WO2012012871A1 - Method and apparatus for electrochemical recovery of mercury from solutions - Google Patents
Method and apparatus for electrochemical recovery of mercury from solutions Download PDFInfo
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- WO2012012871A1 WO2012012871A1 PCT/CA2011/000837 CA2011000837W WO2012012871A1 WO 2012012871 A1 WO2012012871 A1 WO 2012012871A1 CA 2011000837 W CA2011000837 W CA 2011000837W WO 2012012871 A1 WO2012012871 A1 WO 2012012871A1
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/06—Separation of liquids from each other by electricity
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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
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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
Definitions
- the present invention relates to a method and apparatus for
- the necessary processing solutions may release gases, which may then be treated to recover mercury and particulates, the resulting scrubber bleed solution may then be treated to separate the liquids from the solids, which are then taken to a leaching process. Then the liquids may be mixed with Zinc, in a mix tank, and the solids and liquids are separated and through a chemical reaction mercury is extracted as a mercurous chloride precipitate and the supernatant solution is disposed of.
- PCT/GBOO/01388 to Gilroy filed April 12, 2000, describes a cylindrical electrochemical cell comprising a cylindrical flow through cathode for the electrochemical deposition of mercury and gallium.
- the cathode surrounded by a cylindrical anode, the anode and cathode compartments of the cell are separated by a proton conducting membrane.
- US patent 5,292,412 to Pitton Issued on March 8, 1994, describes metal alloy porous electrodes, and electrochemical cells wherein solution flow is directed across the face of the electrodes.
- the electrode may have a surface area of at least about 500m 2 per 1 m 2 of geometric surface.
- an electrochemical cell comprising an electrode according to an embodiment.
- a cathode according to an embodiment for electrochemically depositing from solution a metal substantially liquid at room temperature.
- the metal is mercury.
- an electrochemical cell comprising a cathode according to an embodiment and an anode, wherein the cathode and the anode may each comprise substantially flat geometrical surfaces and the substantially flat cathode and anode geometrical surfaces are mutually opposed and are substantially uniformly distanced.
- the distance between the electrode geometrical surfaces is less than about 2 cm and the cathode and the anode are in direct fluid contact.
- distance between the anode and cathode is less than about 1 cm.
- the electrochemical cell further comprises a solution inlet positioned to direct at least a portion of the solution to flow through the cathode.
- the electrochemical cell is configured so that substantially all of the solution flows through the cathode.
- the electrochemical cell may further comprise a collector for collecting the metal under gravity induced flow when the metal is electrochemically deposited at the cathode.
- an apparatus for treating a scrubber bleed solution comprising the electrode according to an embodiment.
- an apparatus for treating a scrubber bleed solution comprising the electrochemical cell according to an embodiment.
- an apparatus comprising a plurality of electrochemical cells according to embodiments.
- a method for recovering from solution a metal substantially liquid at room temperature comprising collecting metal electrochemically deposited at a cathode according to an embodiment.
- a method for recovering mercury from solution comprising collecting mercury electrochemically deposited at a cathode according to an embodiment.
- a method for recovering from a solution a metal substantially liquid at room temperature comprising the step of electrolytically depositing the metal at a flow through cathode positioned in the solution, wherein the solution directly contacts both the cathode and a corresponding anode.
- the cathode and the anode each have a substantially flat geometric surface and the anode geometric surface and the cathode geometric surface are mutually opposed and substantially uniformly separated by a distance of less than about 2cm.
- the cathode may have a surface area of at least about 500m 2 per 1 m 2 of geometric surface.
- the cathode may be a carbon fibre cathode or may be a carbon cathode or may comprise carbon, pyrolyzed parylene C (PCC), .carbon foam, carbon nanofoam, carbon coatings, carbon films, carbon pastes, carbon beads, carbon microbeads, carbon microtubes, carbon nanotubes, graphite, graphene, pyrolytic graphite, highly oriented pyrolytic graphite, randomly oriented graphite, carbon black, carbon fiber, evaporate a- C, a-C:H, pyrolyzed photoresist film, boron doped diamond, or N-doped amorphous tetrahedral carbon.
- the current density between the anode and the cathode may be less than about 10V per m 2 of geometrical cathode surface.
- the solution may be a scrubber bleed solution.
- the metal may be mercury.
- an electrochemical cell adapted to receive an electrode according to an embodiment and comprising a solution inlet adapted to direct an electrolyte to flow through the electrode.
- an electrochemical cell adapted to receive the electrode according to an embodiment and comprising a solution inlet adapted to direct an electrolyte to flow through the electrode.
- FIG. 1 is a perspective view of an electrode according to a first embodiment.
- FIG. 2 is a schematic representation of a general process comprising the bleed and destruction systems according to an embodiment.
- FIG. 3 is a schematic representation of the recovery system according to an embodiment.
- FIG. 4 is a side view of the interior of an electro-chemical cell in accordance with a first embodiment.
- FIG. 5 is an end view of the interior of an electrochemical cell according to FIG. 4, taken at right angles to FIG. 4.
- FIG. 6 is a top plan view of the interior of the cell according to FIGS. 4 and 5.
- FIGS. 7A and 7B are enlarged views of portions of FIG. 4.
- FIGS. 8A and 8B are enlarged views of portions of FIG 5.
- FIG. 9 is a cut away sectional view of a second embodiment
- FIG. 10 is a sectional view of the embodiment according to FIG. 10.
- pore or "pores” means any interstice, space, passage, channel, opening, perforation, cavity or similar structure by means of which a substance may pass through a structure.
- the term “porosity” or “porousness” refers to the ratio or relative relationship of the number or volume of pores in a substance, structure or mass relative to the total geometrical volume or geometrical area as defined by the gross external dimensions of the substance or structure or mass of the substance or structure. Porosity is generally referred to as a ratio of the volume of the pores relative to the gross geometrical volume of the structure.
- electrodes or substances may be porous and may be highly porous.
- a porous electrode which may be highly porous and may be a cathode, may be or may be greater than, about 20%, great than about 25%, greater than about 30%, greater than about 35%, greater than about 40%, greater than about 45%, greater than about 50%, greater than about 55%, greater than about 60%, greater than about 65%, greater than about 70%, greater than about 75%, greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95% porous or more, or may be in a range delimited by values of about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%. about 97%, about 98%, about 99% about 99% or greater porosity.
- the term "highly porous” indicates a porosity of greater than about 50%, greater than about 55%, greater than about 60%, greater than abut 65%, greater than about 70%, greater than about 75%, greater than about 80%, greater than about 85%, greater than about 90%, greater than about 95% or more, or and may indicate a range of porosity delimited by values of about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 95%, about 97%, about 98%, about 99%, or greater porosity.
- felt means a structure formed from matted or compressed fibers and "carbon felt” means a felt or structure formed from matted or compressed carbon fiber.
- carbon felt means a felt or structure formed from matted or compressed carbon fiber.
- electrodes may be constructed in any conventional shapes or materials all of which will be readily identified, understood and adopted by those skilled in the art.
- electrodes may be anodes or cathodes or both, and may be constructed to present an enlarged surface area, relative to the geometrical volume or surface of the electrode material itself.
- a cathode may be porous and may be constructed to present a large geometrical surface area by shaping the cathode in the form of one or more flattened or curved plates, sheets or membranes, or as a plurality of wires, threads, fibers or tubes, or the electrode may comprise any other structure or conformation suited to present an increased surface area for contact with an electrolyte which may be a scrubber solution.
- a cathode may comprise an electrically conductive felt or reticulated material, non-limiting examples of which include a conductive felt, mesh or net of any kind and examples include carbon felt or reticulated carbon.
- the carbon felt may be formed of carbon fibres, which fibres may be formed, for example, by the carbonization and/or graphitization of synthetic polymer fibres, for example, polyacrylonitrile or ester fibres.
- the felt may be formed from a pad of such carbon fibres and the pad may be compressible.
- the fibres may suitably have a diameter of the order of about 6 to 8 microns, especially about 6 microns.
- fibers may have diameters of, or of greater than or less than about 0.001 , 0.005, 0.01 , 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, or more microns, micrometers, or millimeters.
- an electrode having the desired properties may be made in a form other than a felt or fibrous structure or may comprise a coated fibrous or non-fibrous structure and may comprise a solid or semi solid structure with pores provided therethrough and may comprise or may comprise an electrolytic surface that comprises one or more of carbon, pyrolyzed parylene C (PCC), .carbon foam, carbon nanofoam, carbon coatings, carbon films, carbon pastes, carbon beads, carbon microbeads, carbon microtubes, carbon nanotubes, graphite, graphene, pyrolytic graphite, highly oriented pyrolytic graphite, randomly oriented graphite, carbon black, carbon fiber, evaporate a-C, a-C:H, pyrolyzed photoresist film, boron doped diamond, N-doped amorphous tetrahedral carbon and other materials which will be readily apparent to those skilled in the art who will readily select between them and adapt their compositions and structures for particular purposes.
- PCC parylene C
- electrodes may comprise or have associated therewith or may be shaped to cooperate with, suitable supporting frames, clips, mountings or other structures which may maintain the structure, integrity or position of the electrodes.
- suitable supporting frames, clips, mountings or other structures which may maintain the structure, integrity or position of the electrodes.
- Such structures and frames may include but are in no way limited to internal and external frames of metals, plastics, carbon, and any other material of sufficient strength and rigidity to maintain the desired geometrical shape of the electrode in operation. This may also comprise the provision of a net or mesh interwoven with the electrode material or covering and containing the electrode material.
- an electrode or a geometrical surface of an electrode is flat or substantially flat or generally flat means that at least one geometrical surface of the electrode is generally planar, or has only limited curvature or divergence from a plane. It will be recognised however that, while such a surface may be generally flat, some degree of irregularity or lack of smoothness may be permissible in embodiments, and those skilled in the art will readily determine the degree of smoothness or the tolerance that is necessary or desirable for acceptable or desirable performance of electrodes, electrode pairs and electrochemical cells according to embodiments.
- reference to a geometric surface or geometric surface area of an electrode or structure means the external surface or gross external shape of the electrode or structure and is to be distinguished from more general references to surface and surface area of an electrode, which, unless the context otherwise requires, indicate the potentially reactive surface of the electrode at which electrical contact between the electrode and an electrolyte may occur.
- the total surface area of the electrode includes surface area presented within the pores.
- the geometrical surface area of the electrode will be defined by the areas of such square faces and any plate edges. It will therefore be apparent that in the case of a porous electrode, the total surface area of the electrode will be substantially greater than the geometrical surface of the electrode.
- reference to the geometrical volume of an electrode refers to the volume defined by the external dimensions of an electrode.
- an indication that an electrode has a high surface area to volume ratio means that the area of electrode surface that is potentially available to electrically contact an electrolyte is high relative to the external geometrical volume of the electrode or area, as defined by the external dimensions of the electrode. It will be further understood that in an electrode with a high surface area to volume ratio, the ratio of total surface for contact with the electrolyte to geometrical surface of the electrode will be greater than 1 :1.
- such a high surface area to volume ratio may be, or may be greater than, about 1 ,000:1 , 2,000:1 , 3,000:1 , 4,000:1 , 5,000:1 , 6,000:1 , 7,0001 , 8,000:1 , 9,000:1 or 10,000:1 , 15m000:1 , 20,000:1 , 25,000:1.
- the ratio may be between about 50:1 and about 1000:1 , about 100:1 and about 1000: 1 , about 200: 1 and about 1000: 1 , about 300: 1 and about 1000: 1 , about 400:1 and about 1000:1 , about 100:1 and about 900:1 , about 100:1 and 800:1 , about 100:1 and about 700:1 , about 100:1 and about 600:1.
- a high surface area to volume ratio may have any value within these ranges.
- the geometrical shape and size of an electrode may be of any desired dimensions, but in particular embodiments the dimensions will be chosen to reduce the current density between opposed anodes and cathodes.
- the geometrical surface area of a cathode or the opposed geometrical surfaces of a cathode/anode pair may be chosen to be as large as practicable to reduce the unit current flow between electrodes over a given area.
- any one of the edges of the substantially flat surface of a cathode or anode may be greater than about 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, or more meters or greater than about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10 or more feet.
- the geometrical surface area of a cathode or anode may be greater than about 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 100 or more square meters.
- a cathode may have about 20 m 2 of geometric surface area, although greater or lesser surface areas and particular geometrical dimensions can be selected and will be readily selected from by those skilled in the art.
- a cathode may provide a total cathode surface of about 250,000 m 2 but different ratios of total surface to geometric surface will be readily created and selected amongst by those skilled in the art. It will be appreciated that the current flow per unit area may depend primarily on the opposed geometrical surfaces of opposed or paired electrodes rather than by the entire external surfaces of the electrodes.
- an “electrochemical cell” also referred to as a "cell” means any device designed to pass electrical current between an anode and a cathode through an electrolyte liquid.
- the electrolyte may be a solution, may be a scrubber bleed solution, or may be derived from a scrubber bleed solution.
- a typical electrochemical cell for treating a scrubber bleed solution may have dimensions of about 5 ft. x 4 ft. x 6 ft although it will be understood that any convenient dimensions may be chosen to suit operational requirements and to accommodate desired electrode dimensions, and such possible dimensions will be readily selected from by those skilled in the art to suit particular operational requirements.
- a cell may be operated with a potential difference across the cell of about 10V, and the gap between cathode and anode may be less than about 2cm, and in some cases about 1 cm or less than about 1cm.
- Alternative voltages will be readily selected by those skilled in the art to suit particular cell properties and dimensions, and by way of example, in alternative
- a potential difference of up to or greater than about 1 V, 2V, 3V, 4V, 5V, 6V, 7V, 8V, 9V, 10V, 11V, 12V, 13V, 14V, 15V, 16V, 17V, 18V, 19V, 20V or greater may be applied to the cell.
- the rate of flow of an electrolyte, which may be a scrubber bleed solution, through an electrochemical cell may be relatively low and may be less than about 50,000 cm 2 /sec/m 2 , and may be less than about 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 14,000, 13,000, 12,000, 1 1 ,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1 ,000 or fewer cm 2 /sec/m 2 .
- the flow rate of electrolyte through an electrochemical cell of an embodiment may be above or below about 1 ,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11 ,000, 12,000, 13,000, 14,000, 15,000, 16,000, 17,000, 18,000, 19,000, 20,000, 21 ,000, 22,000, 23,000, 24,000, 25,000, 26,000, 27,000, 28,000, 29,000, 30,000, 31 ,000, 32,000, 33,000, 34,000, 35,000, 36,000, 37,000, 38,000, 39,000, 40,000, 45,000, 50,000 cm 3 /sec/m 2 and those skilled in the art will readily adjust the flow rate to suit particular purposes and to achieve desirable performance parameters with particular cell geometries and electrolyte compositions.
- those skilled in the art will readily adjust the flow rate to suit particular purposes and to achieve desirable performance parameters with particular cell geometries and electrolyte compositions.
- those skilled in the art will readily adjust the flow rate to suit particular purposes
- the pressure difference between the inlet and outlet of the cell may be very low and may be close to zero.
- hydrogen potential of an electrode and particularly a cathode means the reduction potential of the electrode.
- cathodes may have high hydrogen potentials and may have hydrogen potentials of up to or greater than or about 2000mV (two thousand millivolts).
- the hydrogen potential of an electrode may be modified by the electrolyte in which it is immersed.
- reference to a metal that is "liquid at room temperature” or is “substantially” or “normally” liquid at room temperature means that the metal is or, is normally, or is in part, liquid at room temperature or temperatures approximating room temperature, or at a temperature of greater than about 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12 °C, 13 °C, 14°C, 15 °C, 16 °C, 17 °C, 18 °C, 19 °C, 20 °C, or 21 °C, and less than about 95 °C, 90 °C, 85°C, 80 °C, 75 °C, 70 °C, 65 °C, 60 °C, 55 °C, 50 °C, 45 °C, 40 °C, or 45C.
- the metal may be Mercury.
- a cell may potentially operate at any temperature between the freezing and boiling points of the aqueous solution, or of the metal substantially liquid at room temperature, subject to any operational limits that may be imposed by a user for safety reasons or for any other reasons. All such adjustments and determinations will be readily made by those skilled in the art.
- the cell may be operated at any temperature that is consistent with the safe operation of the cell.
- substantially liquid or “normally liquid” or “liquid” where used to describe a metal, indicates the ability of the metal to flow, and encompasses the full range of possible viscosities that may be compatible with the operation of a cell or electrode according to embodiments disclosed herein.
- paired anodes and cathodes of embodiments may present mutually opposed geometrical surfaces that are separated by a distance.
- the opposed anode and cathode surfaces may be separated by a distance of less than about 2.0cm, 1.9cm, 1.8cm, 1.7cm, 1.6cm, 1.5cm, 1.4cm, 1.3cm, 1.2cm, 1.1cm, 1.0cm, 0.95cm, 0.90cm, 0.85cm, 0.80cm, 0.75cm, 0.70cm, 0.65cm, 0.60cm, 0.55cm, 0.50cm.
- such separation distance may be substantially constant over the opposed area of the electrode surfaces.
- substantially constant is meant that the separation distance may vary from point to point to an extent that does not prevent the effective or desired operation of an electrochemical cell according to embodiments. It will be appreciated that if the separation of the opposed plates becomes less uniform, this may affect the performance of the cell in ways that will be readily understood and managed by those skilled in the art who will readily determine acceptable parameters for an electrode pair for particular applications and will understand when an electrode is in need of repair or replacement. In particular embodiments where an electrode has a geometrical surface of about 20 square meters, then the separation distance between opposed anode and cathode faces may be between about 0.5cm and about 2cm.
- an electrolyte or a solution or a liquid flows or may, or may in part, flow "through" an electrode, which may be a cathode, indicates that the electrode is, or is in part, porous so that the electrolyte, solution or liquid is able to pass through such pores from one side of the electrode to another side of the electrode, without having to flow around the geometrical surface of the electrode.
- scrubber bleed solution means the solution generated from processing of off-gases from a range of processes, including roasting of ores and tailings.
- a scrubber bleed solution may typically have an initial mercury concentration of up to 500 ppm.
- a scrubber bleed solution may contain any concentration of Mercury or of any other liquid normally or substantially liquid at room temperature and may contain more or less than about 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, lOOOppm or greater of either alone or in combination with any other metals or other chemical components.
- an electrolyte or electrolyte solution may contain similar or greater or lesser concentrations of Mercury.
- references to a “continuous flow”, “recycling” or “recirculation” of electrolyte means that the electrolyte is continuously circulated through one or more electrochemical cells, and may be supplemented, replenished, added to, diluted or otherwise modified during such recirculation process. This is to be distinguished from a batch process wherein the electrochemical cells or their associated containing structures are drained, or the electrolytic process temporarily or permanently halted after the processing of each batch of electrolyte.
- a continuous flow process may mean that the extraction of mercury or other metal substantially liquid at room temperature may be continued for extended periods, for example in embodiments the processing may be continued for 24 hours a day, 7 days a week, or for such period as may be necessary or desirable thus allowing the continuous processing of solution in response to its source.
- a continuous flow process may be desirable for the processing of a relatively dilute electrolyte. It will be understood that even when electrolyte is processed in a continuous flow manner, it may be necessary or desirable to shut the process down from time to time to permit maintenance and adjustments to the apparatus or process.
- a low current density means a current density of less than about 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 3, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, or 50V per square meter.
- a “collector” “collection device” or the like refers to a device or design feature for collecting deposited metal normally liquid at room temperature may comprise any suitable structure or structures, including trays, pipes, channels, grooves, valves or other devices or constructions. Those skilled in the art will readily recognise and construct a wide range of suitable collectors and adapt and implement them into embodiments of the subject matter disclosed.
- an electrode pair are in direct electrical contact through an electrolyte, or are both in direct contact with the electrolyte, indicates that the two electrodes are not separated by a membrane or other divider, such as a proton conductive membrane and that the same electrolyte solution is in direct physical contact with both electrodes.
- a scrubber solution may be derived from any source including but not limited to the roasting of mineral ores including tailings.
- the ore may be gold ore.
- an ore or a mineral ore refers to any ore, rock or tailings, that may be processed to extract components therefrom. Embodiments are hereafter generally described with reference to FIGS. 1 through 10.
- a substantially flat, flow through electrode assembly which may be a cathode.
- FIG. 1 shows a simplified diagram of an electrode for use in the first
- the electrode 400 may comprise a porous electrode body 412.
- the porous electrode 412 may be confined and supported by supporting grids 416 and 418.
- Metal feeder sheet 413 may be secured between porous cathode material 412 and grid 418 or may be positioned external to the grid. It will be understood that a variety of alternative arrangements of the components and a variety of alternative materials may be selected for particular requirements and will be readily understood and implemented by those skilled in the art. When mounted in a suitable electrochemical cell it will be understood that additional supporting structures, gaskets, and wiring to apply an electrical current to the electrode, may all be incorporated in the electrode. For simplicity and clarity these details are omitted from FIG. 1 but will be readily understood by those skilled in the art and such structures and the arrangement of an electrode within a cell are further explained elsewhere in this disclosure with reference to FIGS. 4 through 8.
- the feeder sheet 13 comprises a plurality of openings 433 distributed upon the sheet to allow electrolyte to access and flow through the electrode 412.
- the geometric surface of the electrode body 412 is defined by spatial dimensions X, Y, Z. This is to be distinguished from the actual total surface area of the electrode which may include pores, and notwithstanding the geometric surface of the electrode, the electrode may have a total surface area of at least about 500m 2 for each 1 m 2 of geometric surface and may be a cathode.
- the porous electrode 412 may be made of or may comprise carbon felt or may comprise other materials.
- the electrode may be a cathode and may be used for depositing from solution a metal substantially liquid at room temperature, and the metal may be mercury.
- a cathode 412 according to the first embodiment may be porous or otherwise constructed to present a large surface area and may be in the form of an electrically conductive felt or reticulated material, especially a carbon felt or reticulated carbon.
- a carbon felt or reticulated carbon may provide a high porosity particularly in excess of 90%; the high porosity provides a high cathode surface area and in embodiments this may provide an increased reaction rate and may be suitable for use with dilute solutions.
- carbon felt may be formed of carbon fibres, which may be formed form the carbonization and/or graphitization of synthetic polymer fibres, for example, polyacrylonitrile or ester fibres.
- the fibres may suitably have a diameter of the order of 6 to 8 microns, especially about 6 microns. Since a pad of fibres may be mechanically fragile, it may be mechanically supported in a frame or assembly which serves to hold the felt in a planar state. The felt may be supported under compression so as to have a planarity whereby a constant gap or separating distance is maintained between the cathode and an opposed anode.
- the cathode should, of course, be resistant to materials and conduction which may be present in the cell where it is used, which materials and conditions may be extreme and may include exposure to the presence of chlorine and chloride ions, heat, cold, acidity, alkalinity, oxidation and reduction conditions.
- Carbon felt and reticulated carbon are generally suited to these requirements.
- the material of the cathode may have a high hydrogen over potential which may allow mercury or other metal normally or substantially liquid at room temperature to be deposited in preference to liberation of hydrogen at the cathode 412.
- FIGS 4 through 8 illustrate an electrochemical cell generally designated 100 comprising an electrode according to the general design of the first
- a cathode 12 may be paired with an anode 10 in a suitable electrochemical cell 100.
- An anode 10 is generally essentially impermeable to the electrolyte solution, which may be or may comprise scrubber bleed solution or a treated extract or derivative thereof.
- an anode 10 may comprise a dimensionally stable electrode and may typically have a core of titanium sheet coated with a metal oxide, for example, one or more oxides of tantalum, iridium and platinum.
- a metal oxide for example, one or more oxides of tantalum, iridium and platinum.
- a range of alternative suitable materials will be readily identified and implemented by those skilled in the art. Without limitation, any forms of inert or relatively inert and conductive metal and/or metal oxide may be suitable for use as or in anodes according to
- the anode 10 suitably may have a low oxygen overpotential such that hydroxide ions are discharged liberating oxygen in preference to chloride ions releasing chlorine.
- the cathode 12 and the anode 10 each may comprise substantially flat geometrical surfaces and the substantially flat cathode and anode geometrical surfaces 210, 212 are mutually opposed and are substantially uniformly distanced 214.
- the distance between electrode geometrical surfaces 210, 212 is less than about 2 cm and the cathode 12 and the anode 10 are in direct fluid contact, and in embodiments the distance 214 is about 1cm or less than about 1cm.
- Electrochemical cells 100 may further comprise a solution inlet 102 positioned to direct at least a portion of the electrolyte solution to flow through the cathode 12.
- the cell which may comprise one or more collecting trays 100, may be configured so that substantially all of the solution flows through the cathode 12.
- Electrochemical cells may also comprise one or more collectors 220 for collecting a metal substantially liquid at room temperature under gravity induced flow when the metal is
- the inflow passage 17 may be angled or shaped so that any deposited metal is guided to collect at a collection point 222, or any trays 220.
- the collector structure itself may have any suitable design and may be a simple drain to allow the deposited metal to flow out of the cell 100 to be harvested in a suitable container.
- a cathode and anode may form an electrolysis electrode assembly 106 in a cell 100.
- electrode assemblies 106 each assembly having a cathode 12 and an anode 10 whose opposed faces are separated by a distance 214 therebetween.
- a flow path for flow of solution being treated extends from an inlet 102 to an outlet 104 of the cell.
- the flow path provides a contact time between the flowing solution and the electrode assemblies 106 sufficient for deposition of the mercury metal at the porous cathode 12.
- the flow path may, in particular, comprise an inflow passage 17 and an outflow passage extending across the cell in opposed generally parallel arrangement, with the electrode assemblies 106. These may be provided or in multiples and in embodiments a plurality of electrode
- a plurality of discrete branch passages between the electrode assemblies may communicate with the inflow passage 17 into the plurality of branch passages and from there through an adjacent porous cathode 12 into the gap 214 between such cathode 12 and its anode 10, the gap forms a gap passage communicating with the outflow passage and the solution flows along the gap passage against the anode 10 and into the outflow passage 2 and from there exits from the cell 100.
- a gas passage is maintained as small as possible, for example, 1 cm or less.
- a plurality of discrete treatment flow paths is formed within the cell 100 thereby maximizing the electrochemically active surface area of the cell per cell volume.
- apparatus for treating a scrubber bleed solution comprising the electrode according to embodiments.
- the apparatus may comprise a plurality of electrochemical cells.
- the electrochemical cells may be connected in series or in parallel and the scrubber bleed solution may be recycled through them with periodic or ongoing addition of fresh scrubber bleed solution.
- Electrochemical cell 100 has an inlet 102 and an outlet 104.
- Inlet 102 communicates with and inflow passage 17 and outlet 104 is in communication with an outflow passage 2.
- a plurality of electrode assemblies 106 is housed in cell 100 including a pair of end electrode assemblies 108, 110 and a plurality of intermediate electrode assemblies 112.
- Each of end assemblies 108 and 110 includes a cathode assembly 114 supporting a porous cathode 12 spaced form a dimensionally stable anode 10.
- Each of intermediate electrode assemblies 1 12 includes a pair of cathode assemblies 114 each supporting a porous cathode 12 spaced from a single dimensionally stable anode 10, therebetween.
- Flow passages 16 are defined between adjacent intermediate electrode assemblies 112 and between intermediate electrode assemblies 112 and end electrode assemblies 108 and 110, respectively.
- the flow passages 16 communicate with in-flow passage 17 but are closed adjacent out-flow passage 2 by caps 4.
- the electrode assemblies 106 are pressed together as an assembly between a pair of end supports 160 comprising inner end plates 1 , suitably of PVC, and outer end plates 18, suitably of steel.
- Cell 100 includes a plurality of cathode supports 19 each comprising cathode feeder 3 suitably in box section of mild steel sheet.
- each cathode assembly 114 comprises a frame 6 and a porous cathode 12 suitably a carbon fibre felt supported between a grid 116 and a grid 118.
- a metal feeder sheet 13 conveniently an expanded stainless steel sheet having a plurality of orifices, is supported between cathode 12 and grid 118 but alternatively the grid 116 may be positioned between the feeder 13 and electrode body 12 so long as suitable electrical contact is maintained between electrode body 12 and feeder sheet 13.
- Grid 116 is conveniently of PVC and comprises a plurality of spaced apart vertical members 11 and a plurality of spaced apart horizontal members 23.
- Grid 118 is conveniently of mild steel and comprises a plurality of spaced apart vertical members 5 and a plurality of spaced apart horizontal members 14. The grids 116 and 118 hold the porous cathode 12 with a required degree of planarity, in spaced relationship with anode 10.
- outer gaskets 7 are disposed between feeder sheets 13 and frame 6 adjacent outflow line 2 and outer gaskets 15 are similarly disposed adjacent in-flow passage 17.
- Gaskets 8 and 9 are disposed between opposed sides of anode 0 and grids 116 in the vicinity of out-flow passage 2 and in-flow passage 17.
- the gaskets 7, 8, 9 and 15 are suitably of neoprene but a range of other suitable materials will be readily identified, selected from, and used by those skilled in the art.
- the cathode supports 19 provide electrical contacts and are suitably of mild steel.
- a plurality of insulation and anode supports 20 suitably of PVC, house anode feeds 21, suitably of copper or other electrically conductive metal, connected to each anode 10.
- a mesh 22 suitably of polypropylene is disposed between porous cathode 12 and grid 116.
- a plurality of flow paths 120 in parallel are identified by flow line arrows.
- the cell 100 consists of ten (10) cathodes 12 and eleven (1 ) anodes 10.
- the cathodes 12 and anodes 10 are pressed together between the end plates 1 and the resulting assembly is compressed between end plates 18 which thus provide the rigidity which cell 100 needs to ensure a uniform separation of each anode 10 and is associated cathode 12.
- Each cathode 12 has opposed porous surfaces, the geometric integrity and planarity of which is maintained by there being contained between the three-dimensional grids 116 and 118.
- the cathode assembly 114 may comprise a cathode feeder 3 suitably of box section mild steel, which acts as a frame and a means of distributing electrical current to grid 118.
- the expanded metal feeder sheet 13 is welded onto the vertical member 5 of grid 118.
- Feeder sheet 13 acts as a current distributor to the porous cathode 12 and as a physical constrain to ensure that the porous cathode 12 retains a uniform thickness.
- the porous cathode 12 is pressed against the feeder sheet 13 by the three-dimensional grid 116, suitably of PVC; the polypropylene mesh 22 between grid 116 and cathode 12 ensures the planarity of the surface of cathode 12 facing anode 10.
- Grid 116 is attached to frame 6, suitably of PVC, which is suitably bolted through feeder sheet 13 to a corresponding frame 6 of the adjacent cathode assembly 114.
- Gasket 7 is interposed between frame 6 and feeder sheet 13.
- the electrode assemblies 106 are supported by the cathode feeders 3 which act as electrical contacts and by supports 44 which also conduct current to the electrode .
- the anode 10 suitably consists of a titanium sheet coated with one or more metal oxides to produce a dimensionally stable anode.
- suitable anode types include those produced by El-tech
- the current to the anodes 10 is distributed by anode feeds 21 , suitably four copper strips riveted on each face at either side of an anode 10.
- the anode 10 is supported by the insulation and anode supports 20 on either side which also electrically insulate the anode 10 from the cathodic bussing.
- scrubber bleed solution In operation the scrubber solution after it has been passed through a mercury recovery system is now termed scrubber bleed solution.
- the scrubber bleed solution enters the electrochemical cell 00 through the inlet 102 and passes into the in-flow passage 17.
- the solution passes through the cell 100 in parallel flow paths 120 the distribution of the solution through the cell 100 is governed by the pressure drop associated with each possible flow path 120.
- the only significant pressure drop in the system is that across the face of the porous cathode material of cathode 12. This ensures that each electrode receives a similar flow of solution. Any imbalance is self correcting as an increase in flow through any electrode will result in greater deposition and a consequent rise in the pressure across the electrode.
- From the in-flow passage 17 the solution passes up into the flow passage 16 where its exit is blocked at the top by cap 4.
- the solution exits through the faces of the cathode 12 through the grid 118, the expanded feeder sheet 13, the porous cathode 12, the polypropylene mesh 22 and into the grid 116.
- the solution passes up the grid 116 between the anode and the cathode 12 and into the out-flow passage 2 from where it exits via outlet 104 in the endplates 1 and 18.
- FIGS. 9 and 10 A second embodiment of an electrochemical cell is shown in FIGS. 9 and 10 and is generally designated 300.
- the cell 300 comprises body 301 holding a single anode 310 and a single cathode 312 separated by a distance 314. It will be seen that the interior 304 of the cell forces the electrolye which may be or derive from a scrubber bleed solution and may enter the cell through an inflow 302 leading into inflow chamber 317, to flow through the cathode 312 and around the anode 310 passing to outflow chamber 320 and then exiting the cell 300 through outflow 304.
- the cell 300 incorporates suitable brackets and mountings to hold the cathode 312 and anode 310 in place and comprises an electrical supply to apply a current through the electrodes and electrolyte.
- Mountings are generally designated 350 and 352, but for simplicity the detail of such mountings and of any power supply is omitted from FIGS. 1 , 9 and 10.
- a range of suitable methods and materials for the mounting and application of a potential difference to the electrodes will be readily apparent and will be readily implemented by those skilled in the art.
- cathode 312 The bottom 306 of cathode 312 is engaged by a drainage channel or collector 340 with a collection point 342 for any deposited metal that is substantially liquid at room temperature.
- the cathode 312 which may be a carbon felt cathode or of any other construction, such as the construction illustrated in FIG. 1 and described above
- the metal which may be mercury
- the collection channel may be of any suitable size but in an embodiment may be about 1.25 inches in diameter or may be narrower or wider.
- FIG. 2 and FIG. 3 A general embodiment of a method for treating off gases from ore processing, is shown in FIG. 2 and FIG. 3. It will be seen that in some cases, for clarity, features shown in one of the FIGS. 2 and 3 may be omitted in the other.
- the necessary processing solutions 500 may release gases, which may then be treated 510 to recover mercury and particulates, the resulting scrubber bleed solutions 660 may then be treated at 670 to separate the liquids from the solids, which are then taken to a leaching process 671. Then the liquid is mixed with necessary
- FIG. 3 which shows the general process according to FIG. 2 in the context of associated quench towers, scrubbers and the like
- gas from ore roasting 599 is introduced to a quench tower 600 along with introduced treatment solutions 602, bleed solution 605 is drawn off for processing and output 602 from the quench tower 600.
- the output from quench tower 600 is conveyed to a particulate scrubber 610, mixed with treatment solutions 612, and bleed liquids drawn off at 615 while output 621 from the scrubber 610 flows to the sulphur dioxide scrubber 620 to be mixed with treatment solutions 622.
- Bleed solution 625 is drawn off and the output 621 from the scrubber 620 flows to first mercury scrubber 630.
- Treatment solutions 632 is introduced and the output from the first mercury scrubber 630 flows to second mercury scrubber 640 to be mixed with treatment solution 642.
- the output 641 from the second mercury scrubber 640 flows to tails scrubber 650 for treatment with solutions 652, gas is vented at 651 and bleed solution 655 is removed for processing.
- the bleed solution from the first and second mercury scrubbers 630, 640, is combined in a common feed 660 leading into a separation tank 670 where solids 671 are removed for processing.
- the scrubber bleed solution from this separation process flows to an electrochemical cell 680, where mercury or other metals substantially liquid at room temperature are electrochemically deposited and are harvested. In the case of mercury metal this is typically in solutions the form of mercuric ions.
- the electrochemical cell 680 may be constructed or operated according to the first or second or other embodiments. In flowing through the porous cathode, mercuric ions are discharged electrochemically within the porous structure and the treated solution flowing from cell is thus poor in mercury metal ions. As the porous cathode becomes loaded with deposited mercury metal, the mercury will coalesce and become a free flowing liquid gathering at the base of the electrode. A suitable collector for collecting the liquid mercury is provided for at the base of the cathode or cathodes or more generally in the base of the cell 680.
- the scrubber bleed solution to the cell can be temporarily interrupted without terminating the operation of the process
- a surge tank 690 is provided for the used electrolyte solution, make up solution or additives 691 are added as needed, and the resulting solution 700 is returned to scrubbers 600, 610, 620, 630, 640, 650 as necessary or desirable.
- scrubbers 600, 610, 620, 630, 640, 650 as necessary or desirable.
- the scrubbing process may be operated on an essentially or substantially continuous flow basis.
- scrubber bleed solution may be continuously cycled from the roaster or combustion process scrubber to the electrochemical cell and treated solution recycled to the process.
- a typical cell 680 for treating scrubber bleed solution may have dimensions of about 5 ft. x 4 ft. x 6 ft.
- the cathode may have about 20 m 2 geometric surface area, while the porosity of the cathode may provide a total cathode surface of about 250,000 m 2 .
- the cell may be operated with a potential difference across the cell of about 10V, the gap between cathode and anode may be less than about 2cm, and in some cases about 1 cm or less than about 1cm.
- Such a cell may be operable treat a scrubber bleed solution flow of 20,000 cm 3 /sec/m 2 .
- the scrubber bleed solution may typically have an initial mercury concentration of up to 500 ppm.
- the rate of flow of scrubber bleed solution may be maintained low and in particular embodiments may typically be between about 5,000 cm 3 /sec/m 2 to 20,000 cm 3 /sec/m 2 , depending on the concentration of mercury metal. At high concentrations of mercury metal the flow rate may preferably be maintained at the at the lower end of the 5,000 cm3/sec/m2 to 20,000 cm3/sec/m2 range. In one embodiment the pressure drop between the inflow passage and the outflow passage is effectively zero, so that the pressure drop through the porous cathode governs the flow rate, this flow rate being governed by the porosity.
- a method and apparatus for the removal of a metal which may be mercury from a solution which may be a scrubber solution whereby the resulting solution can be recycled.
- a scrubber solution it may be recycled to the mill process.
- the scrubber solutions may be created by the roasting of ore.
- the mercury is electrochemically deposited and subsequently collected as metallic mercury.
- the scrubber solution may flow through a porous cathode and across the surface of an anode of an electrochemical cell.
- a potential difference is maintained between the cathode and the anode to effect electrochemical deposition of the mercury metal in the porous cathode.
- the porous cathode may have a high electrochemically active surface area per unit volume and in embodiments this be achieved by employment of a cathode material of high porosity in excess of 90%.
- the cathode can be loaded with a high level of mercury metal which is collected by allowing the mercury to exit the electrode at its base by gravity induced flow.
- the cathode materials may have a substantially evenly distributed or substantially homogenous, or substantially uniform porosity.
- the porosity should permit loading of the cathode with a mercury level of more than 0.5 g cm 3 .
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Hybrid Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011800372884A CN103201413A (en) | 2010-07-29 | 2011-07-20 | Method and apparatus for electrochemical recovery of mercury from solution |
| BR112012030295A BR112012030295A2 (en) | 2010-07-29 | 2011-07-20 | method and apparatus for electrochemical recovery of mercury from solutions |
| CA2793925A CA2793925A1 (en) | 2010-07-29 | 2011-07-20 | Method and apparatus for electrochemical recovery of mercury from solutions |
| AU2011284734A AU2011284734A1 (en) | 2010-07-29 | 2011-07-20 | Method and apparatus for electrochemical recovery of mercury from solutions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB1012711.6A GB201012711D0 (en) | 2010-07-29 | 2010-07-29 | Method and apparatus for electrochemical recovery of mercury from solutions |
| GB1012711.6 | 2010-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012012871A1 true WO2012012871A1 (en) | 2012-02-02 |
Family
ID=42799262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CA2011/000837 Ceased WO2012012871A1 (en) | 2010-07-29 | 2011-07-20 | Method and apparatus for electrochemical recovery of mercury from solutions |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20120048745A1 (en) |
| CN (1) | CN103201413A (en) |
| AU (1) | AU2011284734A1 (en) |
| BR (1) | BR112012030295A2 (en) |
| CA (1) | CA2793925A1 (en) |
| GB (1) | GB201012711D0 (en) |
| WO (1) | WO2012012871A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10221499B2 (en) * | 2015-06-25 | 2019-03-05 | Ge-Hitachi Nuclear Energy Americas Llc | Nuclear fuel structure and method of making a nuclear fuel structure using a detachable cathode material |
| SE2430126A1 (en) * | 2024-03-13 | 2025-09-14 | Atium Ab | Device for mercury removal from dental wastewater streams |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4643819A (en) * | 1984-01-09 | 1987-02-17 | Yves Heroguelle | Devices for the galvanic recovery of metals from diluted solutions |
| US5292412A (en) * | 1990-04-12 | 1994-03-08 | Eltech Systems Corporation | Removal of mercury from waste streams |
| US6017428A (en) * | 1997-07-16 | 2000-01-25 | Summit Valley Equipment And Engineering, Inc. | Electrowinning cell |
| WO2000061827A1 (en) * | 1999-04-12 | 2000-10-19 | Ea Technology Limited | An electrochemical cell for use in the recovery of mercury from aqueous solutions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4149943A (en) * | 1977-08-31 | 1979-04-17 | Ppg Industries, Inc. | Method of recovering mercury |
| CA1159008A (en) * | 1978-12-04 | 1983-12-20 | Sankar Das Gupta | Reactor with working and secondary electrodes and polarity reversal means for treating waste water |
| US4627899A (en) * | 1985-02-15 | 1986-12-09 | The United States Of America As Represented By The Secretary Of The Interior | Electrolytic cell and methods combining electrowinning and electrochemical reactions employing a membrane or diaphragm |
-
2010
- 2010-07-29 GB GBGB1012711.6A patent/GB201012711D0/en not_active Ceased
-
2011
- 2011-07-20 AU AU2011284734A patent/AU2011284734A1/en not_active Abandoned
- 2011-07-20 WO PCT/CA2011/000837 patent/WO2012012871A1/en not_active Ceased
- 2011-07-20 CA CA2793925A patent/CA2793925A1/en not_active Abandoned
- 2011-07-20 US US13/187,130 patent/US20120048745A1/en not_active Abandoned
- 2011-07-20 BR BR112012030295A patent/BR112012030295A2/en not_active IP Right Cessation
- 2011-07-20 CN CN2011800372884A patent/CN103201413A/en active Pending
-
2014
- 2014-04-01 US US14/231,985 patent/US20150034497A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4643819A (en) * | 1984-01-09 | 1987-02-17 | Yves Heroguelle | Devices for the galvanic recovery of metals from diluted solutions |
| US5292412A (en) * | 1990-04-12 | 1994-03-08 | Eltech Systems Corporation | Removal of mercury from waste streams |
| US6017428A (en) * | 1997-07-16 | 2000-01-25 | Summit Valley Equipment And Engineering, Inc. | Electrowinning cell |
| WO2000061827A1 (en) * | 1999-04-12 | 2000-10-19 | Ea Technology Limited | An electrochemical cell for use in the recovery of mercury from aqueous solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2793925A1 (en) | 2012-02-02 |
| CN103201413A (en) | 2013-07-10 |
| BR112012030295A2 (en) | 2016-08-09 |
| US20120048745A1 (en) | 2012-03-01 |
| US20150034497A1 (en) | 2015-02-05 |
| GB201012711D0 (en) | 2010-09-15 |
| AU2011284734A1 (en) | 2012-10-18 |
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