WO2014009768A1 - Ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et cellule et procédé correspondants - Google Patents

Ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et cellule et procédé correspondants Download PDF

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Publication number
WO2014009768A1
WO2014009768A1 PCT/IB2012/001776 IB2012001776W WO2014009768A1 WO 2014009768 A1 WO2014009768 A1 WO 2014009768A1 IB 2012001776 W IB2012001776 W IB 2012001776W WO 2014009768 A1 WO2014009768 A1 WO 2014009768A1
Authority
WO
WIPO (PCT)
Prior art keywords
cathode
frame
porous wall
anode
internal
Prior art date
Application number
PCT/IB2012/001776
Other languages
English (en)
Inventor
Luc Albert
Original Assignee
Eramet
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eramet filed Critical Eramet
Priority to PCT/IB2012/001776 priority Critical patent/WO2014009768A1/fr
Priority to UAA201500869A priority patent/UA113886C2/uk
Priority to CN201280074592.0A priority patent/CN104685106B/zh
Publication of WO2014009768A1 publication Critical patent/WO2014009768A1/fr
Priority to ZA2015/00083A priority patent/ZA201500083B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • 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
    • 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 invention relates to an internal cell frame assembly for electrolysis of manganese, intended to be placed in a tank containing a feed solution, the frame assembly comprising :
  • a clamping assembly capable of maintaining the cathode frames, the anode frames, and the diaphragms applied against each other,
  • each cathode frame delimiting an internal compartment for receiving a cathode, the internal cathode receiving compartment emerging axially in a first axial opening facing a first adjacent anode frame and in a second axial opening, facing a second adjacent anode frame.
  • Such a frame assembly is intended to be removably inserted into a tank of a manganese electrolysic cell.
  • Such a frame assembly includes an alternation of cathode frames and of anode frames which are separated from each other by diaphragms. Longitudinal rods and end nuts maintain the frames and the diaphragms applied against each other in order to guarantee a good seal between the compartments delimited by each of the frames.
  • a cathode is introduced into the internal cathode compartment of each cathode frame.
  • a feed solution is carried to the internal compartment through transverse apertures made into the cathode frames.
  • the feed solution forms a catholyte solution.
  • Manganese metal then deposits on the cathode by an electrolytic process.
  • the catholyte solution flows into the internal anode receiving compartments of the anode frames through the diaphragms, in order to form an anolyte solution.
  • the anode At the anode, a part of the water which is available in the anolyte solution is decomposed to form oxygen and hydronium ions. Moreover, other parasitic reactions also occur at the anode.
  • the manganese which is available as a cationic form into the solution which is issued from the cathode is partially oxidized at the anode to form manganese dioxide in a solid form.
  • the diaphragm comprises cloths which are necessary to create a physical porous separation between the cathode receiving compartment and the anode receiving compartment. These cloths slow the diffusion of the hydronium ions from the anode towards the cathode.
  • the pH at the anode is relatively low, and is lower than the pH available at the cathode.
  • the frame assembly must therefore be assembled with great care.
  • the "filter press" design of the known frame assemblies it is sometimes difficult to provide an assembly which ensures that the only contact between the catholyte solution and the anolyte solution occurs through the diaphragm clothes.
  • each frame assembly has to be disassembled on a regular basis during production.
  • sludge resulting in particular from manganese dioxide
  • the sludge has to be removed at regular intervals and the diaphragms must be cleaned.
  • One aim of the invention is therefore to provide a frame assembly for a manganese electrolysis cell which provides an improved yield, while still being easy to assemble and disassemble when needed.
  • the subject-matter of the invention is an internal frame assembly of the afore-mentioned type, characterized in that at least one diaphragm comprises a first porous wall covering a first axial opening of a cathode frame, a second porous wall covering the second axial opening of the cathode frame and at least a connecting wall connecting the first porous wall and the second porous wall along the cathode frame, the first porous wall, the second porous wall and the connecting wall defining an internal space containing or defining the internal cathode receiving compartment.
  • the frame assembly comprises one or more of the following features, taken individually or according to any possible technical combination : - the first porous wall, the second porous wall and the or each connecting wall define a pocket receiving the cathode frame ;
  • the cathode frame defines a lower window for circulation of an anolyte solution, each adjacent anode frame defining a lower window facing the lower window of the cathode frame for reception and circulation of the anolyte solution, the first porous wall and the second porous wall each defining a lower opening located facing the lower windows ;
  • connecting frame surrounding the lower opening defined in the first porous wall and surrounding the lower opening defined in the second porous wall, the connecting frame being sealingly connected to the first porous wall and to the second porous wall, the connecting frame being inserted in the lower window of the cathode frame ;
  • the or each connecting wall comprises a first lateral part integral with the first porous wall and a second lateral part integral with the second porous wall, the first lateral part and the second lateral part being applied on each other, the connecting wall comprising attaching elements between the first lateral part and the second lateral part, the attaching elements being advantageously releasable ;
  • the first porous wall and the second porous wall define an upper opening for insertion of a cathode in the internal cathode receiving compartment ;
  • the cathode frame defines at least one lower side aperture for filling a feed solution containing manganese ions into the internal cathode receiving compartment, the connecting wall defining, for each lower side aperture a lateral window communicating with the lower side aperture ;
  • the cathode frame defines at least one upper side aperture for discharging cathode gases, the connecting wall defining, for each upper side aperture a lateral window located around the upper side aperture ;
  • the cathode frame comprises a first upper cross member delimiting upwardly the first axial opening and a second upper cross member delimiting upwardly the second axial opening,
  • first porous wall and the second porous wall each having an upper attaching element able to engage around respectively the first upper cross member and the second upper cross member ;
  • each adjacent anode frame comprising an axial face applied respectively on the first porous wall and on the second porous wall of the diaphragm, each anode frame comprising a sealing element interposed between the axial face and respectively the first porous wall and the second porous wall ;
  • the anode frame defines an inner anode receiving compartment, the frame assembly comprising, for each anode frame, an anode received in the inner anode receiving compartment, the anode comprising at least one first spacer intended for pressing on the first porous wall of an adjacent diaphragm and at least a second spacer intended for pressing on an opposite second porous wall of an opposite adjacent diaphragm;
  • each cathode frame it comprises, for each cathode frame, a removable cathode received in the internal space between the first porous wall, the second porous wall and the connecting wall.
  • the invention also concerns a cell for electrolysis of manganese, comprising :
  • a tank delimiting an inner volume for receiving a feed solution
  • the cell according to the invention comprises one or more of the following features, taken individually or according to any possible technical combinations :
  • each cathode frame defines at least one side aperture for feeding a feed solution containing manganese ions into the internal compartment and at least an upper side aperture for discharging cathode gases, the upper discharge aperture being positioned above said or each side aperture for feeding a feed solution, the cell comprising a cover assembly sealingly covering the inner volume of the tank around the frame assembly above the upper discharge apertures, the cell including at least one conduit for purging out of the tank discharge gases collected through each upper gas discharge aperture ;
  • the purging conduit extends substantially vertically inside the tank and emerges upwardly in the inner volume.
  • a closing member closing upwardly each cathode receiving compartment around a cathode inserted in the compartment, the closing member advantageously comprising a sealing member protruding axially from an adjacent anode.
  • the invention also relates to a cell for electrolysis of manganese, comprising :
  • a tank delimiting an inner volume for receiving a feed solution
  • the frame assembly comprising:
  • each cathode frame delimiting an internal compartment for receiving a cathode, an upper aperture for introducing a cathode into the internal compartment, and at least one side aperture for feeding a feed solution containing manganese ions into the internal compartment;
  • each cathode frame defines at least an upper side aperture for discharging cathode gases, the upper discharge aperture being positioned above said or each side aperture for feeding a feed solution, to emerge at least partially above the feed solution, and in that the upper discharge aperture emerges in the internal compartment and emerges outside the frame assembly;
  • the cell comprising a cover assembly sealingly covering the inner volume of the tank around the frame assembly above the upper discharge apertures, the cell including at least one conduit for purging out of the tank discharge gases collected through each upper gas discharge aperture,
  • the purging conduit extends vertically inside the tank and emerges upwardly in the inner volume.
  • the cell does not necessarily comprise at least one diaphragm which comprises a first porous wall covering a first axial opening of a cathode frame, a second porous wall covering the second axial opening of the cathode frame and at least a connecting wall connecting the first porous wall and the second porous wall along the cathode frame, the first porous wall, the second porous wall and the connecting wall defining an internal space containing or defining the internal cathode receiving compartment.
  • the invention also concerns a method for electrolysis of manganese, including : - providing a cell as described above;
  • FIG. 1 is a schematic side view of a first cell for manganese electrolysis according to the invention ;
  • - figure 2 is a partial top perspective view of the cell of figure 1 ;
  • - figure 3 is a perspective and partial sectional view along the transverse plane III of figure 2 ;
  • figure 4 is an exploded perspective view of the internal frame assembly of the cell of figure 1 ;
  • FIG. 5 is a perspective view of a cathode frame of the frame assembly of figure 4 ;
  • figure 6 is a perspective view of an anode frame of the frame assembly of figure 4 ;
  • FIG. 7 is a perspective view of a diaphragm according to the invention.
  • figure 8 is a side elevation view of the diaphragm of figure 7 ;
  • - figure 9 is a perspective view of the internal frame of the diaphragm of figure 7 ;
  • - figure 10 is a cross section of the upper part of the diaphragm engaged around a crossbar of the cathode frame ;
  • FIG. 1 1 is a perspective view of a cathode intended to be introduced into the cathode frame ;
  • FIG. 12 is a perspective view of an anode intended to be inserted in an anode frame.
  • Figs. 1 to 12 illustrate a first electrolysis cell 10 according to the invention, intended for carrying out manganese metal electrolysis or « ⁇ ».
  • Manganese metal is advantageously formed on a plurality of cathodes by providing an electric current, in contact with a feed solution containing manganese ions Mn 2+ , optionally in the presence of ammonium sulfate.
  • the thereby formed manganese metal is deposited as a solid on each cathode.
  • the cell 10 is positioned in an installation including several cells 10 in series, for example about a hundred cells 10.
  • the electrolysis cell 10 includes a tank 12 delimiting an inner volume 14 and an internal frame assembly 16 of the «filter press» type positioned in the inner volume 14 of the tank 12.
  • the electrolysis cell 10 further includes an assembly 18 for covering the inner volume 14 intended to capture and to sealingly convey the gases emitted at the cathode during electrolysis.
  • the cell 10 further includes electric power supply means 19 which are partly visible in Figs. 2 and 3, and a heat exchanger 19A for cooling, partly visible in Figure 3.
  • the tank 12 is of a substantially parallepipedal shape with a longitudinal axis A-A'. It includes two end transverse walls 20A, 20B, connected to each other through two longitudinal walls 22, of which only one is visible in Figs. 1 and 2.
  • the tank 12 further includes a bottom wall 24 which closes the inner volume 14 downwards.
  • the transverse walls 20A, 20B and the side walls 22 delimit an upper peripheral flange which protrudes externally at the periphery of the volume 14.
  • Each side wall 22 delimits a planar upper supporting edge 28, advantageously located on the flange.
  • the edge 28 bears an upper supporting strip 30.
  • the strip 30 bears longitudinal electrical contacts 32A, 32B intended for connecting the electric power supply means 19 to the anodes and to the cathodes respectively.
  • the tank 12 further includes at least one conduit 34 for feeding a feed solution into the inner volume 14, at least one conduit 36 for discharging an anolyte solution out of the internal frame assembly 16 and out of the tank 12, and at least one conduit 38 for purging gases produced at the cathode, in order to discharge them out of the inner volume 14.
  • the feeding conduit 34 is connected to pumping or gravity means 40 for feeding a feed solution into the tank 12.
  • the feeding conduit 34 passes above the transverse wall 20A at the flange 26.
  • the feeding conduit 34 crosses the transverse wall 20A at the flange 26.
  • the discharge conduit 36 extends through the transverse wall 20A. It is connected upstream to the frame assembly 16 through a flexible hose (not shown). It is connected downstream to collecting and treating means 42 positioned outside the tank 12.
  • the conduit 38 for purging cathode gases is connected to an installation 44 for collecting and treating these gases. This avoids dissemination of the cathode gases into the atmosphere located around the tank 12.
  • the purging conduit 38 extends vertically inside the inner volume 14, advantageously along the transverse wall 20A.
  • the conduit 38 emerges upwards into a collecting aperture 46 delimited on an upper surface 46A of the conduit 38.
  • the upper surface 46A is located above the liquid level in the inner volume 14.
  • the upper surface 46A is inclined towards the bottom wall 24 in a direction towards the centre of the tank 12.
  • the bottom part of the purging conduit 38 extends through the bottom wall 24.
  • the purging conduit 38 delimits a lumen 46B for evacuation of the cathode gases, whose orientation is substantially vertical.
  • the purging conduit 38 crosses the transverse wall 20A at the upper flange 26. It opens out through collecting apertures 46 which are located above the liquid level in the inner volume 14, in order to remain cleared of liquid permanently, regardless of the feed solution level contained in the inner volume 14.
  • collecting apertures 46 may be positioned on either side of the transverse wall 20A, in the vicinity of the upper corners of this wall 20A, facing intermediate side spaces 60 between the frame assembly 16 and the side walls 22 of the tank.
  • the internal frame assembly 16 is positioned in the volume 14. It extends along an axis B-B' parallel or coinciding with the axis A-A' of the tank 12. It delimits, in the inner volume 14, intermediate side spaces 60 visible in Figure 3, and intermediate axial spaces 62 (fig. 1 and fig. 2) present between the end walls 20A, 20B and the frame assembly 16.
  • the intermediate spaces 60 (fig 3), 62 (fig 1 ) are intended for receiving the feed solution.
  • the intermediate spaces 60, 62 are covered by the cover assembly 18 in order to confine and discharge the cathode gases, as this will be seen below.
  • the heat exchanger 19A is positioned in the intermediate spaces 60, 62.
  • the frame assembly 16 is removably laid in the inner volume 14 of the tank 12. It is thus movable and transportable, through the upper passage delimited between the walls 20A, 20B and 22, between an extracted position out of the inner volume 14 and a position for operating the electrolysis method, laid against the bottom wall 24 in the inner volume 14.
  • the internal frame assembly 16 is of the «filter press» type. It thus includes, with reference to Figure 4, a plurality of cathode frames 64, a plurality of anode frames 66, and a plurality of diaphragm assemblies 68 positioned around each cathode frame 64 between the cathode frame 64 and each adjacent anode frame 66.
  • the frame assembly 16 further includes two end frames 70A, 70B intended to transversely close the axial ends of the frame assembly 16, and a releasable clamping assembly 72 of the frame assembly 16.
  • the frame assembly 16 includes a removable cathode 74 (depicted in Figure 1 1 ) received in each cathode frame 64 and a removable anode 76 (depicted in Figure 12) received in each anode frame 66.
  • each cathode frame 64 includes two side uprights 80A, 80B, an intermediate crossbar 82, and a lower crossbar 84 connecting together the uprights 80A, 80B.
  • It also includes at least one, preferably two parallel upper stiffening cross members 85A, 85B, connecting the upper ends of the two side uprights 80A, 80B.
  • the cathode frame 64 thus delimits an internal compartment 90 for receiving a cathode 74 and, a lower window 92 for circulation of an anolyte solution sealingly isolated from the inner compartment 90.
  • the cathode frame 64 further delimits an upper aperture 94 for introducing the cathode 74 into the internal compartment 90, transverse side apertures 96 for supplying feed solution into the internal compartment 90, and according to the invention, upper side apertures 98 for discharging cathode gases out of the frame assembly 16 and discharge of catholyte.
  • This conformation of the cathode frames 64 allow a circulation of feed solution from the intermediate spaces 60 through the transverse supplying apertures 96, and upwards into the internal compartments 90, driven by the generation of gases at the cathode and the subsequent gas lift effect inside the internal compartments 90. The gases and the liquid solution are then discharged out of the internal compartments 90 through the upper side apertures 96.
  • the height of the cathode frame 66 is substantially equal to the depth of the inner volume 14, taken between the upper edge 28 of the side wall 22 and the bottom wall 24.
  • the uprights 80A, 80B extend parallel to each other along a vertical direction.
  • Each upright 80A, 80B at its upper end has a side lug 100 which transversely protrudes relatively to a longitudinal axis B-B' of the frame assembly 16, visible in Figure 4.
  • Each lug 100 delimits a transverse shoulder 101 for receiving a cover of the cover assembly 18.
  • the shoulder 101 opens out transversely facing the side wall 22, when the internal frame assembly 14 is positioned in the inner volume 14 of the tank 12.
  • the shoulder 101 is located above the cathode gas discharge apertures 98.
  • Each side lug 100 also delimits a lateral notch 102 which opens laterally and transversely away from a centre axis of the cathode frame 64.
  • the notch 102 has a lower portion which is inclined downwardly when moving away from the centre axis of the frame 64, and an upper portion which is horizontal and perpendicular to the centre axis of the frame 64.
  • the aperture 98 emerges out in the notch 102.
  • the notch 102 is hence adapted to receive a frame assembly carrying tool, e.g. a longitudinal bar, extending longitudinally along the frame assembly 16 when the frame assembly 16 has to be extracted out of the inner volume 14 of the tank 12.
  • a frame assembly carrying tool e.g. a longitudinal bar
  • the lower crossbar 84 horizontally connects the lower ends of the uprights 80A, 80B with each other. It delimits downwards the lower window 92 for circulation of anolyte solution.
  • the lower crossbar 84 is attached onto the uprights 80A, 80B.
  • triangle-shaped reinforcement spacers may advantageously be connected to the lower crossbar 84 and to the uprights 80A, 80B at the inner corners delimited by the uprights 80A, 80B and the lower crossbar 84.
  • the intermediate crossbar 82 is positioned parallel to the lower crossbar 84. It delimits the window 92 upwards. It delimits downwards the internal cathode receiving compartment 90. It is added between the uprights 80A, 80B.
  • the intermediate crossbar 82 is solid to sealingly separate the lower window 92 from the cathode receiving compartment 90.
  • Each upright 80A, 80B above the intermediate crossbar 82 delimits a vertical guiding slot 104 opening sideways into the internal compartment 90 and opening out upwards into the upper aperture 94.
  • the slots 104 are intended for guiding the cathode 74 when it is introduced into the internal compartment 90.
  • the internal compartment 90 is delimited downwards by the intermediate crossbar 82 and sideways by the uprights 80A, 80B. It opens out upwards through the introduction aperture 94.
  • Each parallel upper cross member 85A, 85B extends from an upper end of one upright 80A to the upper end of a facing upright 80B.
  • Each cross member 85A, 85B is hence parallel to the intermediate crossbar 82.
  • One cross member 85A is fixed on one axial face of the upright 80A, 80B and the other cross member 85B is fixed on an opposite axial face of the upright 80A, 80B.
  • the upper cross members 85A, 85B define a guiding slot opening upwardly in the upper aperture 94.
  • each cross member 85A, 85B is made of a prong.
  • Each cross member 85A, 85B is advantageously made of a material stiffer than the material of the uprights 80A, 80B and/or of the crossbars 82, 84.
  • the crossbars 85A, 85B are made of metal.
  • the uprights 80A, 80B, and the crossbars 82, 84 are made of plastic.
  • the internal compartment 90 opens out axially along axis B-B' in a first axial opening 105A facing a first adjacent anode frame 66 and into a second axial opening 105B facing a second adjacent anode frame 66.
  • the axial openings 105A, 105B are delimited laterally by the uprights 80A, 80B, downwardly by the intermediate crossbar 82, and upwardly by the upper stiffening cross members 85A, 85B.
  • each upright 80A, 80B delimits one side through-aperture 96 for feeding feed solution into the internal compartment 90.
  • Each aperture 96 transversely extends through the upright 80A, 80B. It opens out on the outside of the frame assembly 12 into the thickness of the upright 80A, 80B facing the intermediate space 60 between the frame assembly 16 and the side wall 22. It interiorly opens into the inner compartment 90.
  • each upright 80A, 80B comprises an aperture 96 located in the vicinity of the intermediate crossbar 82.
  • the section of the apertures 96 is smaller than the maximum thickness of the upright 80A or 80B, taken along the axis B-B'. This section is advantageously circular.
  • each upright 80A, 80B delimits in the lug 100, an upper side aperture 98 for discharging gas.
  • the upper side aperture 98 is located above each aperture 96 for feeding a feed solution.
  • the upper aperture 98 advantageously has a section greater than the maximum section of each aperture 96 for feeding a feed solution.
  • each upper aperture 98 is advantageously oblong.
  • the height of the upper aperture 98 is larger than the maximum thickness of the frame 64, taken along the axis B-B'.
  • the width of the upper aperture 98 taken parallel to the axis B-B' is smaller than the thickness of the frame 64.
  • the upper aperture 98 has a constant section taken in a vertical plane containing the axis B-B'.
  • the aperture 98 extends along a horizontal axis perpendicular to the axis B-B'.
  • the upper aperture 98 connects an upper region of the internal compartment 90 to the outside of the frame assembly 16. It is intended to be placed facing a side wall 22, while being at most partly immersed by the feed solution present in the inner volume 14 between the tank 12 and the frame assembly 16.
  • the ratio of the minimum section of the side gas discharge aperture 98 to the maximum section of each aperture 98 for feeding solution is greater than 1 .
  • each aperture 98 gives the possibility of purging the internal compartment 90 from the gases which it contains, even if this internal compartment 90 is partly immersed by the feed solution.
  • the cathode gases are easily discharged to the outside of the frame assembly 16, from each cathode frame 64.
  • the discharged gases do not pass through another cathode frame 64 or through another anode frame 66, but directly flow out in the intermediate side space 60 into which the aperture 98 opens.
  • the cathode gases are thus collected between the tank 12 and the cover assembly 18, as this will be seen below.
  • the apertures 96 for feeding a solution and the apertures 98 for discharging gases exclusively open into the internal compartment 90 and on the outside of the internal frame assembly 16, without axially opening out along the axis B-B' of the frame assembly 16.
  • the apertures 96, 98 do not open into the transverse faces of the cathode frame 64 and are not in communication with other gas discharge apertures made in other cathode frames 64.
  • each diaphragm assembly 68 comprises a first axial porous wall 106A, intended for covering a first axial opening 105A of a cathode frame 64, a second porous wall 106B, intended for covering a second axial opening 105B of the same cathode frame 64 opposite to the first axial opening 105A, and at least one, preferably two side connecting walls 108C, 108D laterally connecting the first porous wall 106A to the second porous wall 106B, around the cathode frame 64.
  • the diaphragm assembly 68 defines, between the porous walls 106A, 106B and the connecting walls 108C, 108D, an internal space 109 intended for receiving the cathode frame 64 and its internal cathode receiving compartment 90.
  • the diaphragm assembly 68 advantageously comprises a connecting frame 1 1 1 A, inserted in the internal space 109A to connect the first porous wall 106A and the second porous wall 106B and attaching elements 1 1 1 B, 1 1 1 C for attaching each porous wall 106A, 106B on the cathode frame 64.
  • the diaphragm assembly 68 forms a pocket 1 10 surrounding a cathode frame 64, the cathode frame 64 being inserted in the internal space 109.
  • first porous wall 106A and the second porous wall 106B are each made of a porous cloth 1 12.
  • the cloth 1 12 is permeable. It allows the passage of the catholyte solution present in the internal compartment 90 for receiving a cathode, towards an anode frame 66.
  • the cloth 1 12 is for example made in a synthetic woven material, advantageously in a woven having mechanical and chemical resistance properties compatible with its use in the electrolysis cell.
  • the permeability of the cloth 1 12 is defined so as to establish a height difference between the catholyte solution and the anolyte solution. This height difference, variable depending on the fouling of the cloth 1 12 generates a flow of solution from the cathode to the anode through the cloth 1 12.
  • This solution flow slows down back-diffusion towards the cathode of the hydronium ions produced at the anode and allows the pH of the catholyte solution to be maintained.
  • the cloth 1 12 forming the first porous wall 106A and the second porous wall 106B is deformable. In particular, it can be deformed manually by an operator in order to insert the cathode frame 64 into the internal space 109.
  • the first porous wall 106A When the cathode frame 64 is received in the internal space 109, the first porous wall 106A totally covers the first axial opening 105A. It also at least partially covers a first axial face of the cathode frame 64, including the uprights 80A, 80B, the upper cross member 85B, and the intermediate and lower crossbars 82, 84.
  • the first porous wall 106A defines a lower opening 1 13A for passage of the anolyte solution.
  • the lower opening 1 13A is located facing the lower window 92 defined by the cathode frame 64. It is delimited outwardly by the connecting frame 1 1 1 A.
  • the second porous wall 106B totally covers the second axial opening 105B. It also at least partially covers a second axial face of the cathode frame 64, including the uprights 80A, 80B, the upper cross member 85B, and the intermediate and lower crossbars 82, 84, the second axial face being opposed to the first axial face.
  • the second porous wall 106B defines a lower opening 1 13B for passage of the anolyte solution.
  • the lower opening 1 13B is located facing the lower window 92 defined by the cathode frame 64, in register with the lower opening 1 13A. It is delimited outwardly by the connecting frame 1 1 1 A.
  • the lugs 100 protrude out of the inner space 109.
  • the lugs 100 are not covered with the first porous wall 106A and/or with the second porous wall 106B.
  • porous walls 106A, 106B define an upper opening 1 14 for insertion of the cathode 74 inside the internal space 109 and into the internal compartment 90 of the cathode frame 64.
  • the upper opening 1 14 is located in register with the upper aperture 94 delimited by the cathode frame 64.
  • the side connecting wall 108C, 108D respectively connect the lateral edges of the first and second porous wall 106A, 106B together.
  • the side connecting wall 108C, 108D extend longitudinally along a respective upright 80A, 80B.
  • each side connecting wall 108C, 108D is generally higher than 20% of the height of the cathode frame 64.
  • the width of the side wall 108C, 108D is approximately equal to the width of the cathode frame 64.
  • Each connecting wall 108C, 108D defines a lower lateral window 1 15A and an upper lateral window 1 15B opening between the first porous wall 106A and the second porous wall 106B.
  • the lower window 1 15A opens in register with the lower side aperture 96.
  • the upper window 1 15B opens in register with the transverse lug 100.
  • the transverse lug 100 protrudes out of the internal space 109 through the upper window 1 15B.
  • each connecting wall 108C, 108D comprises at least a first flap 1 16A integral with or fixed on the first porous wall 106A, a second flap 1 16B integral with or fixed on the second porous wall 106B, and attaching elements connecting the or each first flap 1 16A with the or each second flap 1 16B in a removable manner.
  • each flap 1 16A is folded substantially perpendicularly to the first porous wall 106A towards the second porous wall 106B.
  • Each second flap 1 16B is folded substantially perpendicularly to the second wall 106B towards the first porous wall 106A. It is pressed on the first flap 1 16A.
  • the attaching elements are for example made of Velcro.
  • each first flap 1 16A is secured on a second flap 1 16B and the porous walls 106A, 106B are securely applied on opposite faces of the cathode frame 64.
  • the connecting frame 1 1 1 A is advantageously made from the same cloth as the porous walls 106A, 106B. It has an outer shape substantially complementary to the inner shape of the lower window 92.
  • the connecting frame 1 1 1 A defines a central passage 1 17 for circulation of the anolyte solution. It has a first axial face 1 18A continuously connected to the first porous wall 106A and a second axial face 1 18B opposite the first axial face 1 18A, continuously connected to the second porous wall 106B around the window 1 13B.
  • the frame 1 1 1 A has a continuous closed contour. It prevents the anolyte solution which circulates in the passage 1 17 from entering the internal space 109.
  • the attaching elements 1 1 1 1 B, 1 1 1 C comprise an upper tongue 1 19 which can be folded on itself around an upper cross member 85A, 85B, and releasable fixing elements 120 to secure the upper tongue 1 19 on an inner face of the porous wall 106A, 106B.
  • the tongue 1 19 is advantageously integral with the porous wall 106A, 106B.
  • the width of the tongue 1 19 is less than the width of the porous wall 106A, 106B to allow the introduction of the tongue 1 19 into the slot defined between the cross members 85A, 85B.
  • the fixing elements 120 are for example made of Velcro. They can maintain the tongue 1 19 folded on the inner face of the wall 106A, 106B located inside the internal space 109.
  • the flaps 1 16A, 1 16B are disconnected from each other.
  • the connecting frame 1 1 1 A is then inserted into a lower window 92 of through a first axial face of the cathode frame 64 along with the second porous wall 106B.
  • the second porous wall 106B is subsequently extracted out of the lower window 92 through the opposite axial face of the cathode frame 64, along with the second flaps 1 16B
  • the first wall 106A is applied on the first axial face of the cathode frame 64 and the first flaps 106A are folded against the side uprights 80A, 80B.
  • the second flaps 1 16B are folded towards the side uprights 80A, 80B on the first flaps 1 16A, and the attaching elements are activated.
  • each attaching elements 1 1 1 1 B, 1 1 1 C is then folded around a corresponding upper cross member 85A, 85B to secure the diaphragm 68 around the cathode frame 64.
  • Each cathode frame 64 is then almost totally received into the internal space 109 defined by the diaphragm 68, with the exception of the side lugs 100.
  • the axial windows 105A, 105B of the inner cathode receiving compartment 90 are totally covered with the porous walls 106A, 106B, which prevents a direct contamination of the internal compartment 90 with the anolyte solution located around the diaphragm 68.
  • the anolyte solution located around the diaphragm 68 has to enter the internal space 109 through the cloth 1 12 forming the walls 1 16A, 1 16B, which hinders the passage of hydronium ions.
  • the diaphragm 68 of the frame assembly 16 according to the invention is easy to assemble and provides a very efficient separation between the solutions located around the anode 72 and around the cathode 74.
  • the diaphragm 68 can easily be disassembled when needed, in particular when sludge is present on the surface of the walls 106A, 106B.
  • each anode frame 66 includes two parallel uprights 140A, 140B and a lower bottom crossbar 142 connecting the lower ends of the uprights 140A, 140B. According to the invention, each anode frame 66 further includes an intermediate crossbar 146 defining a lower window 147.
  • the intermediate crossbar 146 delimits with the uprights 140A, 140B, an upper anode receiving compartment 144.
  • the uprights 140A, 140B have a height substantially equal to that of the uprights
  • Each upright 140A, 140B is intended to be applied against a respective upright 80A, 80B of an adjacent cathode frame 64, with the interposition of an porous wall 106A, 106B of a diaphragm assembly 68 surrounding the adjacent cathode frame 64.
  • the uprights 140A, 140B at their upper ends have side lugs 148 which transversely protrude relatively to the axis B-B'.
  • Each side lug 148 delimits a transverse shoulder 150 for receiving a cover of the cover assembly 18.
  • Each side lug 148 further delimits a side notch 151 of a shape similar to each corresponding side notch 102 of a lug 100.
  • the lower crossbar 142 is mounted between both uprights 140A, 140B. It has a width substantially equal to that of the lower crossbar 84 of the cathode frames 64.
  • spacers may connect the uprights 140A, 140B with the lower crossbar 142 at the right and left lower corners of the inner compartment 144.
  • the uprights 140A, 140B advantageously comprise a series of lateral protrusions 149 for guiding the clamping assembly 72.
  • Each upright 140A, 140B above the intermediate crossbar 146 delimits a vertical guiding slot 152 for guiding the insertion of the anode 76 inside the anode receiving compartment 144.
  • the intermediate crossbar 146 defines at least one, preferably a plurality of vertical through passages 153 for evacuation of the anolyte solution and/or sludge.
  • the passages 153 are opened upwardly in the anode receiving compartment 144 and downwardly in the lower window 147.
  • the anolyte sludge is therefore able to fall spontaneously by gravity from the upper compartment 144 to the lower window 147.
  • the intermediate cross bar 146 is located at the same height as the intermediate crossbar 82 of the adjacent cathode frames 64 in order to be applied on these crossbars 82, with the interposition of an porous wall 106A, 106B.
  • each anode frame 66 further comprises sealing elements 153A, 153B intended to be interposed between each axial face of the anode frame 66 and a corresponding diaphragm 68 applied on the axial face.
  • each sealing element 153A, 153B is made of a continuous gasket extending along a first upright 140A, the lower crossbar 142 and along a second upright 140B, on a respective axial face of the frame 66.
  • the sealing element 153A, 153B is advantageously received in a corresponding groove 154A, 154B provided in the respective axial face.
  • each anode frame 66 When each anode frame 66 is pressed against an adjacent cathode frame 64, the respective sealing element 153A, 154B is applied on a respective porous wall 106A, 106B of the diaphragm 68 surrounding the adjacent cathode frame 64.
  • the sealing element 153A, 153B prevents the circulation of anolyte solution from the anode receiving compartment 144 and/or from the window 147 to the outside of the frame assembly 16 through the lateral gaps between each anode frame 66 and the corresponding diaphragm 68 applied on the anode frame 66.
  • the end frames 70A, 70B each include a solid closing panel 170 intended to be placed facing the inner compartments 144 receiving an anode from the adjacent anode frame 66. They each include a removable lower panel 172 intended to be placed facing the windows 92, 147 for circulation of the anolyte solution.
  • the removable panel 172 is retained by maintaining means 174 which may be disassembled, and may be passed into an open configuration in order to allow access to the respective windows 92, 147 and to the bottom of the compartment 144.
  • one of the end frames 70A, or both end frames 70A, 70B includes a fitting 176 for discharging an anolyte solution, intended to be connected to the anolyte solution discharge conduit 36.
  • the clamping assembly 72 includes a plurality of longitudinal rods 180 crossing the frame assembly 16, and tightening nuts 182 mounted on the rods 180.
  • the rods 180 are positioned in the vicinity of the side faces of the frame assembly 16. They extend parallel to the axis B-B'. They extend longitudinally along the side uprights 80A, 80B of the cathode frames 64 and the side uprights 140A, 140B of the anode frames 66.
  • the rods 180 are distributed over the height of each frame 64, 66.
  • the rods 180 are further positioned on either side of the lateral uprights 1 14A, 1 14B of the supporting frames 1 10, without passing through these uprights 1 14A, 1 14B.
  • the rods 180 are located along the cathode frames 64 and along the anode frames 66 and play exists between the anode frames 66 and the cathode frames 64.
  • the frame assembly 16 then comprises a succession of unit assemblies comprising a cathode frame 64, surrounded by a diaphragm 68, an anode frame 66 and another cathode frame 64 surrounded by another diaphragm 68.
  • the uprights 80A, 80B and the lower crossbar 84 of the cathode frame 64 are respectively applied on the side uprights 140A, 140B, on the lower crossbar 142 of the anode frame 66.
  • porous walls 106A, 106B made of cloth 1 12 are interposed between cathode frames 64 and the anode frames 66 and are maintained in a vertical position.
  • This assembly is robust. It guarantees a good seal between the inner anode receiving compartments 144 and the internal cathode receiving compartments 90 in order to guarantee that the passage between these compartments is exclusively achieved through the cloth 1 12 of the porous walls 106A, 106B. Further it guarantees accurate positioning of the cloth 1 12, at a distance from the anodes and cathodes.
  • This assembly may however be easily disassembled when it has to be cleaned, which reduces the time required for putting back the electrolysis cell 10 into production.
  • the windows 92, 147 are located facing each other. They define in a lower portion of the frame assembly 16, a continuous conduit 190 for circulation of anolyte solution and for discharging anolyte sludges (see figure 4).
  • the conduit 190 communicates with the inner compartment 144 of each anode frame 66, through the through passages 153 made in the intermediate crossbar 146, while being sealably isolated from each internal compartment 90 of the cathode frame 64 by the connecting frame 1 1 1 A.
  • the cathodes 74 comprise metal plates 191 A inserted in the inner compartments 90 of the cathode frame 64 via upper apertures 94 and an electric connection bar 191 B along the upper edge of metal plate 191 A.
  • Each cathode 74 is provided along its upper edge with gripping hooks 160 visible in figure 2.
  • the anodes 72 are inserted into the inner compartments 144 of the anode frames
  • each anode 72 comprises an anode grid 192A, an anode upper electric connection bar 192B and positioning spacers 193A intended to maintain vertically the adjacent porous walls 106A, 106B of the adjacent diaphragms 68.
  • the anode 72 further comprises an upper transverse cover 193B for sealing upwardly the anode compartments 144 and the adjacent cathode compartments 90, by lateral contact against an adjacent transverse cover 193B.
  • the anode grid 192A comprises a plurality of spaced apart vertical metal rods 194A connected together at their lower ends by a transverse cross member 194B.
  • the vertical spacers 193A are advantageously made of electrically insulating material.
  • the spacers 193A extends vertically from the upper electric connection bar 192B to the lower cross member 194B. They protrude axially on each side of the anode 72 to contact and provide an axial support for the adjacent porous walls 106A, 106B of the adjacent diaphragms 68.
  • the spacers 193A contact the opposite porous walls 106A, 106B of the adjacent diaphragms to prevent these walls 106A, 106B from entering the anode receiving compartment 144 and to maintain their vertical planar orientation.
  • the upper transverse cover 193B comprises in this example a hollow tubular cover made of plastic defining a housing receiving the bar.
  • the upper transverse cover 193B protrudes axially on both sides of the anode 72 to seal the cathode compartments 90 and also prevent contact of the connection bar 192B of the anode 72 with an adjacent connection bar 192A of a cathode 74.
  • the hooks 160, 162 allow introduction and extraction of the cathodes 74 and anodes 76 in the frame assembly 16.
  • the cathodes 74 and the anodes 76 are respectively connected to electric power supply means through the paths 32B, 32A on which they rest respectively.
  • the cover assembly 18 closes the inner volume 14 upwards, facing the intermediate spaces 60, 62 defined by the frame assembly 16 (see figure 3).
  • the cover assembly 18 thus includes side covers 200, intended for closing upwards the intermediate side spaces 60, an end cap 202 intended for closing each axial intermediate space 62 and advantageously,
  • Each side cover 200 is mounted between the side wall 22 and the frame 64, 66. It is advantageously received into the shoulders 101 , 150 made in the frames 64 and 66, respectively.
  • each cover 200 is formed by a sealed cover plate. It is advantageously applied onto a rim 202A firmly attached to the upper strip 30 and received into the shoulder 101 , 150.
  • the cap 202 advantageously extends above the upper shoulder 26 along the axial intermediate space.
  • the cap 202 comprises an outer part 203 applied on the upper shoulder 26 and an inner part 204 applied on the outer part 203 to cover the axial intermediate space 62.
  • the outer part 203 and the inner part 204 define through openings 205 for inserting the conduits 34 and additional conduits 205A for feeding the heat exchanger 19A with a cooling fluid such as water.
  • end cap 202 caps the axial intermediate space 62 and connects the side edges 22 to the shoulder 26.
  • the upper transverse covers 193B mounted on the anodes 72 are in contact along their sides, above the upper apertures 94 of the cathode compartments to seal the cathode compartments 90 and prevent gases generated in the cathode compartments 90 to leak upwards through the upper apertures 94.
  • the adjacent transverse covers 193B hence define an upper closing member 204A of the cathode compartments 90.
  • the cap 202 and the side covers 200 thus define a path for collecting the cathode gases, including two axial channels 210 (see figure 3) extending under the side covers 200 facing each upper aperture 98 and a common collecting space 212 (see figure 2) located under the end cap 202 so as to open out facing the apertures 46.
  • the presence of the channels 210 and of the common collecting space 212 ensures efficient recovery of the cathode gases, regardless of the position of the cathode frame 64 from which it is generated, with a minimum pressure loss.
  • the risk of clogging the cathode gas discharge apertures 98 is very limited, which ensures safe conveying of the cathode gases up to the discharge conduit 38.
  • cathode gases are collected since the upper apertures 94 are closed upwards partly by the cathode 74 and partly by the closing member 204. This is the case, including when these cathode gases comprise ammonia or hydrogen.
  • the safety of the cell 10 is therefore reinforced, which makes the cell 10 particularly suitable for a sensitive industrial environment. In particular, the personnel present in the vicinity of the cell 10 is not subject to cathode gas emanations. Further, the cell 10 collects the cathode gases with view to their treatment, without discharging the latter in the atmosphere.
  • the internal frame assembly 16 is assembled.
  • a diaphragm 68 is engaged around each cathode frame 64 as described above.
  • the cathode frames 64, the anode frames 66 are mounted on the longitudinal rods 180 of the clamping assembly.
  • the diaphragms 68 are interposed between each anode frame 64 and each cathode frame 66.
  • End frames 70A, 70B are then mounted at the ends of the frame assembly 16 and the nuts 182 are mounted on the rods 180 for tightening the assembly and forming a structure of the «filter press» type.
  • the internal frame assembly 16 is brought into the inner volume 14 of a tank 12. It is laid against the bottom wall 24 of the tank 12.
  • the anolyte purging conduit 36 is connected to the end fitting 76 on the frame 70A, 70B.
  • the anodes 76 are inserted into the inner compartments 144, the cathodes 74 are inserted into the internal compartments 90.
  • the cathodes 74 and the anodes 76 are thereby electrically connected to the paths 32A, 32B respectively.
  • a feed solution containing manganese ions is pumped via pumping means 40 as far as the inner volume 14 of the tank 12 through the feeding conduit 34.
  • This feed solution includes a manganese ion mass concentration of greater than 30 g/l, and notably comprised between 30 g/l and 40 g/l.
  • the feed solution includes a mass concentration of ammonium sulfate comprised between 100 g/l and 200 g/l, advantageously of the order of 125 g/l.
  • the pH of the feed solution is adjusted so as to be close to 7, and notably comprised between 6 and 7.
  • the feed solution advantageously contains sulfite ions or selenium ions.
  • the feed solution partly fills the inner volume 14 of the tank 12.
  • the level is adapted in order to totally flood the side feed apertures 96, without totally immersing the upper gas discharge apertures 98.
  • the feed solution is brought into the inner compartments 90 so as to come into contact with the cathode 74, through the side apertures 96 made in each cathode frame 64, and thereby form a catholyte solution.
  • a supply electric DC current is provided between the cathode 74 and the anode 76.
  • the electrons provided at the cathode 74 react with the manganese ions in order to form manganese metal on the cathode according to the reaction:
  • the electrons present at the cathode 74 partly react with the hydronium ions present in the catholyte solution in order to form hydrogen.
  • the hydrogen formed at the cathode 74 stirs the catholyte solution in the internal compartment 90 allowing good distribution of the solution around the cathode 74.
  • the gases formed, notably hydrogen and ammonia are then collected in the upper portion of the inner compartment 90 and are confined in the compartment 90 via closing members formed in this example by the adjacent upper transverse covers 193B interposed between the cathodes 74 and the cathode frames 64, in order to close the upper cathode introduction apertures 94.
  • the gases formed are therefore exclusively discharged through the upper gas discharge apertures 98 towards the outside of the internal frame assembly 16.
  • Gas discharge is further highly homogeneous and does not depend on the position of the cathode frame 64 in the frame assembly 16.
  • the discharge gases are then collected in the axial channels 210 by being confined between the surface of the feed solution and the side covers 200.
  • the gases are then collected in the common spaces 212 under the end caps 202 and are discharged through the collecting aperture 46, and then through the purging conduit 38.
  • the thereby collected cathode gases may then be brought towards the collecting and treatment installation 44 with view to their recycling, or to their being discharged into the atmosphere after treatment.
  • Toxic or dangerous gases which may be generated by the electrolysis process are therefore perfectly confined by the cover assembly 18 of the cell 10 according to the invention. This collection is carried out without perturbing the electrolysis process, in a simple and inexpensive way.
  • This solution thus penetrates into the inner compartments 144 of the anode frame 66 and forms an anolyte solution.
  • the water present in the anolyte solution reacts in order to form oxygen, hydronium ions and electrons according to the reaction
  • the pH of the solution present at the anode 76 is therefore much smaller than that of the solution present at the cathode 74.
  • the cloth 1 12 of the walls 106A, 106B prevents passage of the hydronium ions from the inner compartment 144 receiving the anode 76 towards the internal compartment 90 receiving the cathode 74. This maintains the pH of the solution present in the internal compartment 90 in the desired range in order to form manganese metal.
  • the anolyte solution then flows down through the passages 153 in the intermediate crossbar 146, into the lower window 147, and is then discharged towards the end of the frame assembly 16 through the conduit 190 defined by the windows 92, 147.
  • the seal is perfectly achieved at the frame assembly 16 by the « filter-press» structure, the anolyte solution is totally separated from the catholyte solution during its discharge out of the frame assembly 16.
  • the anolyte solution flows upwards in the last anode frame 66 adjacent to each end frame 70A, 70B and is discharged through the end fitting 176 and then through the conduit 36.
  • the presence of manganese ions may lead to parasitic reactions with water present in the solution in order to form manganese oxide, hydronium ions and electrons. Moreover formation of gypsum may also occur in the anolyte compartment.
  • the thereby formed solids make up solid sludges which are discharged downwards under the effect of their weight and partly stored in the compartment 190.
  • the cloths 1 12 Taking into account the efficient holding of the cloths 1 12 by the spacers 193A, the cloths 1 12 have a planar surface which significantly limits accumulation of solids, and notably of anolyte sludge on the cloths 1 12.
  • the fouling of the anodes 76 and of the cloths 1 12 is therefore delayed in the frame assembly 16 according to the invention. This contributes to increasing the productivity of the electrolysis method and to limit the number of cleaning operations which have to be carried out for each frame assembly 16.
  • the frame assembly 16 is lifted up out of the inner volume 14 of the tank 12.
  • the clamping assembly 72 is then partly released in order to allow extraction of the diaphragms 68 and their cleaning, without having to disassemble the whole frame assembly 16.
  • the discharge conduit 190 when the discharge conduit 190 is clogged, it may be cleaned simply by extracting the frame assembly 16 out of the tank 12, and then by opening the mobile closing panels 172 located at the end frames 70A, 70B.
  • the frame assembly 16 according to the invention therefore has a very advantageous design which limits fouling by anolyte sludges and which allows simple cleaning of the frame assembly 16, once the fouling has become too significant.
  • the manganese metal formed on the two electrodes is simply recovered by disassembling the cathodes 74 and by extracting the cathodes 74 through the upper apertures 94, without having to disassemble the whole frame assembly 16.
  • the pocket shape of the diaphragms 68 allows a very efficient sequestration of the catholyte solution into the internal compartments of the cathode frames 64 preventing the anolyte solution from contaminating the catholyte solution.
  • the separation obtained between the internal compartment 90 and the anode receiving compartment 144 is very efficient, without having to make tedious efforts in the assembly of the frame assembly 16.
  • the frame assembly 16 according to the invention remains simple to assemble and disassemble, which increases the productivity of the installation.
  • the cell 10 is as disclosed in PCT patent application n °PCT/FR201 1/051699, except for the configuration of the purging conduit 38 which is as disclosed in figure 1 and 2 of the pending application.
  • the purging conduit 38 extends substantially vertically inside the tank 12 and emerges upwardly in the inner volume 14.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention porte sur un ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et sur une cellule et un procédé correspondants. La cellule comprend une pluralité de bâtis d'anode, une pluralité de bâtis de cathode (64) et une pluralité de diaphragmes (68) interposés entre chaque bâti de cathode (64) et chaque bâti d'anode (66). Au moins un diaphragme (68) comprend une première paroi poreuse (106A) recouvrant une première ouverture axiale (105A) d'un bâti de cathode (64), une seconde paroi poreuse (106B) recouvrant la seconde ouverture axiale (105B) du bâti de cathode (64) et au moins une paroi de liaison (108C, 108D) raccordant la première paroi poreuse (106A) et la seconde paroi poreuse (106B) le long du bâti de cathode (64), la première paroi poreuse (106A), la seconde paroi poreuse (106B) et la paroi de liaison (108C, 108D) délimitant un espace interne (109) contenant ou délimitant le compartiment (90) recevant la cathode interne.
PCT/IB2012/001776 2012-07-09 2012-07-09 Ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et cellule et procédé correspondants WO2014009768A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/IB2012/001776 WO2014009768A1 (fr) 2012-07-09 2012-07-09 Ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et cellule et procédé correspondants
UAA201500869A UA113886C2 (xx) 2012-07-09 2012-07-09 Внутрішній каркас комірки для електролізу марганцю, комірка та спосіб
CN201280074592.0A CN104685106B (zh) 2012-07-09 2012-07-09 用于电解锰的电解槽的内部框架组件、相关的电解槽和方法
ZA2015/00083A ZA201500083B (en) 2012-07-09 2015-01-07 Internal frame assembly of a cell for electrolysis of manganese, associated cell and method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2012/001776 WO2014009768A1 (fr) 2012-07-09 2012-07-09 Ensemble bâti interne d'une cellule pour l'électrolyse de manganèse et cellule et procédé correspondants

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WO2014009768A1 true WO2014009768A1 (fr) 2014-01-16

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UA (1) UA113886C2 (fr)
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Publication number Priority date Publication date Assignee Title
CN107313076B (zh) * 2017-06-28 2023-04-28 四川省讯益节能科技有限公司 一种节能环保电解槽及其使用方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB761794A (en) * 1953-03-05 1956-11-21 Electric Furnace Prod Co Electrolytic cell for electrowinning manganese
US3477937A (en) * 1966-03-11 1969-11-11 Foote Mineral Co Apparatus for the electrowinning of manganese
GB1294175A (en) * 1969-06-03 1972-10-25 Beceka Manganese S A Improvements in and relating to the electrolysis of a manganese salt to produce manganese dioxide
US3836443A (en) * 1970-06-04 1974-09-17 Gregor D Mac Electrowinning of ores
EP0627386A1 (fr) * 1993-05-31 1994-12-07 MIZ Co., Ltd. Dispositif pour la production d'eau électrolysée

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201201979Y (zh) * 2008-05-05 2009-03-04 杨湘清 电解锰玻璃钢电解槽
CN201713589U (zh) * 2010-05-25 2011-01-19 林建平 一种锰电解用的组合式多功能隔膜框

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB761794A (en) * 1953-03-05 1956-11-21 Electric Furnace Prod Co Electrolytic cell for electrowinning manganese
US3477937A (en) * 1966-03-11 1969-11-11 Foote Mineral Co Apparatus for the electrowinning of manganese
GB1294175A (en) * 1969-06-03 1972-10-25 Beceka Manganese S A Improvements in and relating to the electrolysis of a manganese salt to produce manganese dioxide
US3836443A (en) * 1970-06-04 1974-09-17 Gregor D Mac Electrowinning of ores
EP0627386A1 (fr) * 1993-05-31 1994-12-07 MIZ Co., Ltd. Dispositif pour la production d'eau électrolysée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Boulder City Nevada, USBM Bulletin 463", article "Operation of Electrolytic Manganese Pilot Plant", pages: 64,65

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CN104685106B (zh) 2017-05-24
CN104685106A (zh) 2015-06-03
ZA201500083B (en) 2016-01-27

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