WO2007071712A1 - Electrolytic cell for metal deposition - Google Patents
Electrolytic cell for metal deposition Download PDFInfo
- Publication number
- WO2007071712A1 WO2007071712A1 PCT/EP2006/069981 EP2006069981W WO2007071712A1 WO 2007071712 A1 WO2007071712 A1 WO 2007071712A1 EP 2006069981 W EP2006069981 W EP 2006069981W WO 2007071712 A1 WO2007071712 A1 WO 2007071712A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cell
- helical device
- anode
- helical
- cathode body
- Prior art date
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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
Definitions
- the deposition of metals such as copper, nickel, cobalt, zinc is commonly carried out in electrometallurgical plants making use of cells consisting of tanks which contain a multiplicity of intercalated planar anodes and cathodes.
- the cathodes are periodically extracted from the cell using suitable winches and replaced with new lots of thin sheets whereon the metal deposition is continued.
- Such equipments are suitable for being employed in the high capacity plants typical of the so-called primary electrometallurgy wherein metals are deposited starting from concentrated solutions obtained by an attack of ores, but are clearly not compatible with processes of secondary deposition of metals, in particular with processes of deposition from medium-low concentrated solutions such as the case of wastes of the same electrometallurgical plants, or of galvanic plants for jewellery or printed circuit manufacturing.
- the elastic sleeve is shaped as an open cylinder with a clearance (19) between the two facing edges allowing the forced insertion into the cathode body during the assemblage of the cell (1 ): in this situation the two edges practically match, thereby eliminating or strong reducing the clearance (19). Since the elastic sleeve is just put in place with no securing points, its extraction, when a predetermined thickness of the metal deposit is achieved, is very simple: it is in fact sufficient to release the nut (14) and the bolts (10), remove the closing flange (9) and extract the sleeve carrying the metal deposit. To restart the cell, the original sleeve cleaned from the metal or a new elastic sleeve must be forced again into the cathode body, the closing flange repositioned and the nut (14) and bolts (10) locked.
- the present invention is therefore directed to overcome the above discussed drawbacks of the prior art by proposing modifications of the cylindrical cell internal structure of EP 845054 in order to make it capable of maintaining the spiral upward flow along the whole vertical axis and to get rid of the problems of short- circuiting originated from the deformation of the elastic sleeve - metal deposit assembly.
- the invention consists of a cell of vertical cylindrical symmetry, comprising an external cathode body, an elastic sleeve forced into the cathode body, a coaxial central anode and tangentially oriented inlet and outlet nozzles capable of generating a spiral upward flow of electrolyte, the cell being further provided with an internal helical device made of electrically insulating material directed to maintain the spiral upward flow along the cell vertical axis; the internal helical device may consist of a single piece or comprise a multiplicity of independent elements.
- the electrically insulating material is preferably a plastic material selected from the group of polyethylene, polypropylene, polyvinylchloride, polytetrafluoroethylene and perfluorinated polymers or copolymers deriving therefrom, polyvinylidenfluoride.
- the helical internal device is flexible and is housed in the gap comprised between anode and cathodic elastic sleeve.
- the coaxial central anode is made of titanium or titanium alloy and provided with a catalytic coating for oxygen evolution, for instance consisting of a film of noble (platinum group metals) and non-noble (titanium, tantalum, niobium, zirconium) transition metal oxides.
- the cathode body is preferably made of stainless steel, while the material of the cathodic elastic sleeve may be for instance a stainless steel or nickel, a nickel alloy or titanium.
- FIG. 1a partial section of an electrolysis cell in accordance with the prior art, as previously described.
- figure 1b section of the coaxial central anode of the cell of figure 1a, as previously described.
- figure 1c top view of the cell of figure 1a, as previously described.
- figure 1d front view of the cathodic elastic sleeve before insertion in the cathode body of the cell of figure 1a, as previously described
- FIG. 2a partial section of the cell according to the invention provided with internal device of helical structure.
- FIG. 2b fragmented perspective representation of a first embodiment of the helical structure device of the cell of figure 2a.
- FIG. 2c perspective representation of one pair of elements which can be assembled in a second embodiment of helical structure device.
- FIG. 2a shows a cylindrical cell with vertical axis as known in the art wherein (19) represents a continuous helical device starting from the lower extremity (20), located above the inlet nozzle (5), to the upper extremity (21 ) located below the outlet nozzle (6).
- (19) represents a continuous helical device starting from the lower extremity (20), located above the inlet nozzle (5), to the upper extremity (21 ) located below the outlet nozzle (6).
- the components in common with the cell of the prior art of figures 1a, 1b, 1c and 1d are indicated with the same reference numerals.
- the helical device (19) When the cell (1) is assembled, the helical device (19) is placed in the annular recess comprised between the cathodic sleeve (3) and the coaxial central anode (4): for this purpose the device is provided with suitable flexibility so that it can be mechanically forced at the time of its insertion and maintained in position during operation.
- the required flexibility of the helical device is imparted by the construction material, which is preferably a suitable polymer material.
- the helical device may be manufactured by the known powder moulding or injection moulding techniques, preferably, for the sake of simplicity, in form of sectors which are subsequently welded.
- the coils (22) of the helical device are mutually spaced, and the optimum value of the corresponding pitch was determined to be 5 to 10% of the cell vertical axis; such coils further define a central hollow space (23) having the same diameter of the anode (4).
- coils (22) may be obtained out of elementary sectors reciprocally connected by means of joints, (24) in figure 2b, for instance obtained by welding.
- the helical device (19) installed in the cell (1 ) acts as a guide for the flow of solution fed through the nozzle (5): in particular, the biphasic mixture (17) consisting of solution and anodically generated gas bubbles is forced to cross the whole cell (1 ) with that same spiral upward flow particularly suitable for the deposition of medium-low concentrated metals.
- the helical device (19) is also characterised by a further operative advantage as it effectively counteracts the deformations which may affect the cathodic elastic sleeve (3) as a consequence of the internal stresses typical of many metal deposits when certain critical thicknesses are exceeded.
- the helical device may have different shapes from those disclosed in figures 2a and 2b, provided its capability of maintaining the spiral upward flow required for the optimum metal deposition is not hampered.
- the helical device is obtained by inserting a series of independent elements in the gap between cathodic sleeve (3) and anode (4): each of the elements consists of a ring (25) comprising a slit (26), one downward-bent strip (27) secured to the ring (25) in the vicinity of the slit and a central hole (28) with a diameter close to that of the anode (4).
- the cell was fed with 3 m 3 /h of solution containing 15 g/l CuSO 4 at pH 3 through the tangentially oriented lower nozzle (5): the solution-oxygen mixture extracted from the also tangentially-oriented upper nozzle (6) was sent to a collecting tank whence, after an oxygen-degassing step, it was recycled to the cell.
- the electrolysis carried out at a cathodic current density of 400 A/m 2 , was protracted for 240 hours without noticing any short-circuiting problem until depositing 54 kg of copper at a 95% current efficiency.
- the cathodic sleeve (3) integral with the metal deposit and the helical device (19), was easily extracted from the cell: it could be verified that the helical device could be removed with no particular difficulty and that the deposit, sectioned along a few different generatrices, was substantially uniform with an average thickness of 12 mm and a maximum thickness of 14 mm in correspondence of some sparse and casually distributed globular formations. No presence of acicular dendrites was detected. The cathodic sleeve showed a small deflection towards the cathode, blocked by the helical device which had undergone just a modest deformation in the contact point.
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- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a vertical cylindrical electrolytic cell suitable for metal deposition comprising an external cathode body, a central coaxial anode and a helical device suitable for maintaining a spiral upward electrolyte flow.
Description
ELECTROLYTIC CELL FOR METAL DEPOSITION
DESCRIPTION OF THE INVENTION
The deposition of metals such as copper, nickel, cobalt, zinc is commonly carried out in electrometallurgical plants making use of cells consisting of tanks which contain a multiplicity of intercalated planar anodes and cathodes. The cathodes are periodically extracted from the cell using suitable winches and replaced with new lots of thin sheets whereon the metal deposition is continued. Such equipments are suitable for being employed in the high capacity plants typical of the so-called primary electrometallurgy wherein metals are deposited starting from concentrated solutions obtained by an attack of ores, but are clearly not compatible with processes of secondary deposition of metals, in particular with processes of deposition from medium-low concentrated solutions such as the case of wastes of the same electrometallurgical plants, or of galvanic plants for jewellery or printed circuit manufacturing. An efficient deposition of metals from such kind of solutions requires a high mass transport, a condition which can only be met by aid of particularly turbulent hydrodynamic regimes, which is certainly not the case of cells for primary electrometallurgy. An interesting cell design suited to this purpose is disclosed in EP 845054: the proposed cell has a vertical cylindrical design and a sketch thereof is reported as reference in figures 1a, 1 b, 1c and 2, wherein (1 ) indicates the cell as a whole, (2) the external cylindrical cathode body made for instance of stainless steel and provided with longitudinal electrical contacts (not shown) for the connection to the negative pole of a rectifier, (3) an elastic metal sleeve, made of some stainless steel, nickel, nickel alloys or titanium and mechanically forced into the cathode body, (4) a coaxial central anode formed by a cylindrical metal rod preferably made of titanium coated with a catalytic film for oxygen evolution and provided with threaded extremities (11 ) and (13) which are connected to the positive pole of the rectifier and which, in co-operation with suitable nuts (12) and (14) allow fixing the anode inside the cell with simultaneous compression of suitable upper (15) and lower (not shown) sealing gaskets, (5) and (6) respectively the inlet and outlet tangentially-oriented nozzles for the solution to
be electrolysed by means whereof a spiral upward flow (16) is established conveying the gas bubbles (17) generated at the anode and proving particularly suitable for metal deposition even at medium-low concentrations, (7) and (9) respectively the upper and lower sealing flanges of the cell, provided with suitable bolts (8) and (10). As shown in figure 2, the elastic sleeve is shaped as an open cylinder with a clearance (19) between the two facing edges allowing the forced insertion into the cathode body during the assemblage of the cell (1 ): in this situation the two edges practically match, thereby eliminating or strong reducing the clearance (19). Since the elastic sleeve is just put in place with no securing points, its extraction, when a predetermined thickness of the metal deposit is achieved, is very simple: it is in fact sufficient to release the nut (14) and the bolts (10), remove the closing flange (9) and extract the sleeve carrying the metal deposit. To restart the cell, the original sleeve cleaned from the metal or a new elastic sleeve must be forced again into the cathode body, the closing flange repositioned and the nut (14) and bolts (10) locked.
In the practice, it was observed that when the cells of the above type have a remarkable height, for instance of 800 to 1200 mm as required in many practical applications, the quality of the metal deposit in the upper section turns out to be poor: an analysis of the flow showed that in these zones the spiral upward flow- path, particularly suited to the deposition of metals from medium-low concentrated solutions, is in fact lost. It is believed that such behaviour is due to the internal friction of the solution and to the action of the gas bubbles generated at the anode. A further inconvenience in the cell of EP 845054 is given by the deflection that the elastic sleeve may undergo toward the coaxial anode as the thickness of the metal deposit increases under the effect of the internal stresses that the latter may present: such kind of deformations, usually localised in the middle part of the cell, lead to harmful short-circuits with the anode after a prolonged operation, not only forcing to discontinue the electrolysis but also obstructing the extraction of the elastic sleeve with the deposited metal, which partially melts generating weld spots on the cathode body.
The present invention is therefore directed to overcome the above discussed drawbacks of the prior art by proposing modifications of the cylindrical cell internal
structure of EP 845054 in order to make it capable of maintaining the spiral upward flow along the whole vertical axis and to get rid of the problems of short- circuiting originated from the deformation of the elastic sleeve - metal deposit assembly.
The invention consists of a cell of vertical cylindrical symmetry, comprising an external cathode body, an elastic sleeve forced into the cathode body, a coaxial central anode and tangentially oriented inlet and outlet nozzles capable of generating a spiral upward flow of electrolyte, the cell being further provided with an internal helical device made of electrically insulating material directed to maintain the spiral upward flow along the cell vertical axis; the internal helical device may consist of a single piece or comprise a multiplicity of independent elements. The electrically insulating material is preferably a plastic material selected from the group of polyethylene, polypropylene, polyvinylchloride, polytetrafluoroethylene and perfluorinated polymers or copolymers deriving therefrom, polyvinylidenfluoride.
In one preferred embodiment of the invention, the helical internal device is flexible and is housed in the gap comprised between anode and cathodic elastic sleeve. In most applications, the coaxial central anode is made of titanium or titanium alloy and provided with a catalytic coating for oxygen evolution, for instance consisting of a film of noble (platinum group metals) and non-noble (titanium, tantalum, niobium, zirconium) transition metal oxides.
The cathode body is preferably made of stainless steel, while the material of the cathodic elastic sleeve may be for instance a stainless steel or nickel, a nickel alloy or titanium. The invention is described hereafter making reference to the following drawings:
- figure 1a: partial section of an electrolysis cell in accordance with the prior art, as previously described.
- figure 1b: section of the coaxial central anode of the cell of figure 1a, as previously described.
- figure 1c: top view of the cell of figure 1a, as previously described.
- figure 1d: front view of the cathodic elastic sleeve before insertion in the
cathode body of the cell of figure 1a, as previously described
- figure 2a: partial section of the cell according to the invention provided with internal device of helical structure.
- figure 2b: fragmented perspective representation of a first embodiment of the helical structure device of the cell of figure 2a.
- figure 2c: perspective representation of one pair of elements which can be assembled in a second embodiment of helical structure device.
A first embodiment of the invention is sketched in figure 2a, which shows a cylindrical cell with vertical axis as known in the art wherein (19) represents a continuous helical device starting from the lower extremity (20), located above the inlet nozzle (5), to the upper extremity (21 ) located below the outlet nozzle (6). The components in common with the cell of the prior art of figures 1a, 1b, 1c and 1d are indicated with the same reference numerals. When the cell (1) is assembled, the helical device (19) is placed in the annular recess comprised between the cathodic sleeve (3) and the coaxial central anode (4): for this purpose the device is provided with suitable flexibility so that it can be mechanically forced at the time of its insertion and maintained in position during operation. The required flexibility of the helical device is imparted by the construction material, which is preferably a suitable polymer material. The helical device may be manufactured by the known powder moulding or injection moulding techniques, preferably, for the sake of simplicity, in form of sectors which are subsequently welded. As shows the fragmented perspective view of figure 2b, the coils (22) of the helical device are mutually spaced, and the optimum value of the corresponding pitch was determined to be 5 to 10% of the cell vertical axis; such coils further define a central hollow space (23) having the same diameter of the anode (4). For the sake of manufacturing simplicity, coils (22) may be obtained out of elementary sectors reciprocally connected by means of joints, (24) in figure 2b, for instance obtained by welding. During the electrolysis the helical device (19) installed in the cell (1 ) acts as a guide for the flow of solution fed through the nozzle (5): in particular, the biphasic mixture (17) consisting of solution and anodically generated gas bubbles is forced to cross the whole cell (1 ) with that same spiral upward flow particularly
suitable for the deposition of medium-low concentrated metals. The helical device (19) is also characterised by a further operative advantage as it effectively counteracts the deformations which may affect the cathodic elastic sleeve (3) as a consequence of the internal stresses typical of many metal deposits when certain critical thicknesses are exceeded.
As it will be evident for those skilled in the art, the helical device may have different shapes from those disclosed in figures 2a and 2b, provided its capability of maintaining the spiral upward flow required for the optimum metal deposition is not hampered. In one possible alternative embodiment, the helical device is obtained by inserting a series of independent elements in the gap between cathodic sleeve (3) and anode (4): each of the elements consists of a ring (25) comprising a slit (26), one downward-bent strip (27) secured to the ring (25) in the vicinity of the slit and a central hole (28) with a diameter close to that of the anode (4). Once the insertion is completed, the strip (27) of each element is in contact with the annular surface of the corresponding underlying element in the proximity of the latter's slit (26): in this way, a forced pathway for the solution is constructed along an upward spiral, equivalent to the one disclosed for the helical device illustrated in figure 2b.
The above described invention was evaluated making use of a cell of the type illustrated in figure 2a, comprising:
- a cylindrical external cathode body of AISI 316L stainless steel, respectively of height, diameter and thickness equal to 1200, 150 and 2 mm
- a coaxial central anode consisting of a 50 mm thick titanium tube provided with suitable electrical connections, coated with a catalytic film for oxygen evolution consisting of iridium and tantalum mixed oxide as known in the art
- a continuous profile helical device such as the one illustrated in figure 2b with 1 mm thick coils spaced apart by 70 mm, obtained by welding together helical sectors made of polyvinylchloride.
The cell was fed with 3 m3/h of solution containing 15 g/l CuSO4 at pH 3 through the tangentially oriented lower nozzle (5): the solution-oxygen mixture extracted
from the also tangentially-oriented upper nozzle (6) was sent to a collecting tank whence, after an oxygen-degassing step, it was recycled to the cell. The electrolysis, carried out at a cathodic current density of 400 A/m2, was protracted for 240 hours without noticing any short-circuiting problem until depositing 54 kg of copper at a 95% current efficiency. At the end of the electrolysis, the cathodic sleeve (3), integral with the metal deposit and the helical device (19), was easily extracted from the cell: it could be verified that the helical device could be removed with no particular difficulty and that the deposit, sectioned along a few different generatrices, was substantially uniform with an average thickness of 12 mm and a maximum thickness of 14 mm in correspondence of some sparse and casually distributed globular formations. No presence of acicular dendrites was detected. The cathodic sleeve showed a small deflection towards the cathode, blocked by the helical device which had undergone just a modest deformation in the contact point.
A similar electrolytic process, previously carried out with the same vertical cylindrical cell but for the presence of the helical device of the invention, was discontinued after 190 hours of electrolysis due to the short-circuit between anode and copper deposit originated by a remarkable deflection of the cathodic sleeve - relevant metal deposit assembly. The deposit examined after extraction from the cell, made difficult by the melting of the metal on the short-circuiting spot, appeared scarcely coherent and of irregular thickness in the upper section of the cell.
The foregoing description is not intended to limit the invention, which may be used according to different embodiments without departing from the scopes thereof, and whose extent is univocally defined by the appended claims. Throughout the description and claims of the present application, the term "comprise" and variations thereof such as "comprising" and "comprises" are not intended to exclude the presence of other elements or additives.
Claims
1. Cell for electrolytic deposition of metals from solutions comprising an external cylindrical cathode body in contact with an extractable elastic sleeve suited to receive a deposit of metal, a coaxial central cylindrical anode spaced apart from said sleeve so as to define an annular recess, inlet and outlet nozzles for the solution having a tangential orientation in order to establish a spiral upward flow and a helical device located inside said annular recess.
2. The cell of claim 1 wherein said helical device is flexible.
3. The cell of claim 1 or 2 wherein said helical device comprises coils manufactured out of electrically insulating material.
4. The cell of claim 3 wherein said electrically insulating material is selected from the group of polyethylene, polypropylene, polyvinylchloride, polytetrafluoroethylene and perfluorinated polymers or copolymers deriving therefrom, polyvinylidenfluoride.
5. The cell of claim 3 wherein said coils are mutually spaced apart with a pitch comprised between 5 and 10% of the vertical axis of the cell.
6. The cell of claim 1 wherein said helical device is a single piece.
7. The cell of claim 1 wherein said helical device is formed by elementary sectors connected by joints.
8. The cell of claim 7 wherein said joints are welds.
9. The cell of claim 1 wherein said helical device is a series of independent rings comprising a slit, a downward-bent strip secured in proximity of said slit and a central hole with diameter equal to the one of said coaxial anode.
10. The cell of claim 1 wherein said coaxial central anode is provided with a catalytic coating suitable for oxygen evolution comprising at least one oxide of transition metals selected from the group of noble metals, titanium, tantalum, niobium, zirconium.
11. The cell of claim 1 wherein said cathode body is made of stainless steel.
12. The cell of claim 1 wherein said extractable elastic sleeve s made of stainless steel, nickel, nickel alloy or titanium.
13. Process of metal electrodeposition from solution characterised by being carried out by impressing an electric current to the solution in the cell of one of the previous claims.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20052422 ITMI20052422A1 (en) | 2005-12-20 | 2005-12-20 | ELECTROLYSIS CELL FOR METAL DEPOSITION |
| ITMI2005A002422 | 2005-12-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2007071712A1 true WO2007071712A1 (en) | 2007-06-28 |
Family
ID=37771099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2006/069981 WO2007071712A1 (en) | 2005-12-20 | 2006-12-20 | Electrolytic cell for metal deposition |
Country Status (4)
| Country | Link |
|---|---|
| AR (1) | AR058711A1 (en) |
| IT (1) | ITMI20052422A1 (en) |
| TW (1) | TW200724722A (en) |
| WO (1) | WO2007071712A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282823A (en) * | 1962-09-10 | 1966-11-01 | Swimquip Inc | Electrolysis cell for production of chlorine |
| US4169033A (en) * | 1978-06-19 | 1979-09-25 | Rkc Corporation | Electroplating cell |
| US4440616A (en) * | 1982-09-30 | 1984-04-03 | General Dental Inc. | Metal collector |
| WO1996038602A1 (en) * | 1995-06-01 | 1996-12-05 | Electrometals Mining Limited | Mineral recovery apparatus |
-
2005
- 2005-12-20 IT ITMI20052422 patent/ITMI20052422A1/en unknown
-
2006
- 2006-11-29 TW TW095144070A patent/TW200724722A/en unknown
- 2006-12-20 AR ARP060105685A patent/AR058711A1/en not_active Application Discontinuation
- 2006-12-20 WO PCT/EP2006/069981 patent/WO2007071712A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282823A (en) * | 1962-09-10 | 1966-11-01 | Swimquip Inc | Electrolysis cell for production of chlorine |
| US4169033A (en) * | 1978-06-19 | 1979-09-25 | Rkc Corporation | Electroplating cell |
| US4440616A (en) * | 1982-09-30 | 1984-04-03 | General Dental Inc. | Metal collector |
| WO1996038602A1 (en) * | 1995-06-01 | 1996-12-05 | Electrometals Mining Limited | Mineral recovery apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI20052422A1 (en) | 2007-06-21 |
| AR058711A1 (en) | 2008-02-20 |
| TW200724722A (en) | 2007-07-01 |
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