US20170058414A1 - Insertable electrode device that does not generate acid mist or other gases, and method - Google Patents

Insertable electrode device that does not generate acid mist or other gases, and method Download PDF

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US20170058414A1
US20170058414A1 US15/307,994 US201515307994A US2017058414A1 US 20170058414 A1 US20170058414 A1 US 20170058414A1 US 201515307994 A US201515307994 A US 201515307994A US 2017058414 A1 US2017058414 A1 US 2017058414A1
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ied
acid mist
strategic
gases
electrode device
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Jaime Roberto SIMPSON ALVAREZ
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Borquez Victor Araya
Pantoja Marco Cortes
Protech SpA
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Assigned to PANTOJA, MARCO CORTES, ALVAREZ, JAIME ROBERTO SIMPSON, BORQUEZ, VICTOR ARAYA reassignment PANTOJA, MARCO CORTES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALVAREZ, JAIME ROBERTO SIMPSON
Publication of US20170058414A1 publication Critical patent/US20170058414A1/en
Assigned to PROTECH S.P.A. reassignment PROTECH S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAYA BORQUEZ, Victor, CORTES PANTOJA, Marco, SIMPSON ALVAREZ, Jaime Roberto
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    • 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
    • C25C7/02—Electrodes; Connections thereof
    • 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
    • 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
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present patent of invention discloses an insertable electrode device (IED) for metal electrowinning processes, to solve the problem of pollution generated by existing processes, as it does not generate acid mist or other gases.
  • the principle is based on that within the (IED) an oxidation half-cell reaction occurs which is complemented with the reduction half-cell which occurs in the metal electrowinning cell that uses it.
  • the (IED) does not generate gases and consequently no acid mist is emitted to the environment.
  • the insertable electrode device (IED) replaces the existing anodes and permits oxidation reactions to occur below the energy threshold of the electrolytic decomposition of water, thus preventing the electro generation of gaseous oxygen, which is the main cause of acid mist.
  • the (IED) is designed to act as an anode in metal electrowinning processes, particularly to replace the anodic reaction corresponding to the electrolytic decomposition of water
  • the (IED) is an electrode device insertable as a contained monolithic unit or cartridge.
  • the (IED) is mainly constituted by an outer polymeric framework which acts as a container, lateral membranes and solution inlet and outlet ducts within the device.
  • a conductive or semiconductive material is included, which we will call a strategic conductor or semiconductor (SCS), which is immersed in an electrolyte with suitable ions for a particular application, which flows from the inlet ducts toward the outlet ducts.
  • SCS strategic conductor or semiconductor
  • the (SCS) inside the device is connected to an external conductive bar located on top of the container of the device.
  • This conductive bar must be designed to withstand the weight of the container as a whole as device and to contact the (SCS) located inside with the system that carries the electric power of the plant.
  • the width of the (IED) enables to locate it in electrolytic cells without making any modifications to the geometries industrially used.
  • the (IED) replaces traditional anodes used in metal electrowinning processes (mainly lead alloys or other conductive or semi conductive electrodes), i.e. as with the anodes currently used in the electrowinning processes, the (IED) is mounted in the electrolytic container contacting it with the lateral electric conductors corresponding to the positive pole and isolating the electrical contact at the negative pole, immersing it in the electrolyte containing the metal of interest usually known as rich electrolyte (RE), inside the container.
  • RE rich electrolyte
  • the field of application of the (IED) is in the mining industry, specifically in the process of electrowinning of metals such as copper, nickel, cadmium, gold, silver, zinc, cobalt and many more.
  • the (IED) further allows to efficiently process solutions coming directly from leaching, without concentrating the element of interest via solvent extraction, ion exchange or activated carbon, because the membranes within do this work. That is, the (IED) can replace the systems of concentration of solutions.
  • the main comparative advantage is that the (IED) of the invention can operate without emission of acid mist and therefore the problems in the facility associated with this matter (pollution, corrosion, increased consumption of water, etc.) are not present.
  • An electrowinning cell operating with the (IED) achieves better energy efficiency with a very low specific consumption of energy compared to the conventional one and similar current efficiencies. There is no acid mist because no water is electrolytically decomposed and consequently there is a saving of water.
  • CEC conventional electrolytic cells or containers
  • the dissolved metal such as copper in +2 oxidation state (Cu 2+ ) migrates to the cathode which is negatively polarized, electro-depositing itself on the surface thereof as metallic copper.
  • H 2 ⁇ O 2 ⁇ H + + 1 2 ⁇ O 2 + 2 ⁇ e _ .
  • the so-called acid mist is caused by the electro generation of small bubbles of oxygen on the surface of the anode which emerge to the surface of the electrolyte, bursting and emitting a set of micro electrolyte particles which are spatially distributed throughout the electrolytic polluting the working environment and the environment surrounding the plant, creating risks for people, flora, fauna and the environment in general.
  • This acid mist corrodes equipment, electrodes and structures, forcing to take operational measures to mitigate these emissions.
  • the law requires the control of the acid concentration inside the building and has set it at 0.8 ppm/m 3 of air at sea level, but this value decreases depending on the altitude of the site, for example at 3000 meters above sea level it requires 0.53 ppm/m 3 . Copper mining has high economic budgets directed to comply with existing regulations but it is quite possible that in the near future environmental requirements increase.
  • the (IED) applied in this case solves these problems associated with the existing procedure, not generating either gases or acid mist.
  • the field of application is mainly in the mining industry but it is not exclusive of other applications and industrial uses.
  • Acid mist in addition to the severe damages that it may cause to the human organism, today mitigated by the use of increasingly sophisticated PPE but also increasingly more uncomfortable for operators, does not prevent serious damage to structures, electronic equipment and machinery inside the building, as well as damages to the rest of the industrial facilities (which also affects people who work there) and surrounding communities, flora and fauna of the surroundings, by the important fraction of this mist that comes out of the electrolytic building, which could eventually contaminate water resources.
  • H 2 ⁇ O 2 ⁇ H + + 1 2 ⁇ O 2 + 2 ⁇ e _ .
  • the conductive or semi conductive anode is submerged inside the electrolytic container, so that the electrolytic reactions occurring on the surface are produced with the rich electrolyte (RE), i.e. the anode and the cathode share the same electrolyte.
  • RE rich electrolyte
  • Equations 1 to 6 represent these reactions on the anodic surface.
  • a fundamental difference offered by the (IED) is that the (IED) has external contact with the rich electrolyte (RE) through ion exchange membranes that make up the wider was of the device, unlike the conventional process in which the anode is directly in contact with (RE). In other words, the (IED) does NOT use the (RE) directly for its electro chemical reactions.
  • the NAM cell (Application CL/201100617) does not produce acid mist.
  • it is a new electrolytic cell that replaces the existing ones, unlike the (IED) which only replaces the anode, as an insertable electrode device.
  • the insertable electrode device replaces the existing anodes and can produce oxidation reactions below the energy threshold of the electrolytic decomposition of water, thus preventing the electro generation of gaseous oxygen which is the main cause of acid mist.
  • FIG. 1 is an isometric view showing the main elements.
  • FIG. 2 is an exploded isometric view of the device (IED).
  • FIG. 3 is a side cutaway view showing the direction of flow.
  • FIG. 4 is a front cutaway view showing elements and flow.
  • FIG. 5 is a front cutaway view showing a conventional cell.
  • FIG. 6 is a front cutaway view showing the (IED) in a (CEC).
  • FIG. 7 is a cutaway plan view of a conventional cell (CEC).
  • FIG. 8 is a cutaway plan view of the (IED) as an anode in the (CEC).
  • the insertable electrode device (IED) ( 1 ) of the invention is shaped and confined as a housing or cartridge acting as a container and it is a basic movable monolithic unit insertable and removable in the electrolytic cells for metal extraction.
  • the (IED) ( 1 ) allows to vary its configuration of shape and dimensions as a mobile unitary container to adapt it to the shape and dimensions of the cell in which it will be used.
  • the (IED) ( 1 ) considers and allows the possibility of giving it different volumetric shapes, e.g. it can be rectangular, cylindrical and may even have special geometries as required by a given specific application.
  • FIG. 1 shows the cartridge or container which as a unit forms the device (IED) ( 1 ), which has a polymeric structure which constitutes a peripheral frame ( 2 ) which gives it the structural strength and ensures the water tightness of the assembly, preventing leakage of solutions from inside to outside or vice versa, wherein the peripheral frame ( 2 ) works in conjunction with side wails which are formed by a ion exchange membranes ( 3 ) located on both sides of the cartridge, wherein a strategic electrode ( 4 ) that is a strategic conductive or semiconductive material (SCS) is located in the inner cavity that these ion exchange membranes ( 3 ) form.
  • IED device
  • FIG. 2 shows in isometric exploded view the insertable electrode device (IED) ( 1 ), showing that the device as cartridge is configured and confined by containment walls which are surfaces or ion exchange membranes ( 3 ). These membranes are supported by the peripheral frame ( 2 ) which includes two peripheral seals on both sides.
  • the peripheral frame ( 2 ) is formed based on polymers resistant to corrosive environment, this structure allows to vary the volumetric shape as required, depending on the aqueous medium containing the metal to electro-win. It shows the horizontal conductive bar ( 7 ), the inlet ( 5 ) and outlet ( 6 ) ducts.
  • FIG. 3 shows in side cutaway view how inside the insertable electrode device (IED) ( 1 ) a strategic electrode ( 4 ) is located which can be configured or provided with the condition of mass electrode, mesh electrode or plate electrode.
  • the strategic electrode's materials ( 4 ) may be conductors or semiconductors (metals, graphite, graphene, iridium oxide coated metals, tantalum or ruthenium). It indicates the position of a distributor bar ( 11 ) connected to the inlet duct ( 5 ) and the position of a discharge bar ( 12 ) connected to the outlet duct ( 6 ) and the direction of circulation of the conductive electrolyte ( 10 ).
  • FIG. 4 shows the direction of circulation of the conductive electrolyte ( 10 ) wherein entry is through the inlet duct ( 5 ) and it is distributed perpendicular and horizontally by the distribution bar ( 11 ) from which circulation is towards the discharge bar ( 12 ) which is connected to the outlet duct ( 6 ), wherein both bars have circulation inlet bores or ducts ( 13 ) allowing passage of the conductive electrolyte ( 10 ).
  • the conductive electrolyte ( 10 ) is called strategic electrolyte and it is an aqueous medium containing the ion pair to be used for the half cell anodic reaction and which in the case of copper will be the Fe (II)/Fe (III) couple.
  • the circulation of the conductive electrolyte ( 10 ) within the cartridge ( 1 ) forming the (IED) ( 1 ) is carried out through circulation outlet ducts ( 14 ), wherein the entry of the fluid is injected through the inlet connector or duct ( 5 ), wherein the fluid entering does it at constant pressure and descends vertically, distributing perpendicularly and horizontally on the entire inner surface of the cartridge ( 1 ) because of the distribution bar ( 11 ), the pressure of the fluid allowing it to be captured evenly by the discharge bar ( 12 ) to discharge it from the (IED) ( 1 ) through the outlet duct ( 6 ).
  • FIG. 5 shows in front cutaway view a conventional electrowinning or electrolytic cell (CEC), indicating the positive polarity connector ( 15 ) and the capping board ( 16 ) which permits to isolate the anode from the contact with negative polarity.
  • CEC electrowinning or electrolytic cell
  • FIG. 6 shows in front cutaway view a conventional electrowinning or electrolytic cell (CEC) and the cartridge or device (IED) located inside.
  • the (IED) at the top has a horizontal conductive bar ( 7 ) which is electrically connected with the strategic electrode ( 4 ) by means of vertical conductive bars ( 8 ) which further allow to physically hold the cartridge as a whole.
  • the (IED) must be in electrical contact with the conductive bars with positive polarity ( 15 ) of the conventional cells, by means of the support of the horizontal conductive bar ( 7 ) of the device.
  • This horizontal conductive bar ( 7 ) must rest on the capping board ( 16 ) that allows to electrically isolate the negative pole of the conductive bars or base ( 15 ) of the cells.
  • the connection between the vertical conductive bars ( 8 ) and the horizontal conductive bar ( 7 ) is by means of a system of clamps or handles ( 9 ).
  • the (IED) remains in electrical contact with the conductive bars with positive polarity ( 15 ) of the conventional cells, CEC, by supporting the horizontal conductive bar ( 7 ) of the device.
  • This horizontal conductive bar ( 7 ) must rests on the capping board ( 16 ) that allows to electrically isolate the negative pole of the conductive bars or base ( 15 ) of the cells (CEC).
  • the connection between the vertical conductive bars ( 8 ) and the horizontal conductive bar ( 7 ) is by means of clamps or handles ( 9 ).
  • FIG. 7 shows a cutaway plan view of a conventional electrolytic cell (CEC) and the arrangement of the traditional cathode ( 18 ) and traditional anodes ( 17 ) and the conductive bars or base with positive polarity ( 15 ) of the cells (CEC).
  • CEC conventional electrolytic cell
  • FIG. 6 shows a cutaway plan view of a conventional electrolytic cell (CEC) and the arrangement of the traditional cathode ( 19 ) and the location of the insertable electrode device (IED) or cartridge, wherein in the case of copper electrowinning the (IED) or cartridge considers a maximum thickness for proper insertion as a device within a conventional electrolytic cell, without changing the original design of the traditional cathode ( 19 ), which allows variation ranges between 10 to 15 millimeters approximately between the anode ( 17 ) to anode ( 17 ) or cartridge to cartridge centers.
  • the (IED) or cartridge acts as an insertable and removable anode inside a conventional electrowinning cell (CEC).
  • the insertable electrode device (IED) ( 1 ) replaces the existing anodes ( 17 ) and can produce oxidation reactions below the energy threshold of the electrolytic decomposition of water, thus avoiding the prior art problem resulting from the electro generation of gaseous oxygen which is the main cause of acid mist.
  • the (IED) is designed to act as an anode in metal electrowinning processes, particularly to replace the anodic reaction corresponding to the electrolytic decomposition of water
  • a conductive or semiconductive material is included which is the strategic electrode ( 4 ), which is immersed in an electrolyte with suitable ions for a particular application, which flows from the inlet ducts ( 5 ) to the outlet ducts ( 6 ).
  • the membrane ( 3 ) is a polymeric material with electrically charged fixed groups inside. If the functional groups are positive, it is a cationic exchange membrane ( 3 ) and if the groups are negative, it corresponds to an anion exchange membrane ( 3 ).
  • the importance of the membranes ( 3 ) is to maintain a physical separation between the rich electrolyte (RE), which contains the metal to be recovered, and the fluid flowing into the (IED), but enabling to maintain the electrical conductivity between the (RE) and the fluid circulating inside the (IED) thanks to selective ion exchange in a single direction, from the RE into the (IED).
  • the fluid flowing inside the (IED), of conductive properties and containing a suitable redox couple, is called strategic electrolyte (SE).
  • the (SCS) within the device is connected to a horizontal conductive bar ( 7 ) external to the (CEC), located on top of the container device.
  • This horizontal conductive bar ( 7 ) must be designed to support the weight of the container as a whole as a device or cartridge and to contact the (SCS) located inside with the system that carries the electric power of the plant.
  • the geometry of the (IED) allows to piece it in the existing industrial cells, keeping the amount of cathodes of each cell and without any changes in the geometry of the existing cells.
  • the (IED) or cartridge replaces traditional anodes used in metal electrowinning processes (mainly lead alloys or other conductive or semi conductive electrodes), i.e. as with the anodes currently used in the electrowinning processes, the (IED) is mounted in the electrolytic container, contacting the lateral electric conductors corresponding to the positive pole and isolating the electrical contact at the negative pole, immersed in the electrolyte containing the metal of interest usually known as rich electrolyte (RE), within the container.
  • the walls which correspond to the membranes must remain submerged in the outer electrolyte containing the metal to be recovered.
  • a cathode is located between two cartridges or units of (IED), so in an electrolytic cell there will always exist n+1 cartridges ( 1 ) or (IED) for each n cathodes. This is very similar to the existing situation. For that reason no changes are to be made to the existing electrolytic cells nor to the electrical conductors nor to the electrical insulators. No modifications to the lifting and material displacement equipment in the electrolytic building are considered, either.
  • the sequence of the process will occur as follows: inside the (IED) a ferrous ion contained in the (SE) is contacted with the (SSC) located inside the (IED) housing, electrolytically reacting on the surface of the (SCS), wherein the electrolytic transformation of ferrous ion to ferric ion occurs so that the (SE) leaving the (IED) has a high content of ferric ion.
  • the conversion reaction of ferrous ion to ferric ion involves the loss of electrons which are carried by the electrical conductors to the cathode, negatively polarizing it.
  • the reduction of cupric ion occurs at the cathode, which captures electrons deposited as metallic copper.
  • the oxidation reactions within the (IED) and the reduction of cupric ion occurs, it results in an imbalance of positive charges within the (IED) and negative charges in the ER which is offset by the selective passage of anions through the exchange membranes ( 3 ) from the (RE) into the (IED).
  • the main ion that is transferred is the SO 4 2 ⁇ ion.
  • the electrical conductivities involved are now the corresponding to the (RE), the conductivity in the membrane ( 3 ) and the conductivity in the SE, all being resistances of the system.
  • ferrous ion to ferric ion occurs at an energy threshold much lower than the electrolytic decomposition of water and, because of this, it does not produce acid mist because it does not generate micro bubbles of gaseous oxygen emerging and burst at the surface of electrolyte, which are responsible for the emission of acid mist.
  • the mounting procedure (IED) in a conventional cell includes the following steps:
  • the (IED) allows to electro deposit metals without emitting acid mist to the working environment or the environment surrounding the facilities, so existing acid mist mitigation systems can be eliminated.
  • the main objective of the (IED) is to eliminate acid mist emitted from existing electrowinning systems that apply and use the electrolytic decomposition of water, which generates micro oxygen bubbles which emerge to the surface of the electrolytes, where they break open and emit a distribution of micro droplets that pollute the environment.
  • the (IED) eliminates the root of the problem and does not generate acid mist.
  • the energy threshold not to electrolytically decompose water allows to eliminate the production of gaseous chlorine.
  • the number of (IED) units required for a given level of production is calculated by means of Faraday's law, commonly used for these calculations and linking the production of a metal of interest with current density and area of the (IED).
  • the (IED) In the case of copper, the (IED) must be arranged in cells of 15, 30 or 60 cathodes which exist in market.
  • the (SE) fed is a solution in sulphuric atmosphere in an acidity range between 150 to 180 g/L of sulphuric acid with a total Fe concentration in solution between 50 to 90 g/L, mostly as Fe (II).
  • the operating temperature can be moved from room temperature to 90° C.
  • the (SE) exiting in the (IED) contains 150 to 180 of sulphuric acid with a concentration of total Fe in solution between 50-90 g L, mostly as Fe (III).
  • the operating temperature can be moved from room temperature to 90° C.
  • the flow rate to each (IED) can fluctuate between 1 to 60 L/min.
  • the (SCS) may be a conductive or semi conductive material in the form of a plate, mesh, metallic wool or pieces of these materials filling the cavity of the cartridge ( 1 ), provided they have electrical contact with the top horizontal conductive bar ( 7 ).
  • the selection of the (SCS), the (SE) and the redox couple to be used as well as the most suitable ion exchange membrane ( 3 ) is performed by laboratory tests which consider performing linear voltammetries in a unit scalable to industrial size and tests in a scalable unit, also at the laboratory, of electrowinning tests where all metallurgical responses that may enable to properly select these materials are measured.
  • the metals that can be recovered with this new technology are zinc, copper, gold, silver, cadmium, nickel, palladium, platinum, cobalt and rhodium, whose half-cell reactions are the reduction of these ionic species to their metallic form, a reaction which necessarily occurs on the negatively polarized surface of the cathode.
  • the anodic reaction is any oxidation reaction that in the series of standard potentials is located above the reduction of the metal species and below the water oxidation reaction, not forming any gases.
  • the Fe (II)/Fe (III) couple is any oxidation reaction that in the series of standard potentials is located above the reduction of the metal species and below the water oxidation reaction, not forming any gases.
  • the Fe (II)/Fe (III) couple is any oxidation reaction that in the series of standard potentials is located above the reduction of the metal species and below the water oxidation reaction, not forming any gases.
  • the Fe (II)/Fe (III) couple for example, the Fe (II)/Fe (III) couple.
  • the anion to be transferred into the (IED) is the SO 4 2 ⁇ ion.
  • the anionic ion exchange membrane ( 3 ) used in the (IED) only allows the passage of anions, thus the electrolyte rich in copper and other species will keep the cations that compose the same in the same way the cations that form the anolyte. This allows the current efficiency to be very high since no undesired oxide reducing reactions of impurities occur as in the conventional process.
  • the energy threshold will be less than the decomposition of water so the energy requirements are lower; no acid mist is generated and no chlorine oxidizes.
  • the physical barrier of the outer frame of the IED protects the membranes and the (SCS) electrode located inside from accidental bumps when the cathodes are handled during harvesting of the deposited product.
  • the change of anodic reaction decreases water consumption, which is expected to drop by about half.
  • water consumption For example, in the conventional process one mole of water, an increasingly scarce supply, is consumed for depositing 1 mole of copper.
  • the water that must be replenished should be first treated to ensure its purity and it must be heated so as not to make sudden changes in temperature. With the addition of the IED, no water is consumed by this concept and only the water that evaporates and the equivalent of system purges must be replaced.

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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)
  • Water Treatment By Electricity Or Magnetism (AREA)
US15/307,994 2014-04-30 2015-04-24 Insertable electrode device that does not generate acid mist or other gases, and method Abandoned US20170058414A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CL1133-2014 2014-04-30
CL2014001133A CL2014001133A1 (es) 2014-04-30 2014-04-30 Dispositivo electródico insertable (dei) que reemplaza al ánodo tradicional en procesos de electro obtencion de metales, que no genera neblina ácida u otros gases, que comprende un marco perimetral dispuesto en ambos lados del dispositivo, membranas de intercambio ionico, electrodo estrategico que es un conductor o semiconductor, ducto de entrada y salida, barras conductoras electricas verticales; procedimiento de aplicacion del dispositivo.
PCT/CL2015/000027 WO2015164990A1 (es) 2014-04-30 2015-04-24 Dispositivo electródico insertable que no genera neblina acida u otros gases, incluye procedimiento

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AU (1) AU2015252689B2 (es)
CL (1) CL2014001133A1 (es)
PE (1) PE20170107A1 (es)
WO (1) WO2015164990A1 (es)
ZA (1) ZA201608283B (es)

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CN107475747A (zh) * 2017-07-28 2017-12-15 东营方圆有色金属有限公司 一种低成本复新铜电解导电棒的方法
CN117263468A (zh) * 2023-11-20 2023-12-22 内蒙古美力坚科技化工有限公司 一种混纺染料生产废水脱色处理装置

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ES2580552B1 (es) * 2016-04-29 2017-05-31 Industrie De Nora S.P.A. Ánodo seguro para celda electroquímica.
CN109735893B (zh) * 2019-02-19 2020-12-08 杭州知桔科技有限公司 一种引线框架电镀用阳极组件

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WO2013060786A1 (en) * 2011-10-26 2013-05-02 Industrie De Nora S.P.A. Anodic compartment for metal electrowinning cells
US20140246306A1 (en) * 2011-10-26 2014-09-04 Industrie De Nora S.P.A. Anodic compartment for metal electrowinning cells
US20140199577A1 (en) * 2012-01-16 2014-07-17 Ceramatec, Inc. Alkali metal intercalation material as an electrode in an electrolytic cell

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CN107475747A (zh) * 2017-07-28 2017-12-15 东营方圆有色金属有限公司 一种低成本复新铜电解导电棒的方法
CN117263468A (zh) * 2023-11-20 2023-12-22 内蒙古美力坚科技化工有限公司 一种混纺染料生产废水脱色处理装置

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WO2015164990A1 (es) 2015-11-05

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