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EP2064369B1 - Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorures métalliques riches en fer - Google Patents

Procédé électrochimique pour la récupération de valeurs de fer métallique et de chlore à partir de déchets de chlorures métalliques riches en fer Download PDF

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EP2064369B1
EP2064369B1 EP07701657A EP07701657A EP2064369B1 EP 2064369 B1 EP2064369 B1 EP 2064369B1 EP 07701657 A EP07701657 A EP 07701657A EP 07701657 A EP07701657 A EP 07701657A EP 2064369 B1 EP2064369 B1 EP 2064369B1
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Prior art keywords
iron
alloy
electrochemical process
metal chloride
chloride solution
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EP2064369A1 (fr
EP2064369A4 (fr
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François CARDARELLI
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Rio Tinto Fer et Titane Inc
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Qit Fer et Titane Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof

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  • the present invention relates to an electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes. More specifically, the present invention is concerned with an electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes such as carbo-chlorination wastes, spent acid leaching liquors, pickling liquors, or any other iron-rich metal chloride liquor or solution.
  • chlorine gas is one of the most widely used inorganic chemicals.
  • polyurethanes, halogenated hydrocarbons and white titanium dioxide pigment are commonly manufactured in processes using chlorine gas.
  • feedstock is chlorinated with chlorine gas.
  • Chlorinated species are reduced to waste by-products such as: hydrogen chloride (HCl gas ), hydrochloric acid (HCl aq ) or inorganic metal chlorides (e.g., FeCl 3 , FeCl 2 , MgCl 2 ).
  • titanium tetrachloride TiCl 4
  • titaniferous ores feedstock e.g., weathered ilmenite, titanium slag or synthetic rutiles
  • by-products may comprise either ferrous or ferric chlorides or a combination thereof, depending on the reaction conditions of the chlorinator.
  • the actual by-products are in fact more complex as these consist of a chlorination waste which is essentially made of a blend of particulate iron chlorides contaminated with unreacted titanium feedstocks, petroleum coke, silica and silicates, and other metal chlorides.
  • Table 1 The approximate chemical composition of the metal chlorides collected from the cyclones of chlorinators operating with titanium slag only is presented in Table 1 below.
  • Table 1 Average composition ranges of the metal chlorides in an as- received chlorinator dust, expressed as anhydrous salts (wt.%) Metal chlorides Formula Percentage Iron (II) chloride FeCl 2 30-70 Aluminum (III) chloride AlCl 3 5-15 Magnesium (II) chloride MgCl 2 5-20 Manganese (II) chloride MnCl 2 4-15 Sodium chloride NaCl 1-8 Vanadium (IV) oxychloride VOCl 2 1-6 Chromium (III) chloride CrCl 3 0.5-6 Titanium (III) chloride TiCl 3 0.1-3
  • Table 2 Average composition ranges of spent acid Cations or chemicals Concentration ( c /g.dm -3 ) HCl (free) 40-70 Fe(total) 30-60 Fe(II) 20-45 Mg(II) 10-30 Al(III) 4-12 Fe(III) 4-12 Ca(II) 0.5-2 V(III) 0.5-2 Mn(II) 0.5-3 Cr(III) 0.3-2 Ti(IV) 0.1-1
  • Harris suggested that ferric chloride can be treated with oxygen in a fluidized-bed reactor in the vapor phase. The process produces chlorine gas, which can be recycled to a ilmenite or rutile chlorination process, and iron oxide by-product rather than soluble chloride wastes.
  • GB Patent 1,407,034 2 discloses oxidation of gaseous ferrous chloride with oxygen in excess at temperatures sufficiently high to avoid condensation of the ferrous chloride.
  • US Patent 3,865,920 3 to RZM Ltd. discloses a process consisting in preheating ferrous chloride at 980°C to 1110°C and then oxidizing it by passing pure oxygen to form a mixture of iron chlorides, iron oxide, oxygen and chlorine, which mixture is thereafter cooled and the residual iron chloride converted to iron oxide and chlorine.
  • JP 2006/241568 discloses an economical electrowinning method to recover metal iron from an iron ion-containing acid chloride aqueous solution, using an electrolytic cell composed of a cathode chamber and an anode chamber partitioned by a diaphram, wherein the acid chloride aqueous solution is fed to the cathode chamber to electrolytically deposit a part of the iron ions, is successively introduced into the anode chamber provided with an oxygen generation type insoluble anode through the diaphram to oxidize the iron ions, and is thereafter exhausted from the anode chamber.
  • thermodynamics requires low temperature, i.e., usually below 400°C, to shift the equilibrium in favor of the oxidation of the ferric chloride.
  • temperature i.e., usually below 400°C
  • ferrous chloride FeCl 2
  • FeCl 3 ferric chloride
  • Fe 2 O 3 ferric oxide
  • the first well-documented attempt apparently dates back to 1928 with the patents of LEVY 10 .
  • the inventor disclosed a simple electrochemical process for recovering both nascent chlorine and pure electrolytic iron from a solution of pure ferrous chloride.
  • the electrolyser was divided with a diaphragm as separator made of porous unglazed clay to prevent the mixing of products.
  • the electrolysis was conducted at 90-100°C under a current density of 110 - 270 A.m -2 with an average cell voltage of 2.3-3.0 V.
  • the Faradaic current efficiency was 90-100%.
  • the anolyte was a concentrated chloride solution (e.g., CaCl 2 , NaCl) while the catholyte was an aqueous solution containing 20 wt.% FeCl 2 .
  • the anode was carbon-based while the cathode was a thin plate, mandrel or other suitable object.
  • the catholyte which is made of high purity ferrous chloride and constantly adjusted to a pH of 3 to 5 with ammonia, and the anolyte made of sodium chloride, recirculate in loop inside their respective compartments, while the iron-rich chloride-containing solution to be electrolysed circulates through the central compartment, that is, the gap existing between the two ion-exchange membranes.
  • the cathode used is preferably iron but may also be stainless steel, titanium or titanium alloy, and the anode used is made of insoluble graphite.
  • this 3-compartment process apparently allows, in contrast to that using a two-compartment electrolytic process, to avoid polluting the resulting electro-crystallized iron by embedded impurities such as metal oxides.
  • maintaining the catholyte pH between 3 and 5 allows avoiding hydrogen evolution at the cathode.
  • the present invention generally relates to an electrochemical process for the recovery of metallic iron and chlorine gas from iron-rich metal chloride wastes.
  • an aspect of the present invention relates to an electrochemical process for the recovery of metallic iron and chlorine gas from an iron-rich metal chloride solution comprising the following steps:
  • step (a) of providing an iron-rich metal chloride solution includes the following steps:
  • the pH of the catholyte is adjusted to range between about 0.3 and about 1.8, preferably between about 0.6 and about 1.5, more preferably between about 0.6 and about 1.1, most preferably between about 0.9 and about 1.1.
  • the cathode has an overvoltage, at 200 A.m -2 , greater than about 425 mV in 0.5 mol.dm -3 HCl at 25°C.
  • the cathode is constructed from or coated with a material selected from the group consisting of titanium, titanium alloy, zirconium, zirconium alloy, zinc, zinc alloy, cadmium, cadmium alloy, tin, tin alloy, copper, copper alloy, lead, lead alloy, niobium, niobium alloy, gold, gold alloy, mercury and metallic amalgam with mercury.
  • Another aspect of the present invention relates to a process for the recovery of metallic iron and chlorine gas from an iron-rich metal chloride solution, which process comprises:
  • Figure 1 is a flow-sheet diagram illustrating the various steps of the entire electrochemical process according to a first embodiment of the present invention, based on a two-compartment electrolyser and performing electrolysis with a pH-adjusted iron-rich metal chloride solution;
  • Figure 2 is a flow-sheet diagram illustrating the various steps of the entire electrochemical process according to a second embodiment of the present invention, based on a two-compartment electrolyser and performing electrolysis with a pH-adjusted iron-rich metal chloride solution from which the vanadium has been removed by precipitation prior to its introduction in the cathodic compartment;
  • Figure 3 is a flow-sheet diagram illustrating the various steps of the entire electrochemical process according to a third embodiment of the present invention, using a three-compartment electrolyser and performing electrolysis with a non-adjusted iron-rich metal chloride solution;
  • Figure 4 is a schematic illustration of a two-compartment electrolyser used in some embodiments of the present invention with major electrochemical reactions occurring at each electrode;
  • Figure 5 is a schematic illustration of a three-compartment electrolyser used in some embodiments of the present invention with major electrochemical reactions occurring at each electrode;
  • Figure 6 is a photograph obtained by a scanning electron microscope (SEM) showing an overview of a co-deposition of iron and vanadium, as obtained in Example 2a;
  • Figure 7 is a photograph obtained by a scanning electron microscope (SEM) showing a detail view of a co-deposition of iron and vanadium pentoxide, as obtained in Example 2a;
  • Figure 8 is a photograph showing a smooth iron electrodeposit with a small amount of vanadium, as obtained in Example 2b;
  • Figure 9 is a photograph showing an electrodeposited thin plate of iron metal, as obtained in Example 5.
  • Figure 10 is a photograph showing an iron metal deposit plate, as obtained in Example 6;
  • Figure 11 is a graphical illustration showing the polarization curves as obtained in Example 8 (selection of a cathode material).
  • Figure 12 is a graphical illustration showing the polarization curves as obtained in Example 9 (selection of an anion exchange membrane).
  • Figure 13 is a graphical illustration showing the polarization curves as obtained in Example 10 (selection of an anolyte).
  • feedstocks may be used in a process according to the present invention, including, but not limited to, carbo-chlorination wastes, for example from carbo-chlorination of titaniferous ores, spent acid leaching liquors, pickling liquors or any other iron-rich metal chloride liquor or solution.
  • carbo-chlorination wastes for example from carbo-chlorination of titaniferous ores, spent acid leaching liquors, pickling liquors or any other iron-rich metal chloride liquor or solution.
  • the feedstock may be solid, anhydrous, in slurry form or in solution.
  • electrolyser generally designates a two-compartment or three-compartment electrolyser. All electrolysers used in the process of the present invention at least comprise an anodic compartment and a cathodic compartment, separated by at least one ion exchange membrane.
  • non-anodic compartment designates the cathodic compartment of a two-compartment electrolyser and/or the central compartment of a three-compartment electrolyser. For more clarity, it does not designate the cathodic compartment of a three-compartment electrolyser.
  • overpotential generally designates the difference between the electrical potential of an electrode under the passage of current and the thermodynamic value of the electrode potential in the absence of electrolysis for the same experimental conditions.
  • the term "hydrogen overpotential" designates an overpotential associated with the liberation of hydrogen gas at the cathode.
  • a cathode having high hydrogen overpotential minimizes hydrogen evolution during electrolysis, and thus facilitates iron electrodeposition.
  • materials having high hydrogen overpotential are given, for example, in Cardarelli 13 and in US Patent 5,911,869 to Exxon Research and Engineering and Co. 14 .
  • the cathode material also allows stripping of the iron metal deposit.
  • Non limiting examples of suitable cathode materials include titanium (of commercial or higher purity), titanium alloy (for example titanium palladium ASTM grade 7), zirconium (of commercial or higher purity), zirconium alloy, zinc (of commercial or higher purity), zinc alloy, cadmium (of commercial or higher purity), cadmium alloy, tin (of commercial or higher purity), tin alloy, copper (of commercial or higher purity), copper alloy, lead (of commercial or higher purity), lead alloy, niobium (of commercial or higher purity), niobium alloy, gold (of commercial or higher purity), gold alloy, mercury or metallic amalgam with mercury.
  • a cathode having high hydrogen overpotential may consist of a bulk of a material having high hydrogen overpotential or may simply be coated with such a material.
  • the expression "having a hydrogen overpotential higher than that of iron” means that, in absolute value, the cathode has an overvoltage, at 200 A.m -2 , greater than about 425 mV in 0.5 mol.dm -3 HCl at 25°C.
  • vanadium-separation step essentially designates a step wherein vanadium is separated from iron. Thus it may correspond to, but it is not necessarily a step wherein vanadium gets recovered as a substantially pure vanadium compound.
  • the process generally first consists in leaching the feedstock, such as an anhydrous chlorinator dust by-produced during carbo-chlorination of titania-rich feedstocks (e.g., weathered ilmenite, titanium slag, natural and synthetic rutiles), with either one of: hot acidic process water, hot diluted hydrochloric acid, hot spent acid coming from the high pressure acid leaching of titanium slags or even from spent liquors by-produced during the pickling of steel.
  • anhydrous chlorinator dust by-produced during carbo-chlorination of titania-rich feedstocks (e.g., weathered ilmenite, titanium slag, natural and synthetic rutiles)
  • hot acidic process water hot diluted hydrochloric acid
  • hot spent acid coming from the high pressure acid leaching of titanium slags or even from spent liquors by-produced during the pickling of steel.
  • the resulting slurry is filtered to separate the remaining insoluble solids comprising unreacted titania slag, silica and silicates, titanium dioxide fines and coke fractions from soluble metal chlorides in the form of an iron-rich metal chloride liquor or solution.
  • the filter cake obtained is carefully washed with a minimum of acidic water, dewatered, dried and eventually sent back to the carbo-chlorination plant or discarded and landfilled (depending on its titanium and coke values and content of silica), while the wash water may be reused in the first leaching step.
  • the leaching may help dissolve the soluble solids before a solid-liquid separation, for example by filtration.
  • the leaching step is of no particular interest.
  • three main process variants can be used for recovering both chlorine and metal values from the iron-rich metal chloride solution, based on the same general principle of simultaneous recovery of metal iron and chlorine values from an iron-rich metal chloride solution by electrolysis, using a catholyte adjusted to a pH below 2 and a cathode having a hydrogen overpotential higher than that of iron.
  • the pH of the iron-rich metal chloride solution is first adjusted to between about 0.6 and about 1.8, with alkaline reagents such as, but not limited to, magnesia or ammonium hydroxide or a mixture thereof, after which the solution is ready for electrolysis.
  • alkaline reagents such as, but not limited to, magnesia or ammonium hydroxide or a mixture thereof
  • the electrolytic stage consists in circulating the pH-adjusted iron-rich metal chloride solution inside the cathodic compartment of an electrolyser.
  • the iron-rich metal chloride solution thus acts as catholyte.
  • the electrolyser consists of two compartments separated by an anion-exchange membrane (as illustrated in Figure 4 ).
  • the cathodic compartment comprises a cathode made of titanium or titanium alloy (usually ASTM grade 7), while the anodic compartment has a dimensionally stable anode for the evolution of chlorine (DSATM-Cl 2 ).
  • the anolyte that circulates in loop in the anodic compartment is made of a mixture of about 20 wt.% hydrochloric acid and about 17 wt.% magnesium chloride with about 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor.
  • chloride anions migrate through the permeable anion exchange membrane towards the anodic compartment and discharge as chlorine gas at the surface of the anode according to the following electrochemical reactions: Fe 2+ (aq) + 2e - ⁇ Fe 0 (s) (cathode, -) 2Cl - (aq) ⁇ Cl 2 (g) + 2e - (anode, +)
  • the cathode materials used in the process according to the present invention have hydrogen overpotential higher (in absolute value) than that of iron in given electrolysis conditions.
  • the pH of the catholyte is maintained between about 0.6 and about 1.8, more preferably between about 0.6 and about 1.5, still more preferably between about 0.6 and about 1.1, and most preferably between about 0.9 and 1.1.
  • using an inert atmosphere of nitrogen above the cathodic compartment may help preventing the oxidation of the ferrous cations.
  • the utilization of a dimensionally stable anode for chlorine evolution may impede the evolution of oxygen gas, thereby ensuring the production of a high purity chlorine gas.
  • the electrolysis is usually conducted between about 40°C and about 110°C under a galvanostatic control.
  • the overall current density is comprised between about 200 and about 2000 A/m 2 with a cell voltage ranging from about 1.2 to about 3.5 V per cell.
  • the faradaic efficiency is usually greater than about 90% and the average specific energy consumption is between about 2.1 and about 6.2 kWh per kg of iron and between about 1.1 and about 3.5 kWh per kilogram of chlorine gas.
  • the wet chlorine gas evolved is recovered by conventional methods. For example, as shown in Figure 1 , it may be recovered by suction, cooled by passing it through a graphite heat exchanger, and dried by passing it through a mist eliminator and several concentrated sulfuric acid spray-towers (scrubbing). Finally the dry and cold chlorine gas may be compressed and liquefied, thus being ready to be transported or stored on-site for future use.
  • the thick plates of electrodeposited iron metal are mechanically stripped from the titanium cathode.
  • the plates are then immersed into a hot lye of concentrated sodium hydroxide (50 wt.% NaOH) to selectively dissolve the vanadium oxides; traces of oxydiser, such as, but not limited to, potassium chlorate, are added to convert all the vanadium into pentavalent vanadium and pure iron metal is separately recovered.
  • Ammonia along with ammonium chloride (NH 4 Cl) and/or ammonium hydroxide are then added to the remaining liquor in order to precipitate all the vanadium as ammonium metavanadate (NH 4 VO 3 ).
  • a vanadium-separation step occurs after the electrolysis step.
  • Sulfuric acid is added to the spent iron-free electrolyte, or iron-depleted solution, exiting the electrolyser, for removing calcium as insoluble calcium sulfate dihydrate (CaSO 4 .2H 2 O) and entraining optional traces of radioactivity, mostly as radium sulfate.
  • the remaining spent magnesium- and aluminum-rich brine is then pyro-hydrolysed to yield refractory spinel beads, pellets or granules ready to be used in the manufacture of refractories or proppants, while recovering azeotropic hydrochloric acid.
  • the exact vanadium content of the iron-rich metal chloride solution is determined by a conventional method and a stoichiometric amount of potassium chlorate (KClO 3 ) is introduced to oxidize all the vanadium into vanadium (V) (not shown).
  • a corresponding amount of iron (III) chloride is then added and the pH of the solution is adjusted to between about 0.5 and about 3 with alkaline reagents such as for instance magnesia or ammonium oxide, hydroxide or a mixture thereof. This precipitates together vanadium (V) and chromium (VI), entrained by co-precipitation with the ferric hydroxide (Fe(OH) 3 ).
  • the gelatinous vanadium-rich precipitate is then removed from the slurry by a known technique of either decantation, centrifugation or filtration.
  • the so-obtained vanadium-rich precipitate for example in the form of a filter cake, is then dissolved in a minimum amount of concentrated solution of sodium hydroxide and oxidised with traces of oxydiser.
  • the remaining ferric and chromic hydroxides are discarded and the vanadium is selectively precipitated as ammonium metavanadate (NH 4 VO 3 ) by addition of ammonium hydroxide (NH 4 OH) and/or ammonium chloride (NH 4 Cl), and recovered.
  • the clear filtrate or supernatant from the vanadium separation step is pH-adjusted at a pH below 2, preferably between about 0.6 and about 1.8 and thus ready for electrolysis, in the form of a vanadium-depleted and pH adjusted iron-rich metal chloride solution (not shown).
  • the electrolysis consists in circulating the vanadium-depleted and pH-adjusted iron-rich metal chloride solution inside the cathodic compartment of an electrolyser.
  • the iron-rich metal chloride solution thus acts as catholyte.
  • the electrolyser consists of a cell divided by an anion-exchange membrane (as illustrated in Figure 4 ).
  • the cathodic compartment has a cathode made of titanium metal or a titanium alloy (usually ASTM grade 7).
  • the anodic compartment has a dimensionally stable anode for the evolution of chlorine (DSATM-Cl 2 ).
  • the anolyte that circulates in loop is made of a mixture of about 20 wt.% hydrochloric acid and about 17 wt.% magnesium chloride with about 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor.
  • ferric iron Fe 3+
  • pure iron metal is deposited at the cathode, while chloride anions migrate through the permeable anion exchange membrane to the anodic compartment and discharge as chlorine gas at the surface of the anode according to the following electrochemical reactions: Fe 2+ (aq) + 2e - ⁇ Fe 0 (s) (cathode, -) 2Cl - (aq) ⁇ Cl 2 (g) + 2e - (anode, +)
  • the pH of the catholyte is maintained between about 0.6 and about 1.8, more preferably between about 0.6 and about 1.5, still more preferably between about 0.6 and about 1.1, and most preferably between about 0.9 and 1.1.
  • using an inert atmosphere of nitrogen above the cathodic compartment may help preventing the oxidation of the ferrous cations.
  • the utilization of a dimensionally stable anode for chlorine evolution may impede the evolution of oxygen gas, thereby ensuring the production of a high purity chlorine gas.
  • the electrolysis is usually conducted between about 40°C and about 110°C under a galvanostatic control.
  • the overall current density is comprised between about 200 and about 2000 A/m 2 with a cell voltage ranging from about 1.9 to about 3.5 V per cell.
  • the faradaic efficiency is usually greater than 90% and the specific energy consumption is usually between about 2 and about 3.7 kWh per kg of iron and between about 1.6 and about 3 kWh per kilogram of chlorine gas.
  • the wet chlorine gas evolved is recovered by suction, is cooled by passing it through a graphite heat exchanger, and dried by passing it through a mist eliminator and several concentrated sulfuric acid spray-towers (scrubbing). Finally the dry and cold chlorine gas is compressed and liquefied, thus being ready to be transported or stored on-site for future reutilization.
  • the thick electrodeposited plates of pure iron metal are mechanically stripped from the titanium cathode.
  • Concentrated sulfuric acid is added to the spent iron-free electrolyte, or iron-depleted solution, exiting the electrolyser for removing calcium as insoluble calcium sulfate dihydrate (CaSO 4 .2H 2 O and entraining optional traces of radioactivity, mostly as radium sulfate.
  • the remaining spent magnesium- and aluminum-rich brine is then pyrohydrolysed to yield refractory spinel beads, pellets or granules ready to be used in the manufacture of refractories or proppants while recovering azeotropic hydrochloric acid.
  • the iron-rich metal chloride solution is sent without any prior treatment (such as pH adjustment) to the electrochemical plant.
  • the electrolyser design used in this process (as illustrated in Figure 5 ) has three compartments: (i) a cathodic compartment with a titanium plate cathode, (ii) an anodic compartment comprising a dimensionally stable anode for the evolution of chlorine, and (iii) a central compartment separated from the cathodic compartment by a cation-exchange membrane and from the anodic compartment by an anion exchange membrane.
  • the catholyte circulating inside the cathodic compartment is a saturated solution of ferrous chloride (about 350 g/L FeCl 2 ) with magnesium chloride (about 220 g/L MgCl 2 ), while the anolyte is made of about 20 wt.% hydrochloric acid and about 17 wt.% magnesium chloride with about 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor.
  • the pH of the catholyte is adjusted below pH 2, preferably between about 0.6 and about 1.8, more preferably between about 0.6 and about 1.5, still more preferably between about 0.6 and about 1.1, most preferably between about 0.9 and about 1.1.
  • the iron-rich metal chloride solution is passed through the central compartment continuously.
  • ferrous cations of the iron-rich metal chloride solution migrate through the cation exchange membrane and are reduced to pure iron metal onto the titanium cathode while the chloride anions migrate through the anion exchange membrane towards the dimensionally stable anode where they are oxidized, thereby producing chlorine gas that evolves.
  • the electrochemical reactions involved are as follows: Fe 2+ (aq) + 2e - ⁇ Fe 0 (s) (cathode, -) 2Cl - (aq) ⁇ Cl 2 (g) + 2e - (anode, +)
  • the electrolysis is conducted between about 40 and about 110°C under galvanostatic control with an overall current density comprised between about 200 and about 2000 A/m 2 with a cell voltage ranging from about 1.9 to about 3.5 V per cell.
  • the faradaic efficiency is usually greater than about 90%.
  • the pure and wet chlorine gas evolved is recovered by suction, is cooled by passing it through a graphite heat exchanger and dried by passing it through a mist eliminator and several concentrated sulfuric acid spray-towers. Finally the dry and cold chlorine gas is compressed and then liquefied, thus being ready to be transported or stored on-site for future utilization.
  • the thick plates of electrodeposited pure iron metal are mechanically stripped from the titanium cathode.
  • Hydrogen peroxide H 2 O 2
  • H 2 O 2 Hydrogen peroxide
  • MgO magnesium oxide
  • the precipitate is removed by decantation, filtration or centrifugation, dried and calcined to yield flakes of vanadium pentoxide (V 2 O 5 ) (not shown).
  • the pH of the iron-rich metal chloride solution may or may not be adjusted prior to electrolysis when using a three-compartment electrolyser. Such an adjustment could, for example, serve to effect a vanadium precipitation along with iron deposition, as above, although it is not a preferred embodiment here.
  • Cathode materials suitable for use in the process of the present invention are materials having a high overpotential for the evolution of hydrogen, more specifically a hydrogen overpotential higher than that of iron in given electrolysis conditions.
  • the cathode material also allows stripping of the iron metal deposit.
  • Non limiting examples of suitable cathode materials include titanium (of commercial or higher purity), titanium alloy (for example titanium palladium ASTM grade 7), zirconium (of commercial or higher purity), zirconium alloy, zinc (of commercial or higher purity), zinc alloy, cadmium (of commercial or higher purity), cadmium alloy, tin (of commercial or higher purity), tin alloy, copper (of commercial or higher purity), copper alloy, lead (of commercial or higher purity), lead alloy, niobium (of commercial or higher purity), niobium alloy, gold (of commercial or higher purity), gold alloy, mercury or metallic amalgam with mercury.
  • Anode materials suitable for use in the process of the present invention include (as bulk or coating materials) (1) dimensionally stable anodes for the evolution of chlorine (DSA TM -Cl 2 ) of the type [M/M x Oy-A z O t ] made of a metallic substrate or base metal M coated with a mixed metal oxides (MMO) as electrocatalyst, wherein M is a refractory metal or an alloy with a valve action property such as titanium, titanium alloy, zirconium, zirconium alloy, hafnium, hafnium alloy, vanadium, vanadium alloy, niobium, niobium alloy, tantalum, tantalum alloy, M x O y is a metallic oxide of a valve metal forming a thin and impervious layer protecting the base metal such as TiO 2 , ZrO 2 , HfO 2 , NbO 2 , Nb 2 O 5 , TaO 2 , and Ta 2 O 5 , and A
  • the anolyte composition used in the process of the present invention advantageously comprises hydrochloric acid, a salt such as MgCl 2 , NaCl, CaCl 2 or mixtures thereof and Fe(III) as corrosion inhibitor.
  • suitable anolyte compositions may vary in the following ranges: about 10 to about 37 wt.% hydrochloric acid (preferably about 20%); about 1 to about 20 wt.% MgCl 2 , NaCl, KCI, LiCl, CaCl 2 or mixtures thereof (preferably about 16%) with about 10 to about 12,000 ppm wt. Fe(III) as corrosion inhibitor (preferably 8,000 to 10,000 ppm wt).
  • the catholyte composition may vary in the following ranges: about 1 to about 450 g/L of iron (II) chloride (preferably about 335 g/L), about 1 to about 350 g/L MgCl 2 (preferably about 250 g/L), about 1 to about 350 g/L CaCl 2 (preferably about 250 g/L) or about 350 g/L of a mixture of MgCl 2 and CaCl 2 (preferably about 250 g/L); it may also further comprise 0 to about 10 g/L of free HCl.
  • the catholyte pH generally ranges between about 0.6 and about 1.5, preferably about 0.6 to about 1.1, more preferably about 0.9 to about 1.1.
  • the reaction temperature may range between about 40 and about 110°C, preferably between about 80 and about 95°C. Most preferably, the operating temperature is about 85°C.
  • the volume flow rate of both anolyte and catholyte advantageously ranges between about 0.1 and about 100 Umin, preferably between about 0.1 and about 30 Umin. Most preferably, the volume flow rate is about 2 L/min.
  • the cathodic current density during electrolysis, to produce a dendrite-free smooth deposit of iron advantageously ranges between about 50 and about 1000 A/m 2 .
  • the cathodic current density is about 500 A/m 2 .
  • the cathodic current density during electrolysis, to produce an iron powder advantageously ranges between about 3000 and about 5000 A/m 2 .
  • the cathodic current density is about 4000 A/m 2 .
  • Separators used in the process of the present invention may be passive, such as a conventional diaphragm separator, or active such as ion exchange membranes.
  • the separators used are ion exchange membranes.
  • Anion exchange membranes and cation exchange membranes used in the process of the present invention are conventional membranes. Non-limiting examples of suitable anion exchange membranes are presented in the Examples below ( Figure12 ).
  • the interelectrode gap may also be varied, with a well-known impact on the ohmic drop. It is advantageously about 6 mm.
  • the Buchners were installed ontop of a 10-liter Erlenmeyer vacuum flask (Kimax) connected to a vacuum pump.
  • the filtration media used were disks of ash-less filter paper No. 42 (Whatman). In order to increase throughput, four of these Buchner-Erlenmeyer assemblies were operated simultaneously in parallel.
  • wash water and the four filtrates totalized 18 L, which were collected into a large 5 US-gallons cylindrical tank made of polypropylene.
  • concentration of metal chlorides in this initial solution after leaching is presented in Table 4. Since the concentration of iron (II) chloride in the filtrate (i.e 83.7 g/L) was too low for performing the electrolysis at a cathodic current density sufficient to obtain a smooth deposit, the solution was further concentrated by evaporation into a large Erlenmeyer flask heated onto a hot plate (Coming). The evaporation was stopped when the volume of the solution was reduced by four (4.5 L).
  • the concentration of metal chlorides was greatly increased and reached 335 g/L for iron (II) chloride when sampled at 80°C (see Table 4, concentrated solution).
  • the solution was immediately transferred into a 10-L jacketed glass reactor (Kimble-Contes) heated by circulating hot water supplied by a heating bath (Lauda GmbH). The temperature of the solution was maintained at 80°C at all times.
  • the solution was also acidified by adding minute amounts of concentrated hydrochloric acid to maintain the concentration of free acid around 10 g/L.
  • Example 2a Electrolysis of the initial concentrated iron-rich metal chloride solution at pH 1.1 ).
  • the previous iron-rich metal chloride concentrated solution from Example 1 was simply adjusted at a pH of 1.1 by adding minute amount of magnesia and then circulated inside the cathodic compartment of an electrolyser.
  • the electrolyser consisted of a filter press design model MP cell from Electrocell AB (Sweden) with two compartments separated by an anion-exchange membrane made of Excellion® I-200 (SnowPure LLC). The geometric electrode and membrane surface area was 100 cm 2 and the spacing between each electrode and the separator was 6 mm.
  • the cathodic compartment comprised a cathode plate made of a titanium palladium alloy (ASTM grade 7; Ti-0.15Pd) supplied by Titanium Industries. Prior to electrolysis the cathode was chemically etched by immersing it into a fluoro-nitric acid mixture (70 vol% conc. HNO 3 , 20 vol.% conc. HF and 10 vol.% H 2 O) and then rinsing it thoroughly with deionised water until no trace of acid remained.
  • a fluoro-nitric acid mixture 70 vol% conc. HNO 3 , 20 vol.% conc. HF and 10 vol.% H 2 O
  • the anodic compartment was equipped with a dimensionally stable anode (DSATM-Cl 2 ) supplied by Magneto BV (Netherlands) made of a plate of a titanium-palladium alloy substrate coated with a high loading of ruthenium dioxide (RuO 2 ) acting as electrocatalyst for promoting the evolution of chlorine (Ti-0.15Pd/RuO 2 ).
  • the anolyte that recirculated in loop consisted of an aqueous solution of 20 wt.% hydrochloric acid with 17 wt.% magnesium chloride (MgC1 2 ) and 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor, the balance being deionised water.
  • the electrolysis was performed galvanostatically at an overall current density of 500 A/m 2 .
  • the operating temperature was 80°C and the volume flow rate of both catholyte and anolyte was 1 Umin. At that current density, the measured overall cell voltage was 2.528 V.
  • pure iron metal deposited at the cathode.
  • chloride anions migrated through the permeable anion exchange membrane towards the anodic compartment and discharged as chlorine gas at the surface of the anode according to the following electrochemical reactions: Fe 2+ (aq) + 2e - ⁇ Fe 0 (s) (cathode, -) 2Cl - (aq) ⁇ Cl 2 (g) + 2e - (anode, +);
  • the wet chlorine gas evolved was recovered by suction using downstream a peristaltic pump (Masterflex US Digital Pump) with Viton tubing.
  • the chlorine gas was first cooled by passing it through an empty washing borosilicated glass bottle immersed into a ice bath, the mist and moisture content were then removed by passing the gas through several flasks filled with concentrated sulfuric acid (98 wt.% H 2 SO 4 ), and finally the dry and cold chlorine gas was totally absorbed into a saturated solution of potassium iodide (KI) liberating iodine according to the following reaction: Cl 2 (gas) + 3K + aq + 3I - aq ⁇ 3K + aq + I 3 - aq + 2Cl - aq
  • the anodic faradaic efficiency in chlorine was established at 78%.
  • the difference between the two current efficiencies (anode and cathode) is most probably due to some hydrogen evolution at the cathode and some oxygen evolution at the anode.
  • the anodic specific energy consumption at 500 A/m 2 was hence 2.45 kWh per kilogram of pure chlorine gas (i.e., 7.652 kWh per m 3 (NTP: 0°C, 101.325 kPa)).
  • Example 2b Electrolysis of the initial concentrated iron-rich metal chloride solution at pH 0.30 .
  • the iron-rich metal chloride concentrated solution from Example 1 was adjusted at a rather low pH of 0.30, so as to prevent an increase of pH above the precipitation pH of vanadium pentoxide at the cathode surface, but not too low however, so as not to favour the evolution of hydrogen. This was done by adding and circulating hydrochloric acid in the cathodic compartment of the electrolyser.
  • the electrolyser was identical to that described in Example 2a but this time the electrolysis was performed galvanostatically at a current density of 1000 A/m 2 . At that current density and low pH, the measured cell voltage was 2.865 V.
  • the wet chlorine gas evolved was recovered by the same method as that described in Example 2a.
  • the pure ammonium metavanadate was later calcined inside a porcelain boat in dry air at 400°C in a box furnace (Fisher Isotemp) to give off ammonia (NH 3 ) and water vapor (H 2 O), thereby yielding a red-orange powder of vanadium pentoxide.
  • the powder was then transferred into an Inconel crucible and melted at 700°C in air and the melt was cast onto a cool steel plate.
  • the resulting solidified black mass with a submetallic luster was then ground into a two disks vibratory cup mill with a hardmetal liner (Fritsch GmbH) using acetone as grinding aid and coolant.
  • the product thus obtained was technical grade vanadium pentoxide powder.
  • ferric chloride FeCl 3
  • FeCl 3 ferric chloride
  • Red brown hydrated vanadium (V) pentoxide starts to precipitate at about pH 1.8 while brown iron (III) hydroxide starts to precipitate at about pH 2.0.
  • brown iron (III) hydroxide starts to precipitate at about pH 2.0.
  • both species co-precipitate at pH 1.8 - 2.0.
  • the pH of the solution was raised by careful addition of a slurry of slacked magnesia (Mg(OH) 2 ) until the pH reached 2.0 but never above to avoid the precipitation of black mixed ferroso-ferric hydroxides.
  • Mg(OH) 2 magnesia
  • the complete co-precipitation of hydrated vanadium pentoxide (V 2 O 5 ⁇ 250H 2 O) and iron (III) hydroxide occurred in the form of a gelatinous red brown precipitate.
  • the coprecipitates were separated by filtration using a similar set-up to that described in Example 1.
  • the resulting filtrate was then acidified again to adjust pH close to 0.5 and stored into the jacketed reactor until the next electrolysis step.
  • the red-brown gelatinous filter cake was removed from the filter paper and digested into a warm caustic lye of sodium hydroxide (NaOH 50 wt.%). Upon cooling, both solution and sludge were poured into 250 mL centrifugation polypropylene bottles and centrifuged with a robust benchtop centrifuge (CL4 from Thermo Electron) at 10,000 revolutions per minute. The insoluble and dense gelatinous residue, mainly composed of iron hydroxide (Fe(OH) 3 ), was separated at the bottom, carefully washed with hot alkaline water (pH 10), centrifuged again and then discarded.
  • Fe(OH) 3 iron hydroxide
  • the solidified black mass with a submetallic luster was then ground into a two disks vibratory cup mill with a hardmetal liner (Fritsch GmbH) using acetone as grinding aid and coolant.
  • the product thus obtained was technical grade vanadium pentoxide powder containing some chromium, iron and manganese as major impurities.
  • Electrolysis of the vanadium-free iron rich solution from Example 4. The iron-rich metal chloride solution from which vanadium was removed during Example 4 was adjusted at a pH of 0.9 by adding minute amount of magnesia and circulated inside the cathodic compartment of an electrolyser. Its composition prior to electrolysis is presented in Table 4, last column. The electrolyser was identical to that described in examples 2a and 2b. The electrolysis was also performed galvanostatically at a current density of 200 A/m 2 . The operating temperature was 85°C and the volume flow rate of both catholyte and anolyte was 1 Umin. At that current density, the measured cell voltage was 1.85 V.
  • Electrolysis of the iron-rich metal chloride solution with a three compartment electrolyser was simply adjusted at a pH of 1.1 by adding minute amount of magnesia and then circulated inside the central compartment of an electrolyser.
  • the electrolyser consisted of a filter press design model MP cell from Electrocell AB (Sweden) with three compartments separated by an anion-exchange membrane (Excellion® I-100) and a cation exchange membrane (Excellion® I-200), both manufactured by SnowPure LLC.
  • the geometric electrode and membrane surface area was 100 cm 2 and the spacing between each electrode and the separator was 6 mm and also 6 mm between each membrane.
  • the cathodic compartment comprised a cathode plate made of a titanium palladium alloy (ASTM grade 7; Ti-0.15Pd) supplied by Titanium Industries. Prior to electrolysis the cathode was chemically etched by immersing it into a fluoro-nitric acid mixture (70 vol% conc. HNO 3 , 20 vol.% conc. HF and 10 vol.% H 2 O) and then rinsing it thoroughly with deionised water until no trace of acid remained.
  • a fluoro-nitric acid mixture 70 vol% conc. HNO 3 , 20 vol.% conc. HF and 10 vol.% H 2 O
  • the anodic compartment was equipped with a dimensionally stable anode (DSATM) supplied by Magneto BV (Netherlands) made of a plate of a titanium-palladium alloy substrate coated with a high loading of ruthenium dioxide (RuO 2 ) acting as electrocatalyst for promoting the evolution of chlorine (Ti-0.15Pd/RuO 2 ) .
  • DSATM dimensionally stable anode
  • RuO 2 ruthenium dioxide
  • the catholyte that circulated in loop within the cathodic compartment was an aqueous solution of 350 g/L iron (II) chloride and 300 g/L magnesium (II) chloride adjusted at a pH of 1.1, while the anolyte that circulated in loop within the anodic compartment consisted of an aqueous solution of 20 wt.% hydrochloric acid with 17 wt.% magnesium chloride (MgCl 2 ) and 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor the balance being deionised water.
  • MgCl 2 17 wt.% magnesium chloride
  • Fe 3+ ferric iron
  • the electrolysis was performed galvanostatically at a current density of 500 A/m 2 .
  • the operating temperature was 80°C and the volume flow rate of both catholyte, anolyte and initial solution was 1 L/min. At that current density, the measured overall cell voltage was 3.502 V.
  • ferrous cations from the iron-rich metal chloride solution crossed the Excellion® I-100 cation exchange membrane, and pure iron metal deposited at the cathode.
  • chloride anions migrated through the permeable anion exchange membrane towards the anodic compartment and discharged as chlorine gas at the surface of the anode.
  • Vanadium was also recovered by standard methods from the iron-depleted solution exiting the central compartment as follows. A stoechiometric amount of sodium chlorate (NaClO 3 ) was added to the iron-depleted solution to oxidize all the vanadium cations (V 4+ , V 5+ ) into pentavalent vanadium (V 5+ ) according to the reaction: 5VO 2+ + ClO 3 - + 2H 2 O ⁇ 5VO 2 + 0.5Cl 2 (g) + 4H +
  • the red brown precipitate was separated by filtration using a similar set-up to that described in Example 4.
  • the red-brown gelatinous filter cake was removed from the filter paper and dried into an oven and later calcined inside a porcelain boat in dry air at 400°C in a box furnace (Fisher Isotemp) the water vapour (H 2 O), thereby yielding a red-orange powder of vanadium pentoxide.
  • the powder was then transferred into an Inconel crucible, melted at 700°C in air and cast onto a cool steel plate.
  • the solidified black mass with a submetallic luster was then ground into a two disks vibratory cup mill with a hardmetal liner (Fritsch GmbH) using acetone as grinding aid and coolant.
  • the product thus obtained was technical grade vanadium pentoxide powder containing some chromium, iron and manganese as major impurities.
  • cathode material for conducting electrolysis in Examples 2a, 2b, 5 and 6 -
  • the selection of cathode material was conducted with an electrolyser and set-up identical to that used in Example 2a but with a synthetic catholyte circulating in loop and made of an aqueous solution of 350 g/L iron (II) chloride and 300 g/L magnesium (II) chloride adjusted at a pH of 1.1 while the anolyte that circulated in loop consisted of an aqueous solution of 20 wt.% hydrochloric acid with 17 wt.% magnesium chloride (MgCl 2 ) and 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor the balance being deionised water.
  • the electrolysis was performed galvanostatically at 80°C during two hours.
  • the polarization curves that is, the cell voltage vs. the current density were recorded for each cathode material.
  • the materials tested were a titanium-palladium alloy ASTM grade 7 (Ti-0.15Pd) from Titanium Industries, Zircadyne® 702 from Wah Chang, austenitic stainless steel AISI grade 316L, aluminum grade 6061 T6 and pure copper. As expected, only titanium and zirconium allowed the easy stripping of the iron deposit.
  • the polarization curves are presented in Figure11 .
  • the selection of the anion exchange membrane was conducted with an electrolyser and set-up identical to that used in Example 2a.
  • the synthetic catholyte circulating in loop in the cathodic compartment was made of an aqueous solution of 350 g/L iron (II) chloride and 300 g/L magnesium (II) chloride adjusted at a pH of 1.1 while the anolyte that circulated in loop in the anodic compartment consisted of an aqueous solution of 20 wt.% hydrochloric acid with 17 wt.% magnesium chloride (MgCl 2 ) and 10,000 ppm of ferric iron (Fe 3+ ) as corrosion inhibitor, the balance being deionised water.
  • the electrolysis was performed galvanostatically at 80°C during two hours.
  • the polarization curves that is, the cell voltage vs. the current density were recorded for each anion exchange membrane.
  • the membranes tested were a Excellion® I-100 (SnowPure LLC), Neosepta® AMH, ACM, and AHA (Tokuyama Co. Ltd. - Eurodia), Selemion (Asahi Glass) and Ultrex® AMI-7001 (Membrane International).
  • the polarization curves are presented in Figure 12 .
  • Fe(III) as a corrosion inhibitor.
  • the electrolysis was performed galvanostatically at 80°C during two hours.
  • the polarization curves that is, the cell voltage vs. the current density were recorded for each anolyte composition.
  • the polarization curves are presented in Figure13 .

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Abstract

L'invention concerne un procédé électrochimique pour la récupération simultanée de fer métallique et de chlore gazeux à partir d'une solution de chlorure métallique riche en fer, comprenant l'électrolyse de la solution de chlorure métallique riche en fer dans un électrolyseur comprenant un compartiment cathodique équipé d'une cathode ayant une surtension d'hydrogène supérieure à celle du fer et contenant un catholyte ayant un pH inférieur à environ 2, un compartiment anodique équipé d'une anode et contenant un anolyte, et un séparateur permettant le passage d'anions, l'étape d'électrolyse comprenant la mise en circulation de la solution de chlorure métallique riche en fer dans un compartiment non anodique de l'électrolyseur, ce qui entraîne le dépôt électrolytique du fer sur la cathode et l'émission de chlore gazeux à l'anode, et laisse une solution appauvrie en fer. La solution de chlorure métallique riche en fer peut provenir de déchets de carbo-chloration, de liqueurs de lixiviation acides usées ou de liqueurs de décapage.

Claims (15)

  1. Procédé électrochimique permettant de récupérer du fer métallique et du chlore gazeux à partir d'une solution de chlorures métalliques riche en fer, lequel procédé comporte les étapes suivantes :
    a) préparer une solution de chlorures métalliques riche en fer ;
    b) réaliser l'électrolyse de cette solution de chlorures métalliques riche en fer, dans un électrolyseur qui comporte un compartiment cathodique équipé d'une cathode dont la surtension hydrogène est supérieure à celle du fer et contenant un catholyte dont le pH est inférieur à 2, un compartiment anodique équipé d'une anode et contenant un anolyte, et un séparateur qui laisse passer les anions, laquelle étape d'électrolyse comprend le fait de faire circuler ladite solution de chlorures métalliques riche en fer dans un compartiment non-anodique dudit électrolyseur, ce qui provoque la formation par électrolyse d'un dépôt de fer au niveau de la cathode et un dégagement de chlore gazeux au niveau de l'anode et laisse une solution appauvrie en fer ;
    c) et récupérer séparément ledit fer déposé par électrolyse et ledit chlore gazeux.
  2. Procédé électrochimique conforme à la revendication 1, dans lequel l'étape (a) de préparation d'une solution de chlorures métalliques riche en fer comporte les étapes suivantes :
    al) lessiver un rebut solide de carbochloration avec une solution aqueuse chaude, ce qui donne une suspension aqueuse ;
    a2) et soumettre cette suspension aqueuse à une opération de séparation des solides, ce qui donne un gâteau de matières insolubles et permet d'isoler une solution de chlorures métalliques riche en fer, laquelle opération de séparation des solides est de préférence réalisée selon un procédé physique de séparation, et de préférence par décantation, filtration ou centrifugation.
  3. Procédé électrochimique conforme à la revendication 1 ou 2, dans lequel le pH de la solution de chlorures métalliques riche en fer et le pH du catholyte sont ajustés dans l'intervalle allant de 0,3 à 1,8.
  4. Procédé électrochimique conforme à l'une des revendications 1 à 3, dans lequel la cathode présente, à 200 A/m2 et dans une solution à 0,5 mol/L de HCl à 25 °C, une surtension supérieure à 425 mV.
  5. Procédé électrochimique conforme à la revendication 4, dans lequel la cathode est faite ou revêtue d'un matériau choisi dans l'ensemble formé par les suivants : titane et alliages de titane, zirconium et alliages de zirconium, zinc et alliages de zinc, cadmium et alliages de cadmium, étain et alliages d'étain, cuivre et alliages de cuivre, plomb et alliages de plomb, niobium et alliages de niobium, or et alliages d'or, mercure et amalgames métalliques à base de mercure.
  6. Procédé électrochimique conforme à l'une des revendications 1 à 5, dans lequel ledit anolyte contient du chlorure d'hydrogène HCl, un sel choisi parmi les chlorures MgCl2, NaCl, LiCl, KCl et CaCl2 et leurs mélanges, et du fer trivalent Fe(III) comme inhibiteur de corrosion.
  7. Procédé électrochimique conforme à l'une des revendications 1 à 6, dans lequel l'anode est une anode stable en dimension, du type [M/MxOy-AzOt] où M représente un métal réfractaire ou un alliage à effet de valve, comprenant du titane ou un alliage de titane, du zirconium ou
    un alliage de zirconium, du hafnium ou un alliage de hafnium, du vanadium ou un alliage de vanadium, du niobium ou un alliage de niobium, ou du tantale ou un alliage de tantale, MxOy représente un oxyde d'un métal-valve formant une mince couche imperméable qui protège le métal de base, comprenant de l'oxyde TiO2, ZrO2, HfO2, NbO2, Nb2O5, TaO2 ou Ta2O5, et AzOt représente un oxyde électrocatalytique d'un métal noble, un oxyde d'un métal de la mine de platine, comprenant RuO2, IrO2 ou PtOx, ou un oxyde métallique comprenant SnO2, Sb2O5 ou Bi2O3.
  8. Procédé électrochimique conforme à l'une des revendications 1 à 7, dans lequel l'étape d'électrolyse est réalisée dans un électrolyseur à deux compartiments dans lequel le séparateur est une membrane échangeuse d'ions.
  9. Procédé électrochimique conforme à la revendication 8, dans lequel on fait circuler en boucle, à l'intérieur du compartiment cathodique de l'électrolyseur, ladite solution de chlorures métalliques riche en fer qui joue ainsi le rôle de catholyte.
  10. Procédé électrochimique conforme à l'une des revendications 1 à 6, dans lequel l'étape d'électrolyse est réalisée dans un électrolyseur à trois compartiments dans lequel les compartiments anodique et cathodique sont séparés d'un compartiment central, respectivement, par une membrane échangeuse d'anions et par une membrane échangeuse de cations, et dans lequel la solution de chlorures métalliques riche en fer se trouve à l'intérieur du compartiment central de l'électrolyseur.
  11. Procédé électrochimique conforme à la revendication 10, dans lequel le catholyte contient 1 à 450 g/L de chlorure de fer-II, 1 à 350 g/L de chlorure de magnésium MgCl2 ou de chlorure de calcium CaCl2 ou d'un mélange de ceux-ci, et 0 à 10 g/L de chlorure d'hydrogène HCl libre.
  12. Procédé électrochimique conforme à l'une des revendications 1 à 11, dans lequel l'étape d'électrolyse est effectuée à courant constant, avec une densité de courant qui vaut de 50 à 5000 A/m2, ou bien de 50 à 1000 A/m2, ce qui permet d'obtenir un dépôt de fer lisse et pratiquement dépourvu de dendrites, ou encore de 3000 à 5000 A/m2 ce qui permet d'obtenir du fer qui est essentiellement à l'état pulvérulent.
  13. Procédé électrochimique conforme à l'une des revendications 1 à 12, dans lequel l'étape d'électrolyse est réalisée à une température opératoire valant de 40 à 110 °C.
  14. Procédé électrochimique conforme à la revendication 1, dans lequel la solution de chlorures métalliques riche en fer provient de rebuts de carbochloration, de liquides de lessivage à l'acide épuisés, ou de liquides de décapage.
  15. Procédé électrochimique conforme à l'une des revendications 1 à 14, dans lequel, dans l'étape (c), on récupère le fer en enlevant, par un moyen physique, ledit fer déposé sur la cathode par électrolyse, et l'on récupère le chlore en aspirant le chlore gazeux au-dessus du compartiment anodique.
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CN105132936A (zh) * 2015-07-07 2015-12-09 昆明理工大学 一种用熔盐电解法从钛铁矿中制备CaTiO3粉末的方法
CN105132936B (zh) * 2015-07-07 2017-12-22 昆明理工大学 一种用熔盐电解法从钛铁矿中制备CaTiO3粉末的方法

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AU2007299519B2 (en) 2011-12-15
AU2007299519A1 (en) 2008-03-27
EP2064369A1 (fr) 2009-06-03
JP2010504423A (ja) 2010-02-12
EP2064369A4 (fr) 2009-11-04
US20100044243A1 (en) 2010-02-25
ZA200900950B (en) 2009-12-30
CA2663652C (fr) 2010-07-06
WO2008034212A1 (fr) 2008-03-27

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