping 6 are also coated with a material 10 promoting the splitting up of gas bubbles to become even smaller, such as with an industrial fabric.
- the piping 6 functioning as the system of gas ducts is formed of a sufficient number of interconnected pipes, in which there are gas supply holes 7 at least in that place of the pipe, which is located under the cathode 4. According to an advantageous embodiment of the invention, no more than a 70 % part of the surface area of the wall of the system of gas ducts is gas-permeable.
- the embodiment presented in Figure 4 shows a situation where the piping 6 functioning as the system of gas ducts of the bubbling device is placed in the basin in a parallel position in relation to the direction of suspension B of cathodes.
- the guiding of bubbles 8 on to the surfaces of cathodes is thus promoted with the aid of guiding elements 12.
- the bubbling device 13 is placed in the basin in such a way that the distance A of the top edge 19 of piping 6 from the bottom edge 14 of the cathode is no more than 100 centimetres, such as preferably 5 - 70 cm, so that the bubbles are guided from piping 6 in an optimum manner to both sides of the cathode.
- the guiding elements can be located in the spaces between the cathodes, such as, according to the example, in the anodes located in the spaces between the cathodes.
- the guiding element 12 is an element guiding the flow and guiding the gas bubbles in the desired direction.
- An industrial fabric was wrapped tightly around a metal pipe having holes pointing directly upwards.
- the pipe was placed on the bottom of an electrolysis cell having a height of 1.2 m (width 25 cm, volume 62 L) under a steel plate functioning as a cathode, so that when blowing air into the piping, bubbles were distributed from the bottom edge of the cathode and they ascended uniformly to both sides of the cathode.
- the cell was filled with an electrolyte containing 40 g/1 of copper and 175 g/1 of sulphuric acid. 46.5 L/h of electrolyte was supplied into the cell and the temperature of the electrolyte was 45°C during the test.
- Copper was precipitated on to the cathode surface for 24 h using a current density of 450 Am " , at the same time blowing air through the piping.
- the surface of the copper precipitate formed was examined with a SEM microscope (scanning electron microscope) and with an optical microscope.
- a cross-sectional micro-section was examined with an optical microscope.
- the precipitate had a smooth surface, it was dense, the crystalline growth was uniform and the grain boundaries were difficult to detect in the SEM image. The test was repeated without bubbling, whereby the copper precipitate was rough, porous and the grain size was quite large.
- Example 2 With the equipment of Example 2, a bubbling piping was placed in a transverse position against the cathodes. Guiding components were attached to the anodes to guide the bubbles uniformly on to the cathode surface. The test according to Example 2 was repeated using a current density of 450 Am " and the copper precipitate was examined. The precipitate had a smooth surface, it was dense and the crystalline growth was uniform, as in the case of Example 2, where the copper precipitate was produced with the aid of bubbling.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2815429A CA2815429C (en) | 2010-11-23 | 2011-11-22 | Equipment and method for electrolytic recovery of metal |
| US13/884,999 US9556530B2 (en) | 2010-11-23 | 2011-11-22 | Equipment and method for electrolytic recovery of metal |
| AU2011333623A AU2011333623B2 (en) | 2010-11-23 | 2011-11-22 | A system of gas ducts for transporting gas, equipment and method for electrolytic recovery of metal |
| MX2013005556A MX347672B (en) | 2010-11-23 | 2011-11-22 | A system of gas ducts for transporting gas, equipment and method for electrolytic recovery of metal. |
| RU2013127017/02A RU2554235C2 (en) | 2010-11-23 | 2011-11-22 | System of gas transfer pipes, plant and process for metal electrolytic winning |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20100390A FI125912B (en) | 2010-11-23 | 2010-11-23 | Gas ductwork, equipment and method for electrolytic metal recovery |
| FI20100390 | 2010-11-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012069701A2 true WO2012069701A2 (en) | 2012-05-31 |
| WO2012069701A3 WO2012069701A3 (en) | 2012-10-18 |
Family
ID=43268912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FI2011/051027 Ceased WO2012069701A2 (en) | 2010-11-23 | 2011-11-22 | Equipment and method for electrolytic recovery of metal |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US9556530B2 (en) |
| AU (1) | AU2011333623B2 (en) |
| CA (1) | CA2815429C (en) |
| CL (1) | CL2013001450A1 (en) |
| FI (1) | FI125912B (en) |
| MX (1) | MX347672B (en) |
| PE (1) | PE20140436A1 (en) |
| RU (1) | RU2554235C2 (en) |
| WO (1) | WO2012069701A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013060835A3 (en) * | 2011-10-26 | 2013-06-27 | Barlocci Pennati, Anna | A method for operating a gas diffuser system, and a diffusing apparatus |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1365033A (en) * | 1921-01-11 | Avalt | ||
| CA1020115A (en) | 1973-02-09 | 1977-11-01 | Victor A. Ettel | Air sparging electrowinning cell |
| US3928152A (en) * | 1974-02-25 | 1975-12-23 | Kennecott Copper Corp | Method for the electrolytic recovery of metal employing improved electrolyte convection |
| RU2067084C1 (en) * | 1995-05-12 | 1996-09-27 | Товарищество С Ограниченной Ответственностью "Экополимер" | Aerating device |
| RU2215827C2 (en) * | 2002-02-12 | 2003-11-10 | Федеральное государственное унитарное предприятие Государственный научный центр РФ - научно-исследовательский институт атомных реакторов | Electrolyzer for anode dissolving of hard-to-dissolve metals and alloys |
| CA2536117A1 (en) | 2003-08-22 | 2005-03-03 | Bhp Billiton Innovation Pty. Ltd. | Gas sparging |
| US20100065433A1 (en) | 2008-09-12 | 2010-03-18 | Victor Vidaurre Heiremans | System and apparatus for enhancing convection in electrolytes to achieve improved electrodeposition of copper and other non ferrous metals in industrial electrolytic cells |
-
2010
- 2010-11-23 FI FI20100390A patent/FI125912B/en not_active IP Right Cessation
-
2011
- 2011-11-22 PE PE2013001226A patent/PE20140436A1/en active IP Right Grant
- 2011-11-22 AU AU2011333623A patent/AU2011333623B2/en not_active Ceased
- 2011-11-22 CA CA2815429A patent/CA2815429C/en not_active Expired - Fee Related
- 2011-11-22 WO PCT/FI2011/051027 patent/WO2012069701A2/en not_active Ceased
- 2011-11-22 US US13/884,999 patent/US9556530B2/en not_active Expired - Fee Related
- 2011-11-22 MX MX2013005556A patent/MX347672B/en active IP Right Grant
- 2011-11-22 RU RU2013127017/02A patent/RU2554235C2/en not_active IP Right Cessation
-
2013
- 2013-05-22 CL CL2013001450A patent/CL2013001450A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013060835A3 (en) * | 2011-10-26 | 2013-06-27 | Barlocci Pennati, Anna | A method for operating a gas diffuser system, and a diffusing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| FI20100390L (en) | 2012-05-24 |
| AU2011333623A1 (en) | 2013-05-23 |
| US9556530B2 (en) | 2017-01-31 |
| FI20100390A0 (en) | 2010-11-23 |
| MX347672B (en) | 2017-05-08 |
| AU2011333623B2 (en) | 2016-07-14 |
| CL2013001450A1 (en) | 2013-10-18 |
| RU2013127017A (en) | 2014-12-27 |
| PE20140436A1 (en) | 2014-04-07 |
| CA2815429A1 (en) | 2012-05-31 |
| CA2815429C (en) | 2018-12-04 |
| WO2012069701A3 (en) | 2012-10-18 |
| RU2554235C2 (en) | 2015-06-27 |
| FI125912B (en) | 2016-04-15 |
| MX2013005556A (en) | 2013-07-05 |
| US20140231269A1 (en) | 2014-08-21 |
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