EP2806053A2 - Elektrolysegerät, Anode für dieses Elektrolysegerät und in diesem Elektrolysegerät verwendetes Elektrolyseverfahren - Google Patents

Elektrolysegerät, Anode für dieses Elektrolysegerät und in diesem Elektrolysegerät verwendetes Elektrolyseverfahren Download PDF

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Publication number
EP2806053A2
EP2806053A2 EP20140169276 EP14169276A EP2806053A2 EP 2806053 A2 EP2806053 A2 EP 2806053A2 EP 20140169276 EP20140169276 EP 20140169276 EP 14169276 A EP14169276 A EP 14169276A EP 2806053 A2 EP2806053 A2 EP 2806053A2
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EP
European Patent Office
Prior art keywords
anode
central axis
cathode
electrolyser
branches
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP20140169276
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English (en)
French (fr)
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EP2806053A3 (de
Inventor
Philippe Beauvier
Francis Boiocchi
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Aureus
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Aureus
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Publication date
Application filed by Aureus filed Critical Aureus
Publication of EP2806053A2 publication Critical patent/EP2806053A2/de
Publication of EP2806053A3 publication Critical patent/EP2806053A3/de
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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
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • 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 invention relates to an electrolyser for recovering metals from a bath containing metal ions, an electrolysis process in this electrolyser, and an anode for this electrolyser.
  • an electrolyzer comprising a plurality of concentric cylindrical anodes between which are also cylindrical cathodes.
  • Such an electrolyzer is for example described in the patent application US4039422 .
  • Another electrolyser described in the patent application FR2463822 ( US4276147A ), has a cylindrical cathode and a cylindrical anode in the center of the cathode.
  • electrolysers are also known from: FR2607832A1 , US3784455A and US5873986A .
  • the Applicant has found experimentally that the surface of the electrodes is an important factor in the efficiency of the electrolyser.
  • the efficiency of an electrolyser can be measured by setting the operating conditions of the electrolyser and then by measuring the weight of metal recovered after a predetermined period. In order to be able to compare the efficiency of an electrolyser with that of another electrolyser, the experimental conditions fixed are the same for these two electrolysers. For example, here, the efficiency of an electrolyser corresponds to the weight of metal recovered for one hour with an electric current intensity of 10 A.
  • the depositor realized that the yield increases when the surface of the anode is greater than that of the cathode, the surface ratio being different depending on the electrolyzed metal.
  • the applicant also wished to manufacture an electrolyser which has a limited space requirement.
  • the applicant has therefore sought to design an electrolyzer which remains compact, while having an anode having a surface greater than the surface of the cathode.
  • the invention therefore relates to an electrolyser according to claim 1.
  • An electrolyzer comprising an anode whose guide curve is a star makes it possible to obtain a surface of the anode greater than the surface of the cathode while keeping the anode inside the cathode. Thus, it does not increase the overall size of the electrolyser.
  • the angle at the top must be greater than 10 °, because for lower values, the applicant realized that the performance of the electrolyser was not efficient enough. For values of the apex angle greater than 90 °, the size of the electrolyser is not reduced or only slightly reduced.
  • the width of the flanks greater than 10 mm makes it possible to obtain an elevated anode surface.
  • a lower width does not sufficiently increase the surface of the anode relative to the surface of the cathode.
  • Embodiments of this electrolyser may further include one or more of the features of the dependent claims.
  • the invention also relates to an electrolysis process in an electrolyser having one or more of the above characteristics, wherein the intensity of the electric current flowing between the anode and the cathode is less than 40 A. For a higher intensity , the applicant experimentally realized that the efficiency of the electrolysis was lower.
  • the invention also relates to electrodes for the electrolyser above.
  • the figure 1 represents an electrolyser 2.
  • the electrolyser 2 is intended to recover metals from a bath containing metal ions.
  • the recovered metal may be gold, silver, copper, or any other metal whose associated metal ion is a cation.
  • the metal that one seeks to recover is silver.
  • the bath may be a rinse bath obtained, for example, after jewelry plating operations.
  • the bath can also be a demetallization bath, that is to say a bath in which parts Metals are introduced on which we seek to recover gold, silver or any other metal.
  • the figure 1 is oriented according to an orthogonal reference XYZ where Z is the vertical direction.
  • the XY plane and the planes parallel to the XY plane are horizontal planes.
  • the terms “lower”, “upper”, “above” and “below”, “on” and “below” are defined with reference to the direction Z.
  • the electrolyser 2 comprises a tank 4 closed, in a sealed manner, by a lid 6.
  • the tank 4 and the lid 6 are made of a plastic material, here polyvinyl chloride commonly called PVC.
  • the tank 4 is here a circular section cylinder which extends in the vertical direction.
  • the tank 4 has a symmetry of revolution with respect to a vertical central axis 7.
  • the diameter of the tank 4 is less than 50 cm, and preferably less than 40 cm.
  • the height h in the vertical direction of the tank 4 and its lid 6 is less than 50 cm, and preferably less than 40 cm.
  • the height h is equal to 32 cm.
  • the lid 6 is here circular, with a diameter of 2 to 10 cm greater than the diameter of the tank 4.
  • the lid 6 has a diameter equal to 40 cm.
  • the tank 4 is placed on a support 8.
  • the entire support 8 and the tank 4 must have a limited space.
  • the support 8 is parallelepipedic.
  • the length in the direction X of the support 8 is less than 80 cm, and preferably less than 70 cm.
  • the length is equal to 60 cm.
  • the width in the direction Y of the support 8 is less than 60 cm, and preferably less than 50 cm.
  • the width is equal to 46 cm.
  • the height of the support 8 in the vertical direction is less than 20 cm, and preferably less than 15 cm.
  • the height is equal to 14 cm.
  • the tank 4 is intended to contain a liquid bath 10 containing metal ions, here silver ions Ag + .
  • the bath 10 completely fills the tank 4.
  • the bath 10 is typically a basic bath, here a cyanide bath.
  • the tank 4 here comprises a suction port 12 and a discharge port 14 of the bath 10.
  • the orifices 12 and 14 are here circular orifices, of identical diameters, here equal to 2 cm.
  • the electrolyser 2 also comprises a hydraulic circuit 15.
  • the function of the circuit 15 is to circulate and stir the bath 10 in the tank 4.
  • the circuit 15 comprises a pump 16 and pipes 18.
  • the pump 16 is mechanically connected to the orifices 12 and 14 by pipes 18, here PVC, of diameter equal to the diameter of the orifices 12 and 14.
  • the pump 16 has a flow rate greater than 1 m 3 / h, and preferably greater than 2 m 3 / h.
  • the flow rate of the pump is equal to 3 m 3 / h.
  • the electrolyser 2 also comprises a pipe 19 for evacuating the gases produced during the electrolysis of the bath 10.
  • the pipe 19 passes through the lid 6 and opens into the top of the tank 4. A slight overpressure is created in the tank 4 so that the gases are evacuated through the pipe 19.
  • the electrolyser 2 comprises two electrodes, a cathode 20 and an anode 22, placed inside the tank 4.
  • the cathode 20 and the anode 22 extend according to the vertical direction and are centered on the axis 7.
  • the respective heights of the cathode 20 and the anode 22 in the vertical direction are denoted h 1 and h 2 .
  • the values of h 1 and h 2 are such that neither the cathode 20 nor the anode 22 are in direct mechanical contact with a bottom of the tank 4 resting on the support 8.
  • the height h 1 is equal to 28, 5 cm and the height h 2 is equal to 24.9 cm.
  • the cathode 20 and the anode 22 are connected to a source 24 of electrical power, located outside the tank 4, by connections 26.
  • the connections 26 are located respectively on an upper periphery of the cathode 20 and the anode 22. Holes are arranged in the cover 6 for the connections 26, so that they can be connected to the source 24.
  • the cathode 20 has three electrical connections and the anode 22 has four.
  • the connections 26 are all identical and consist essentially of a vertical metallic rod. To simplify the figure, only four connections 26 are shown. In this embodiment, these connections 26 also make it possible to hold the cathode 20 and the anode 22 suspended above the bottom of the tank 4.
  • the part of the connections 26 which is immersed in the bath 10 is covered with an electrically insulating sheath.
  • the anode 22 is placed inside the space 28.
  • the anode 22 is a cylinder, the shape of which will be described in more detail with reference to the Figures 2 and 3 .
  • the distance between the cathode 20 and the anode 22 measured in a horizontal plane is denoted d.
  • the distance d is less than 30 cm, and preferably less than 20 cm.
  • the distance d is equal to 10.5 cm.
  • the hydraulic circuit 15 also comprises a duct 30 fluidly connected to the orifice 14.
  • the duct 30 is located between the cathode 20 and the anode 22. It extends vertically over the entire height of the cathode 20 and comprises nozzles 32
  • the bath 10 flows through the conduit 30 through the pump 16.
  • Each nozzle 32 is designed to propel the bath 10 in a horizontal and tangential direction to the surface of the cathode 20.
  • the number of nozzles 32 is greater than three, and preferably greater than five.
  • the nozzles 32 are evenly distributed over the height of the duct 30.
  • the anode 22 will now be described in more detail with reference to the figure 2 .
  • the anode 22 is a cylinder whose generator is parallel to the axis 7.
  • the steering curve of the cylinder is a star having several branches 40.
  • the number of branches is greater than ten and preferably greater than fifteen.
  • the number of branches is equal to eighteen.
  • the branches 40 are all identical.
  • Each branch 40 comprises a first flank 42 and a second flank 44.
  • the first flank 42 and second flank 44 extend respectively in a first and a second vertical plane.
  • the apex angle between the first and the second plane is noted ⁇ ( figure 3 ).
  • the measurement of the angle ⁇ is between 10 ° and 90 °, and preferably between 10 ° and 40 °, or between 10 ° and 20 ° in the case where the recovered metal is silver.
  • the angle ⁇ is equal to 14 °.
  • the two flanks 42 and 44 meet to form a vertical edge 46 whose radius of curvature, in a horizontal plane, is less than 1 cm, and preferably greater than 1 mm.
  • Each flank 42 and 44 has a width noted l measured in a horizontal plane.
  • the widths l are all identical and between 10 mm and 70 mm, and preferably between 40 mm and 65 mm, or between 57 mm and 60 mm. Here, the width l is equal to 58.4 mm.
  • a circular ring 48 is fixed without any degree of freedom on an upper part of the anode 22.
  • the ring 48 is centered on the axis 7 and extends in a horizontal plane.
  • the connections 26 are fixed without any degree of freedom and distributed evenly over the ring 48.
  • the branches 40 will now be described in more detail with reference to the figure 3 .
  • Each branch 40 extends radially from a proximal end 50 to a distal end 52 coinciding with the edge 46.
  • each proximal end 50 is located on an inner circle 54, centered on the axis 7.
  • the diameter of the circle 54 noted d 1 is here between 6 cm and 10 cm, and preferably between 7 and 9 cm.
  • the diameter d 1 is equal to 8.1 cm.
  • Each distal end 52 is located on an outer circle 56, centered on the axis 7, of diameter d 2 .
  • the diameter d 2 is here between 18 cm and 21 cm, and preferably between 19 and 20 cm.
  • the diameter d 2 is equal to 19.7 cm.
  • the diameter of the ring 48 ( figure 2 ) is between d 1 and d 2 .
  • the inside of the circle 54 is here hollowed out over the entire height of the anode 22.
  • a filter is arranged inside the circle 54 in order to filter the bath 10.
  • the cathode 20 will now be described with reference to the figure 4 .
  • the cathode 20 comprises, in this embodiment, a plate 60 wound around the axis 7.
  • the plate 60 unwound has a rectangular shape.
  • the plate 60, wound, delimits the space 28. It has two vertical ends overlapping a length, measured along a horizontal direction and tangent to one of these ends, between 0.5 and 2 cm .
  • the total length of the unrolled plate 60 is between 90 cm and 100 cm. The total length here is equal to 95.5 cm.
  • the width of the plate 60 is equal to the height h 1 .
  • An upper periphery of the plate 60 comprises hooks 62, mechanically fixed on the plate 60.
  • On each hook 62 is fixed a connection 26.
  • the cathode 20 has three hooks evenly spaced on the upper periphery of the plate 60.
  • Each hook 62 has the shape of a square, having a vertical side and a horizontal side. The vertical side, here of form rectangular, is fixed without any degree of freedom on the plate 60.
  • the connection 26 is fixed on the upper horizontal side of the catch 62.
  • the anode 22 and the cathode 20 are made of a cyanide-resistant conductive material contained in the bath 10.
  • the cathode 20 and the anode 22 are made of stainless steel, for example 316L stainless steel.
  • the surface of the cathode 20 must be smooth in order to easily recover the silver deposit.
  • the thickness of the flanks 42 and 44, and the thickness of the plate 60 are here identical and between 0.5 and 3 mm, and preferably between 0.8 and 2 mm. Here, the thickness is equal to 1 mm.
  • the cathode 20 and the anode 22 are such that the ratio of the surfaces to the anode 22 and the cathode 20 is 2.2 to 10%, and preferably within 5%, or within 2.5%.
  • the ratio of the surfaces facing each other is that of the surface of the anode on the surface of the cathode.
  • the surfaces opposite the anode 22 comprise the total surface of the flanks 42 and 44, the surface of a flank 42 multiplied by twice the number of branches 40 of the anode 22.
  • the area facing the cathode 20 is equal to the length of the plate 60 multiplied by the height h 2 of the anode 22 because the anode is shorter than the cathode in this embodiment.
  • the Figures 5 and 6 represent another embodiment, respectively, of an anode 70 and a cathode 72 specially designed to improve the performance of an electrolyser when used to recover gold.
  • This electrolyser specially designed to recover gold is identical to the electrolyser 2 except that it comprises the anode 70 and the cathode 72 instead of the anode 22 and the cathode 20, respectively.
  • the bath is a bath containing gold ions, Au 3+ .
  • the anode 70 is identical to the anode 22, except that the number and dimensions of the branches are different. More specifically, the anode 70 here comprises a number of branches greater than twenty, and preferably greater than thirty. Here, it has thirty-two branches.
  • the height of the anode 70 is here equal to 29.4 cm.
  • the width of each sidewall is here between 15 mm and 35 mm, and preferably between 20 mm and 30 mm. Here, the width of each flank is equal to 25.9 mm.
  • the diameter of the outer circle is between 17 cm and 20 cm, and preferably between 18 cm and 19 cm. Here, the diameter of the outer circle is equal to 18.6 cm.
  • the diameter of the inner circle is between 12 cm and 15 cm, and preferably between 13 cm and 14 cm. Here, the diameter of the inner circle is equal to 13.6 cm.
  • the apex angle ⁇ is here between 10 ° and 90 °, and preferably between 15 ° and 40 °. Here, the angle ⁇ is equal to 30 °.
  • the cathode 72 ( figure 6 ) comprises here six flat plates 78 arranged vertically about the axis 7.
  • the plates 78 are all identical and are rectangular.
  • the height of each plate 78 is between 27 cm and 31 cm, and preferably between 28 and 30 cm.
  • each plate 78 has a height equal to 29 cm.
  • the width of each plate 78 is between 8 cm and 11 cm, and preferably between 9 cm and 10 cm.
  • each plate 78 has a width of 9.5 cm.
  • the mechanism 82 here consists of a hook 84 mechanically secured to the plate 78.
  • the hook 84 is in the form of a bracket, a vertical portion of which is in the same vertical plane as the plate 78 and a horizontal portion rests in locked position, on the frame 80.
  • the horizontal part has a hole.
  • the mechanism 82 also includes a screw 86, fixed without any degree of freedom to the frame 80.
  • the screw 86 passes through the hole of the horizontal portion of the hook 84 and is screwed here in a blind nut, not shown here. When the screw 86 is screwed, this makes it possible to fix the horizontal part of the catch 84 on the armature 80.
  • the plate 78 can be detached from the armature 80 and thus the other plates 78.
  • connections 26 are here mechanically fixed without any degree of freedom on the armature 80.
  • the anode 70 and the cathode 72 are such that the ratio of the surfaces to the anode 70 and the cathode 72 is 2.9 to 10%, and preferably within 5%, or within 2.5%.
  • the surface of the cathode 72 opposite the anode 70 is equal to the number of plates 78 (here, six) multiplied by the surface of a plate 78.
  • the surface opposite the anode 70 is here equal to the width of a flank 42 multiplied by the height of a plate 78 (because here, it is the height of the plates 78 which is less than the height of the anode 70) multiplied by twice the number of branches 40 of the anode 70.
  • the figure 7 illustrates the steps of an electrolysis process in the electrolyser 2 in the particular case where the metal to be recovered is gold and where it is the anode 70 and the cathode 72 which are used.
  • the tank 4 is filled with the bath 10.
  • the circuit 15 circulates and mixes the bath 10 in the tank 4.
  • the power source 24 delivers an electric current between the anode and the cathode whose intensity is between 1 A and 40 A.
  • the intensity delivered varies in the time to compensate for the variation of the resistivity of the bath 10 as the gold settles on the cathode 72.
  • a step 96 the electrolysis of the metal ions contained in the bath 10 occurs. A deposit of gold is then formed on the cathode 72. The gases produced by the electrolysis are discharged through the pipe 19.
  • a user stops the operation of the power source 24 and opens the tank 4. It can then freely remove the cathode 72.
  • the user unlocks the mechanism 82.
  • the user unscrews the screws 86 to release the plates 78 and scrapes each plate 78 released to recover the gold deposit formed during the electrolysis.
  • a step 102 the user places the plates 78 on the cathode 72 by locking the mechanism 82, then puts the cathode 72 in the tank 4. The electrolyzer is then ready for use again.
  • step 100 The process of electrolysis of silver is identical except that cathode 20 and anode 22 are used.
  • the user does not have to release the plates 78, but to unroll the plate 60 and then scrape it so as to recover the silver deposit formed during the electrolysis.
  • each branch of the anode extends from a proximal end lying on the same inner ellipse to a distal end also lying on the same outer ellipse .
  • the number of branches of the anodes 22 and 70 may be different, as long as the ratio of the surfaces facing the anode and the cathode remains within the ranges set forth above, respectively, for silver and silver. 'gold.
  • the above-mentioned surface area ratios do not vary if the heights of the cathode and the anode are increased or decreased by the same value.
  • the height of the anode can therefore be adapted, for example, according to the maximum amount of metal capable of being fixed on the cathode before interrupting the electrolysis.
  • the tank 4 may not be cylindrical. It can have a cubic form, for example.
  • the inside of the anode may not be hollowed out.
  • it may be filled with a non-conductive material.
  • the cathode 72 may comprise more than six removable flat plates. If necessary, the cathode 72 can also be used, after adaptation of the dimensions of its plates, for the recovery of other metals than gold.
  • the number of nozzles may be less than three.
  • the number of electrical connections can be different.
  • the catches of the cathode 20 on which the connections 26 are fixed may be made differently.
  • the vertical side of the catch protrudes beyond the upper periphery of the plate 60 to move the connection 26 away from the faces of the plate 60.
  • the admission of the bath into the tank can be performed via a conduit other than the conduit 30.
  • the conduit 30 is omitted.

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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)
EP14169276.4A 2013-05-24 2014-05-21 Elektrolysegerät, Anode für dieses Elektrolysegerät und in diesem Elektrolysegerät verwendetes Elektrolyseverfahren Withdrawn EP2806053A3 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1354724A FR3005965B1 (fr) 2013-05-24 2013-05-24 Electrolyseur, anode pour cet electrolyseur et procede d'electrolyse dans cet electrolyseur

Publications (2)

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EP2806053A2 true EP2806053A2 (de) 2014-11-26
EP2806053A3 EP2806053A3 (de) 2015-07-22

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EP14169276.4A Withdrawn EP2806053A3 (de) 2013-05-24 2014-05-21 Elektrolysegerät, Anode für dieses Elektrolysegerät und in diesem Elektrolysegerät verwendetes Elektrolyseverfahren

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3784455A (en) 1971-12-28 1974-01-08 Western Electric Co Methods of electrolytic regenerative etching and metal recovery
US4039422A (en) 1975-10-14 1977-08-02 Packer Elliot L Metal recovery unit
FR2463822A1 (fr) 1979-08-17 1981-02-27 Sam Ahmad Procede et appareilllage pour isoler des metaux de leurs solutions, cathode utilisee et son procede de preparation
FR2607832A1 (fr) 1986-12-08 1988-06-10 Jehanno Jean Daniel Dispositif de recuperation electrolytique de metaux en solutions diluees
US5873986A (en) 1997-03-19 1999-02-23 Cpac, Inc. Metal recovery apparatus

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3784455A (en) 1971-12-28 1974-01-08 Western Electric Co Methods of electrolytic regenerative etching and metal recovery
US4039422A (en) 1975-10-14 1977-08-02 Packer Elliot L Metal recovery unit
FR2463822A1 (fr) 1979-08-17 1981-02-27 Sam Ahmad Procede et appareilllage pour isoler des metaux de leurs solutions, cathode utilisee et son procede de preparation
US4276147A (en) 1979-08-17 1981-06-30 Epner R L Apparatus for recovery of metals from solution
FR2607832A1 (fr) 1986-12-08 1988-06-10 Jehanno Jean Daniel Dispositif de recuperation electrolytique de metaux en solutions diluees
US5873986A (en) 1997-03-19 1999-02-23 Cpac, Inc. Metal recovery apparatus

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Publication number Publication date
FR3005965B1 (fr) 2016-07-29
EP2806053A3 (de) 2015-07-22
FR3005965A1 (fr) 2014-11-28

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