EP3033443B1 - Appareil et procédé d'électrolyse de sel fondu - Google Patents

Appareil et procédé d'électrolyse de sel fondu Download PDF

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Publication number
EP3033443B1
EP3033443B1 EP14836690.9A EP14836690A EP3033443B1 EP 3033443 B1 EP3033443 B1 EP 3033443B1 EP 14836690 A EP14836690 A EP 14836690A EP 3033443 B1 EP3033443 B1 EP 3033443B1
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EP
European Patent Office
Prior art keywords
metal
cell
anode
alkaline earth
anodes
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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.)
Not-in-force
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EP14836690.9A
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German (de)
English (en)
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EP3033443A2 (fr
Inventor
David Steyn Van Vuuren
Dewald TERBLANCHE
Eugene SWANEPOEL
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Council for Scientific and Industrial Research CSIR
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Council for Scientific and Industrial Research CSIR
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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
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth 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
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • 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
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • the invention relates to alkali and alkaline earth metal production through electrolysis of molten chloride salts thereof.
  • alkali metals such as metallic lithium and sodium and an alkaline earth metal such a magnesium
  • an alkaline earth metal such as magnesium
  • electricity ca 35 kWh/kg Li, 11 kWh/kg sodium and 11 kWh/kg magnesium.
  • the overall energy efficiency of monopolar electrolysis cells currently in use is only about 40% to 50%.
  • a further consequence of using cylindrical anodes is that when the diameter of the anode is increased in order to increase the effective surface area of the anode available for electrolysis, the cross sectional area of the anode increases with the square of the diameter of the anode while the periphery increases only linearly. This is an important consideration since graphite, which is used as anode is a very good conductor of heat but not such a good conductor of electricity. In order to carry the necessary current without causing excessive electrical potential losses, the anodes must have a relatively large cross sectional area. Unfortunately this results in a lot of heat loss through the anode.
  • the cell consists basically of up to 8 cylindrical graphite anodes that protrude through the bottom of the cell body into the cell.
  • Around each anode is a cylindrically shaped diaphragm made of steel mesh, a perforated plate or a slotted steel plate.
  • the steel cathodes are normally connected to the power source of the cell through connections protruding through the side walls of the cell.
  • annular metal collector made of steel that has the function to collect the bulk of the molten metal product that is produced at the cathodes and that floats upwards into the collector from where it is taken out of the cell.
  • the diaphragms are normally connected and supported by the metal collector.
  • a chlorine collector or hood made of a high nickel alloy or of refractory lined steel. All the chlorine produced at the anodes is collected in this hood before it flows out of the cell.
  • the brick-lined cell is divided into four to six compartments by semi-submerged refractory partition walls labelled semi walls.
  • Three to five water- or air-cooled graphite anode plates are installed and tightly sealed in the refractory cover of the cell.
  • the semi walls on each side of the anodes separate the magnesium metal and the chlorine gas.
  • Steel cathode plates are installed through the cell cover or through the sidewalls in the cathode compartments.
  • the sequence of electrodes in the cells is: cathode, anode, cathode, cathode, anode, cathode, cathode anode etc.
  • the design of the cell is such that the flow of electrolyte caused by the chlorine bubbles produced at the anodes is upwards along the anode face, over the cathode into the space below the magnesium collection zone above the zone between the cathodes, downward behind the cathodes and then finally below the cathodes back into the space between a cathode and anode.
  • the design may result in the flow of electrolyte from the space between the electrodes over or through the cathode into a metal collection zone. Small chlorine bubbles may be entrained in this flow and end in the metal collection zone of the cell which is undesirable.
  • (a-c-a) n represents the arrangement wherein the sequence of anodes and cathodes of anode-cathode-anode are repeated n number of times, as required anode, cathode, anode, anode, cathode, anode, anode, cathode, anode, and so on.
  • the alkali metal, M is typically lithium or sodium.
  • the alkaline earth metal M ae is typically magnesium.
  • Diaphragms which may be made of steel mesh, perforated plate, or slotted plates may be installed between each pair of opposed anodes and cathodes.
  • a metal collector assembly may be installed above each cathode to collect molten alkali metal or alkaline earth metal that floats to the top of the electrolyte from where it is withdrawn from the cell.
  • the metal collector assembly may be electrically isolated from both the anodes and cathode of an anode-cathode-anode set while the metal collector assembly and the diaphragms are electrically connected to each other.
  • Both the metal collector assembly and the diaphragms may be cathodically protected by molten alkali metal or alkaline earth metal collected in the assembly for example, by molten Li, Na and/or Mg.
  • chlorine gas produced at the anode or anodes may cause circulation of a molten electrolyte used in the cell upwards along the face of the anode surface in the spaces between each anode and opposing cathode, over the active anode body, then downwards behind the anode body before turning around to flow upwards again over the face of the anode (or anodes).
  • Chlorine produced at the anodes may disengage from the circulating electrolyte at the top of the molten electrolyte above the active electrolysis zones between the anodes and cathodes.
  • the chlorine thus produced in the head space above the electrolyte is withdrawn from the cell and may be used for various purposes.
  • a particular configuration of the apparatus is to install the cathodes through the bottom of the cell and the anodes through the side or opposing sides of the cell. However, it is also feasible to install the cathodes and anodes through the other faces of the cell, including the top of the cell.
  • the electrochemical cell may be lined with chlorine resistant refractory or be made of metal, provided that the metal exposed to chlorine gas in the head space of the cell is sufficiently resistant to attack by chlorine, e.g. nickel or a high nickel containing alloy.
  • Suitable feed means may be installed to feed the salt to be electrolysed into the electrochemical cell and suitable withdrawal means may be provided to withdraw the alkali or alkaline earth metal and chlorine produced in the cell from the cell.
  • suitable heaters may be provided to preheat the electrochemical cell to melt the electrolyte inventory in the cell before commencing electrolysis.
  • a suitable direct current power source may be supplied to provide the electrical potential and current required for the reaction.
  • a process for the production of alkali metals and alkaline earth metals from the molten salts thereof by electrolysis said method including
  • the process may include maintaining the metallic alkali metal or alkaline earth metal under an inert atmosphere during extraction thereof.
  • the molten alkali metal or alkaline earth metal salt may be a sodium, lithium or a magnesium salt.
  • the sodium salt may be NaCl in which case the electrolyte may contain NaCl, CaCl 2 , and BaCl 2 allowing the cell to be operated at temperatures from about 550 to 700°C.
  • the lithium salt may be LiCl in which case the electrolyte may consist predominantly of a mixture of KCl and LiCl allowing the cell to be operated at temperatures from about 400 to 500°C.
  • the magnesium salt may be MgCl 2 in which case the electrolyte may consist predominantly of a mixture of KCl, NaCl, CaCl 2 , BaCl 2 and MgCl 2 allowing the cell to be operated at temperatures from about 660 to 800°C.
  • the alkali metal or alkaline earth metal may be recovered at a temperature above its melting point, in liquid form.
  • the alkali metal or alkaline earth metal may be recovered at a temperature below the melting point of the alkali metal or alkaline earth metal salt from which the alkali metal or alkaline earth metal is recovered.
  • chlorine produced at the anodes may disengage from the circulating electrolyte at the top of the molten electrolyte above the active electrolysis zones between the anodes and cathodes.
  • the chlorine thus produced in the head space above the electrolyte may be withdrawn from the cell and may be used for various purposes.
  • the anodes of the cell may be installed to protrude through the bottom, side or top of the cell whereas the cathodes may be Installed to protrude through the bottom or the side of the cell.
  • Figure 1 shows a vertical cross sectional schematic through the first example of an operating electrochemical cell of the invention where the anodes protrude through two opposing sides of the cell and the cathodes of the cell protrude through the bottom of the cell.
  • Figure 2 shows a horizontal section schematic viewed from the top of the construction of the electrochemical cell shown in Figure 1 .
  • the cell (1) may have a shell (24) that may be constructed from steel.
  • the cell may have a removable lid (11).
  • the cell may have a refractory lining (10) that serves to protect the shell of the cell against the hot molten electrolyte inside the cell, to limit thermally induced stresses caused by temperature increases of the shell, and to limit heat losses from the cell.
  • Four planar anodes (19) and two planar cathodes (23) of the cell (1) are shown in Figure 1 .
  • the anodes and cathodes are arranged in the following order: anode-cathode-anode-anode-cathode-anode, or (a-c-a) 2 ,
  • Each cathode is separated from the opposing pair of anodes by a diaphragm (20) and a metal collector (18) is positioned above each cathode to collect the molten alkali metal or alkaline earth metal (17) that is produced on the surfaces of the cathode.
  • the molten alkali metal or alkaline earth metal (17) has a lower density than the electrolyte (15) and therefore floats into the metal collector (18).
  • the piping to remove the molten metal from the metal collector is not shown in Figure 1 .
  • the alkali metal or alkaline earth metal salt feed (14) to the cell is introduced into a feed vessel (13) where it is dissolved in electrolyte that is circulated from and back to the cell via hot pipe lines (21) between the feed vessel (13) and the cell.
  • the cathodes (23) protrude through the shell (24) and refractory lining (10) of the cell through the bottom of the cell.
  • the mounting (22) of each cathode serves to position the cathode, to insulate it from the shell (24) and also to cool the cathode (23) as dictated by the thermal design requirements of the cell. Details of the mounting are not shown, since means to achieve the mentioned objectives are well-known in the field.
  • Chlorine is produced on the surfaces of the anodes (19) and rises as gas bubbles (16) towards the surface of the electrolyte bath where it disengages from the electrolyte and exits the cell through an exit port (12).
  • the alkaline earth metal is Mg.
  • the gas bubbles (16) form predominantly on the vertical surfaces of the anodes (19) on the sides opposing the vertical surfaces of the cathodes (23). Whereas virtually no bubbles are formed on the vertical surfaces of the anodes on the opposite sides of the anodes, the bulk density of the electrolyte/bubble mixture in the spaces between the anodes and the diaphragm (20) is lower than the bulk density of the electrolyte in the space (25) between two opposing anodes and also to that of the electrolyte in the space between the anodes and the inner surface of the refractory lining (10).
  • Some electrolyte therefore flows through each diaphragm in the upper part of the diaphragm towards the cathode, then downwards and lastly back through the diaphragm (20) in the lower part of the diaphragm towards the anode (19) opposite the specific diaphragm (20).
  • Such flow is essential to replenish the alkali metal or alkaline earth metal cations that are reduced to metal on the cathode (23) surfaces but if such flow is too high, chlorine bubbles may pass through the diaphragm (20) and eventually rise into the metal collectors (18) where it reacts undesirably with the collected molten metal.
  • the electrolyte flow around the anodes (19) are significantly increased relative to the circulating electrolyte flow through the diaphragms (20).
  • FIG 2 it is shown how four units of anode-cathode-anode assemblies can be installed in a single cell with two assemblies on each side of the cell when the anodes (19) protrude through two opposing side walls of the cell and the cathodes (23) protrude through the bottom of the cell. Also shown are anode mountings (26) that similarly to the cathode mountings (22) shown in Figure 1 serve to position the anodes, to insulate the anodes from the shell (24) and to cool the anodes. Details of the anode mountings (26) are not shown.
  • Figure 3 and Figure 4 illustrate diagrammatically the design of a second example of a cell designed in accordance with the invention where the anodes protrude through the bottom and the cathodes through a side wall of the cell.
  • Figure 3 shows a vertical cross sectional schematic through an operating electrochemical cell and
  • Figure 4 shows a vertical cross section through the construction and one of the anodes of the cell at a 90° angle relative to the cross section shown in Figure 3 .
  • slots (27) or other suitable flow channel are provided in the anodes.
  • the circulation is caused by the same density differences as described in the first example.
  • FIG. 4 The installation of the anodes (19) through the bottom of the cell and the cathodes (23) through a side wall of the cell is illustrated in Figure 4 .
  • the slots (27) through the anodes are also shown and a diaphragm (20) behind the anode,
  • a metal collector (18) is positioned on top of the cathode (23) and the shown diaphragm (20) and it may typically be sloped to direct the flow of molten metal towards the top of the collector from where it is withdrawn through pipe work that is not shown.
  • circulation of the electrolyte from the anode surface to the metal collection zone in the current planar electrode arrangements causes mixing of and back reaction of such chlorine with the molten metal in the metal collection zone.
  • LiCl and NaCl in particular have melting points that are substantially higher than the melting points of the electrolytes used with the result that solid salt is deposited in the metal collection zone that can cause blockages of the molten metal withdrawal lines.
  • MgCl 2 also has a higher melting point than the electrolyte, but the difference is substantially less. Many Mg cells actually operate above the melting point of MgCl 2 that is ca 714°C.
  • the electrochemical cell design of the invention causes a large molten electrolyte flow pattern upwards along the face of the anode surface, over the active anode body, then downwards behind the anode body before turning around to flow upwards again over the face of the anode (or anodes),
  • planar anodes and cathodes are used which enhances up-scaling of the cell and also increases the packing density of electrodes in the cell.

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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)

Claims (15)

  1. Appareil pour la production d'un métal choisi parmi les métaux alcalins métalliques, M, et les métaux alcalino-terreux, Mae, à partir de leurs sels fondus, l'appareil comprenant au moins une cellule électrochimique ayant des anodes et des cathodes planes installées dans la séquence suivante: (a-c-a)n afin de produire les métaux alcalins ou les métaux alcalino-terreux de façon électrolytique à partir de leurs sels de chlorure respectifs, n représentant le nombre de fois que la séquence anode-cathode-anode est répétée, et un assemblage de collecteur métallique étant installé au-dessus de chaque cathode pour recueillir le métal alcalin ou le métal alcalino-terreux fondus flottant vers le haut de l'électrolyte d'où il est retiré de la cellule.
  2. Appareil selon la revendication 1, dans lequel le métal alcalin, M, est choisi parmi le lithium et le sodium, et le métal alcalino-terreux Mae est le magnésium.
  3. Appareil selon les revendications 1 ou 2, dans lequel des membranes qui sont faites de treillis métallique, d'une plaque perforée ou de plaques à fentes sont installés entre chaque paire d'anodes et de cathodes opposées.
  4. Appareil selon la revendication 1, dans lequel l'assemblage de collecteur métallique est isolé électriquement à la fois des anodes et de la cathode d'un ensemble anode-cathode-anode tandis que l'assemblage de collecteur métallique et les membranes sont reliés électriquement entre eux.
  5. Appareil selon les revendications 3 ou 4, dans lequel à la fois l'assemblage de collecteur métallique et les membranes sont protégés de façon cathodique par le métal alcalin ou le métal alcalino-terreux fondus, recueillis dans l'assemblage.
  6. Appareil selon l'une quelconque des revendications précédentes, dans lequel la cellule électrochimique est revêtue d'un matériau réfractaire résistant au chlore, ou est en métal, à condition que le métal exposé à du gaz de chlore dans l'espace de tête de la cellule soit suffisamment résistant à une attaque par le biais du chlore.
  7. Appareil selon l'une quelconque des revendications précédentes, dans lequel une source d'alimentation en courant continu est prévue afin d'assurer le potentiel électrique et le courant nécessaires à la réaction.
  8. Procédé pour la production de métal choisi parmi les métaux alcalins et les métaux alcalino-terreux à partir de leurs sels de chlorure fondus par électrolyse, ledit procédé étant caractérisé en ce que
    - trois ou plus d'électrodes sont disposées suivant un agencement (a-c-a)n dans une cellule d'électrolyse, n représentant le nombre de répétitions de la séquence d'électrodes anode-cathode-anode;
    - un potentiel électrique entre les électrodes est maintenu, qui suffit pour la décomposition électrolytique du sel de métal alcalin ou de métal alcalino-terreux dans la cellule d'électrolyse;
    - la cellule d'électrolyse est alimentée en sel de métal alcalin ou métal alcalino-terreux fondus;
    - le gaz produit au niveau de l'anode peut provoquer la circulation de l'électrolyte fondu utilisé dans la cellule vers le haut le long de la face latérale de la surface de l'anode dans les espaces entre chaque anode et cathode opposée, au-dessus du corps d'anode actif, puis vers le bas derrière le corps d'anode avant de faire demi-tour pour circuler vers le haut à nouveau à travers la face latérale de l'anode (ou anodes);
    - le métal alcalin métallique ou le métal alcalino-terreux peut être séparée, par densité, de l'électrolyte fondu et peut donc être récupéré; et
    - le métal alcalin métallique ou le métal alcalino-terreux peut être conservé dans une atmosphère inerte lors de leur l'extraction.
  9. Procédé selon la revendication 8, dans lequel le sel de métal alcalin ou de métal alcalino-terreux fondus est choisi parmi le sodium, le lithium ou un sel de magnésium.
  10. Procédé selon la revendication 9, dans lequel le sel de sodium est le NaCl, dans lequel cas l'électrolyte contient du NaCl, CaCl2 et BaCl2, permettant à la cellule de fonctionner à des températures d'environ 550 à 700°C.
  11. Procédé selon la revendication 9, dans lequel le sel de lithium est le LiCl, dans lequel cas l'électrolyte est constitué principalement d'un mélange de KCl et de LiCl, permettant à la cellule de fonctionner à des températures d'environ 400 à 500°C,
  12. Procédé selon la revendication 9, dans lequel le sel de magnésium est MgCl2, dans lequel cas l'électrolyte est constitué principalement d'un mélange de KCI, NaCl, CaCl2, BaCl2 et MgCl2, permettant à la cellule de fonctionner à des températures d'environ 660 à 800°C.
  13. Procédé selon l'une quelconque des revendications 8 à 12, dans lequel le métal alcalin ou le métal alcalino-terreux est récupéré sous forme liquide à une température dépassant son point de fusion.
  14. Procédé selon l'une quelconque des revendications 8 à 12, dans lequel le métal alcalin ou le métal alcalino-terreux est récupéré à une température au-dessous du point de fusion du sel de métal alcalin ou du sel de métal alcalino-terreux à partir duquel le métal alcalin ou le métal alcalino-terreux est récupéré.
  15. Procédé selon l'une quelconque des revendications 8 à 14, dans lequel le chlore produit au niveau des anodes se dégage de l'électrolyte circulant à la partie supérieure de l'électrolyte fondu au-dessus des zones d'électrolyse actives entre les anodes et les cathodes.
EP14836690.9A 2013-08-16 2014-08-15 Appareil et procédé d'électrolyse de sel fondu Not-in-force EP3033443B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA201306171 2013-08-16
PCT/ZA2014/000038 WO2015024030A2 (fr) 2013-08-16 2014-08-15 Appareil et procédé d'électrolyse de sel fondu

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EP3033443A2 EP3033443A2 (fr) 2016-06-22
EP3033443B1 true EP3033443B1 (fr) 2018-03-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020053478A1 (fr) * 2018-09-11 2020-03-19 Tercosys Oy Procédé et arrangement de gestion d'énergie
DE102022000153A1 (de) 2022-01-17 2023-07-20 KS iPR UG (haftungsbeschränkt) Elektrolyt membran zur trennung von wasserdampf in wasserstoff und sauerstoff mit hilfe von elektrischer energie und/oder erzeugung von elektrischer energie mit hilfe von wasserstoff und sauerstoff durch eine lithiierte eisenoxid - eisen redoxreaktion in einem flüssigen carbonatsalz

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113493918B (zh) * 2020-04-01 2024-09-27 青海北辰科技有限公司 低恒温密闭镁电解装置

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US1501756A (en) 1922-08-18 1924-07-15 Roessler & Hasslacher Chemical Electrolytic process and cell
DE1558726B2 (de) 1951-01-28 1973-09-06 Elektrolysierzelle
US3544444A (en) 1967-05-19 1970-12-01 Du Pont Fused salt electrolysis cell having anode with tapered well therein
US5904821A (en) 1997-07-25 1999-05-18 E. I. Du Pont De Nemours And Company Fused chloride salt electrolysis cell
US6497807B1 (en) * 1998-02-11 2002-12-24 Northwest Aluminum Technologies Electrolyte treatment for aluminum reduction
US6827828B2 (en) * 2001-03-29 2004-12-07 Honeywell International Inc. Mixed metal materials
CN101709485B (zh) * 2009-12-18 2012-07-04 中国铝业股份有限公司 一种采用惰性阳极生产原铝的铝电解槽

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020053478A1 (fr) * 2018-09-11 2020-03-19 Tercosys Oy Procédé et arrangement de gestion d'énergie
US11873565B2 (en) 2018-09-11 2024-01-16 Tercosys Oy Energy management method and arrangement
DE102022000153A1 (de) 2022-01-17 2023-07-20 KS iPR UG (haftungsbeschränkt) Elektrolyt membran zur trennung von wasserdampf in wasserstoff und sauerstoff mit hilfe von elektrischer energie und/oder erzeugung von elektrischer energie mit hilfe von wasserstoff und sauerstoff durch eine lithiierte eisenoxid - eisen redoxreaktion in einem flüssigen carbonatsalz

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WO2015024030A2 (fr) 2015-02-19
EP3033443A2 (fr) 2016-06-22
US20160215405A1 (en) 2016-07-28
WO2015024030A3 (fr) 2015-07-23

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