WO2019057431A1 - Production électrochimique sans co2 de métaux et d'alliages correspondants - Google Patents

Production électrochimique sans co2 de métaux et d'alliages correspondants Download PDF

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Publication number
WO2019057431A1
WO2019057431A1 PCT/EP2018/072640 EP2018072640W WO2019057431A1 WO 2019057431 A1 WO2019057431 A1 WO 2019057431A1 EP 2018072640 W EP2018072640 W EP 2018072640W WO 2019057431 A1 WO2019057431 A1 WO 2019057431A1
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metal
compound
anode
cathode
metals
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PCT/EP2018/072640
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German (de)
English (en)
Inventor
Günter Schmid
Bernhard Schmid
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Siemens Aktiengesellschaft
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Publication of WO2019057431A1 publication Critical patent/WO2019057431A1/fr

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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
    • 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
    • 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
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • 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

Definitions

  • the present invention relates to a method for the manufacture ⁇ lung of a metal M and / or a mixture and / or alloy thereof in an electrolytic cell comprising at least one anode and at least one cathode, wherein a compound of the metal M, and optionally at least one further compound ei ⁇ nes alloying ingredient is converted into an aqueous solution and the metal M and / or a mixture and / or alloy coins ⁇ tion of which is electrochemically deposited on the at least one cathode.
  • x is usually chosen in stoichiometric formulas such that x is itself and (x * n) / 2 is an integer.
  • x can be arbitrary.
  • oxides with mixed oxidation states generally formula, for example, M 3 O 4 or M 4 O 3
  • metals metallurgy as Fe, Ni, Co or Le ⁇ g réellesmetalle as W, Mn, V, Cr be industrially produced in blast furnace processes with fossil fuels such as coal. In this smelting significant amounts of CO 2 are emitted into the atmosphere.
  • the iron or metal production by blast furnace processes is responsible for an average emission of 1.8 - 2 t CO 2 per ton of crude steel (Brazil: 1.25 t C0 2 / t steel, US: 2.9 t C0 2 / t steel; Korea and Mexico: 1.6 t C0 2 / t steel, China and India: 3.1 to 3.8 t C0 2 / t steel). This adds up to 6.7% of global CO 2 emissions.
  • Global crude steel production in 2015 was 1,623 million tons per year. With a current crude steel price of 583 C / t (Jan. 2017), this means a market volume of 954 billion C.
  • the most important method is the smelting of metallic oxides in the blast furnace with carbon from coke or carbon monoxide, e.g. for Fe or steel.
  • alkali metals such as lithium, sodium, potassium or alkaline earth metals such as beryllium, calcium, magnesium, strontium or barium.
  • alkali metals such as lithium, sodium, potassium or alkaline earth metals such as beryllium, calcium, magnesium, strontium or barium.
  • aluminum The best known and most significant metal is aluminum.
  • Newer methods also use sodium.
  • these metals can also be prepared electrochemically for the production of metal, but this process is more complex and therefore not included according to the invention.
  • Metals such as aluminum or else lithium can also be deposited from non-aqueous conductive solutions of their salts, for example halides.
  • Examples include aluminum from ionic liquids or lithium
  • the inventors have developed an efficient electrolysis process in which anode current is used directly or indirectly to dissolve a compound of a metal M selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se or Te and / or a mixture and / or an alloy thereof, is then used to cathodically deposited in the electrolytic cell can be.
  • a metal M selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se or Te and / or a mixture and / or an alloy thereof
  • the present invention relates to a process for the preparation of a metal M which is selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Cd, Ga, In, T1, Ge, Sn, Pb, As, Sb, Bi, Se or Te and / or a mixture and / or alloy thereof, in an electrolytic cell comprising at least one anode and at least one cathode, wherein a compound of the metal M and optionally at least one further compound of an alloying constituent in an aqueous solution is transferred and the metal M and / or a mixture and / or alloy thereof is electrochemically deposited on the at least one cathode, said at least one anode comprising the compound of the metal M, preferably in the We ⁇ sentlichen from the at least is a compound of the metal M, and at least one compound of the metal M electrochemically an anode is at least transferred to an aqueous solution and / or wherein at least one Ver
  • FIG. 1 shows schematically the steps of a first embodiment of the method according to the invention.
  • FIG. 2 shows in more detail the processes at a cathode K and an anode A of the first embodiment of the method according to the invention.
  • FIG. 3 shows schematically the steps of a second embodiment of the method according to the invention.
  • FIGS. 4 and 5 show in more detail the processes at a cathode K and an anode A and at a release of a compound of the metal M in two different modes of operation of the second embodiment of the method according to the invention.
  • the present invention relates to a method for producing a metal M (which also includes semimetals as metals) selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co , Ni, Cu, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se and Te and / or a mixture and / or alloy thereof in an electrolytic cell comprising at least one anode and at least one Cathode, wherein a compound of the metal M and optionally at least one further compound of an alloying component is converted into an aqueous solution and the metal M and / or a mixture and / or alloy thereof is electrochemically deposited on the at least one cathode, wherein the at least one anode comprises the compound of the metal M, preferably essentially consisting of the at least one compound of the metal M, and min ⁇ least one compound of metal M is electrochemically converted at the at least one anode in an aqueous solution and /
  • the metal here is selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, As, Sb, Bi, Se and / or Te and / or a mixture and / or alloy thereof, wherein here no precious metals, ie Au, Ag, Hg, Pd, Pt, Rh, Ir, Ru and Os are included, wherein here in ⁇ particular the metals of the metallurgy, Fe, Ni, Co, Legie ⁇ approximately metals such as W, Mn, V, Cr, bearing metals such as Sb, Bi or corrosion protection coatings are such as Zn of economic importance ⁇ processing and correspondingly cost-efficiently by the inventive procedural ⁇ ren and can be easily made.
  • the lower limit forms the side reaction of water ⁇ material forming the respective pH.
  • E H2 E H ° 2 + - ln ⁇ - 2 2 z ⁇ F a H2
  • the metal M is therefore selected from Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Cd, Ga, In, Sn, Pb, Se and / or Te and / or a mixture and / or alloy thereof.
  • the metal is selected from metals which are not prone to passivation in the process according to the invention, in particular Mn, Fe, Co, Ni, Cd, Ga, In, Sn, Se and / or Te and / or a mixture and / or or alloy thereof.
  • the metal M is selected from Mn, Fe, Co and / or Ni and / or a mixture and / or alloy thereof.
  • the metal M is iron and / or an alloy thereof.
  • the alloys of the said metals are not particularly limited and may, for example, by additions of metals or metal cations, carbon, such as graphite, etc., are ⁇ ge gained using, for example with additives of metal cations in the present method directly ⁇ mixtures of metals can be recovered at the cathode. It is also not excluded that mixtures of compounds of the metals M, wherein more than one metal M is present, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more metals M, in erfindungsge ⁇ MAESSEN Procedures used to make multiple metal cations to convert into an aqueous solution, which can then be sequenti ⁇ ell or simultaneously, for example, sequentially deposited on one or ver ⁇ different sequentially introduced cathodes.
  • Table 1 Exemplary electrode potentials compared to the standard hydrogen electrode under normal conditions (Excerpt from Wikipedia:
  • the electrochemically deposited metals in the process according to the invention for example in electric (regenerative) heated arc furnace, alloyed or further processed with the addition of carbon, etc.
  • the inventive method takes place in an electrolysis ⁇ cell, which is not particularly limited, and which at least one anode and at least one cathode comprises.
  • the material of the electrolytic cell itself as well as the material of the cathode and anode can be adapted to the metal M and / or the compound of the metal M and / or one or more existing electrolytes.
  • the anode, cathode and the electrolyte will now be described more exactly he ⁇ . It should be noted that the fiction, ⁇ proper procedure takes place in aqueous solution, so it is not a fused-salt electrolysis.
  • the compound of the metal M is not particularly limited insofar as it contains the metal M in a form which can be converted into an aqueous solution, that is, can release a metal cation. It may be present, for example, in the form of a salt or a covalent compound, for example in salt form.
  • the compound of the metal M may be present as ore of one or more metals, but also as roasted metal scrap or metal scrap itself, etc. Also mixed compounds of several metals M are possible. In this case, it is not excluded that a counterion of a metal cation is redeposited in the transfer into an aqueous solution in this, wherein the counterion but preferably also goes into solution. If necessary, this counterion can also continue to react.
  • the compound of the metal M for example, ores, foreign metals may be contained, which can be deposited either before or during the electrodeposition. Before deposition, according to certain embodiments, the compounds of the metal M can be converted into a solution, for example salt solutions, and the solutions
  • alkaline earth metals can be separated as sparingly soluble sulfates already in the workup, so that, for example, a use of sulfates and / or sulfuric acid in the electrolysis, for example in the electrolyte, for example in the anolyte and / or catholyte, may be advantageous if Erd ⁇ alkali metals in the compound of the metal M are present.
  • the electrolyte can thus also be adapted in the process according to the invention, for example with regard to counterions (anions) in the preparation of the metal M.
  • the compound of the metal M is hardly or not soluble in water, eg has a solubility in water at 25 ° C and normal pressure of less than 10 g / L, preferably less than 1 g / L, further be - preferably less than 0.1 g / L.
  • the anode may comprise or consist of the compound of the metal M.
  • the compound of the metal M includes an oxide and / or sulfide, or comprises an oxide and / or sulfide of the metal M.
  • This may be a ⁇ polysubstituted by reaction in an aqueous solution are transferred, for example by reaction at the Anode or with min ⁇ least one anodically prepared compound.
  • these are easily accessible and can be easily processed into an anode.
  • the metals M are most of the usual ⁇ as before due to their normal potential in nature as oxides or sulphides.
  • these example ⁇ example, in the second embodiment for example by means of anodically prepared acids, such as acids whose anion can not be oxidized electrochemically at the anode, be solved.
  • An example of this is the use of sulfuric acid with the particularly preferred element iron as metal M.
  • An oxide of iron can be present in the oxidation state +2 or +3. eg oxidation state +3: Fe 2 0 3 + H 2 S0 4 - * Fe 2 (S0 4 ) 3 + H 2 0
  • the acid produced is not particularly limited, and it is also sufficient if proton or hydroxonium ions are prepared at an anode, which are used for producing an acid, for example, in a water electrolysis.
  • H 2 0 - 2e " -> H 0 2 + 2 H +
  • an acid can also be "generated” directly at the anode and react with the compound of the metal M or led out of the electrolysis cell to carry out a solution of the compound of the metal M at a location outside the electrolytic cell and then Metal ⁇ cations lead to the electrolysis cell
  • This also includes a concentration of an acid by, for example, this is concentrated higher by a water electrolysis.
  • acids in addition to sulfuric acid and HF, KHF 2 , CF 3 -S0 2 -OH, etc. into consideration.
  • sulfuric acid it is thus also possible to use other acids for breaking down the compound of the metal M.
  • fluoride ions usually form stable nega tive ⁇ charged complex ions with multivalent ions, for example, iron, aluminum, cobalt or titanium and are DA very suitable for the digestion oxidic ores forth.
  • multivalent ions for example, iron, aluminum, cobalt or titanium
  • sulfuric acid you are usually not oxidized at the anode in a process according to the invention, but concentrated.
  • halogen-hydrogen acids may also be considered. Unlike the previously mentioned their anions can be oxidized to the corresponding halo, which in turn are used as anodically generated connections to shed Kings ⁇ nen.
  • the compound of the metal M thus comprises or consists of a sulfide.
  • sulfuric acid which "set forth ⁇ " anodically, that is, for example, concentrated further, can be for example, iron in the oxidation state +2.:
  • An H 2 S gas burner would be in this case also much easier to construct and operate as for example a "roast burner" with solid "fuels”.
  • the anode consist be or the anode even in Wesentli ⁇ chen or total of the compound of the metal M, so that the anode is as it were dissolved in the electrolysis by an anodic reaction and the metal cations M in the electrolyte, for example the anolyte - or in general but in the only one electrolyte, for example, if no membrane and no diaphragm are present transition.
  • a dissolution of at least one compound of the metal M for example M x Y y , as shown in FIG.
  • step 2 is carried out at an anode so that a metal cation M Y + is in aqueous solution ,
  • This metal cation wanders in step 2 to Katho ⁇ de, and there is deposited in step 3 as metal M at the cathode.
  • Darge ⁇ represents by arrows for an abstract electrolysis cell in Figure 2, wherein the compound M x Y y is converted into an aqueous solution at the anode A, the metal cation M Y + to Ka ⁇ Thode K migrates and there as the metal M is deposited in the deposition 10 in the form of a cathode.
  • the deposition takes place here during the electrolysis by reduction of the metal ⁇ cation by means of a power source, not shown.
  • Y x + represents a suitable represents the counterion of the cation M Y + in the compound of the metal M, which is not restricted, and x and y each denote the valency of the counterion and the metal cation, where x and y are positive, preferably integer, numbers.
  • At least one compound of metal M may be also achieved by an anode prepared in the electrolysis cell compound, said Herge ⁇ presented at the anode compound is not particularly limited insofar as it can dissolve at least one compound of the metal M.
  • the location of the solution of the at least one compound of the metal M is not limited in this case, and a solution may take place inside the electrolytic cell by, for example, introducing the at least one compound of the metal M into the electrolytic cell, for example, an anode compartment, or by reacting the compound produced at the anode is brought outside the electrolytic cell for at least ei ⁇ NEN compound of the metal M is pumped, for example, through a pipe there, etc., and dissolved therein so that the compound of the metal M then in an aqueous Lö ⁇ solution is transferred, which in turn is then introduced into the electrolysis ⁇ cell, for example, to a catholyte.
  • step 1 of FIG. 1 is replaced by steps la, lb and lc, in which case steps 2 and 3 correspond to those of FIG. Step 1 of Figure 1 is divided in accordance with sub-steps, which then, however, again providing the metal cation in the result, which is then redu in Step 3 ⁇ for using movements in step 2.
  • step la of FIG. 3 the production of a compound Z takes place, which can optionally be converted into a compound Z *.
  • step 1b The compound Z or the compound Z * is then used in step 1b for dissolving the compound of the metal M, for example M x Y y , so that once again a metal cation M Y + goes into aqueous solution, which ches then in step lc to migrate to the cathode tediousge ⁇ represents is, either in the electrolytic cell is ceremoniesge ⁇ represents or is introduced into the electrolytic cell, then the required solution of the compound of the metal M outside the electrolytic cell.
  • these processes are through
  • the compound Z for example chlorine
  • the compound M x Y y is used directly for dissolving the compound M x Y y , so that these are in an aqueous solution is transferred, during which * is converted into a compound Z, a compound Z, for example an acid or also a H + ion produced in Fi ⁇ gur 5, such as sulfuric acid, the x for releasing the Verbin ⁇ dung M Y y is used.
  • the ions of the metal M to be deposited may under certain circumstances be strong so-called cation acids, for example for Fe 3+ in, for example, Fe 2 (S0 4 ) 3, owing to their high Lewis acidity.
  • the metal cation M Y + again travels to the cathode K analogously to FIG. 2, where it is deposited as a precipitate 10.
  • the "compounds" Z and Z * are not particularly limited, although here they are exemplified as chlorine and
  • a direct anodic Include oxidation of the metal in certain cases, a direct anodic Include oxidation of the metal.
  • the oxidation state of the metal in the anode need not match that of the metal ion dissolved.
  • the smelting of siderite ore (FeCOs) can be cited. eg.
  • the cathode is not particularly limited insofar as the metal M can be deposited thereon. It can be provided in any form, for example as a solid electrode and / or electrode sheet, porous electrode, etc. and in any form auftre ⁇ th, for example, as a strip, pen, cylinder, etc. Gas ⁇ diffusion electrodes are not necessary here erfindungsge ⁇ Gurss but also not excluded.
  • the cathode - as well as the anode and also the entire electrolysis cell or the electrolyzer can also be constructed in plate design or concentric. For example, with rotating cathodes with scrapers for the metal, a concentric design may be advantageous.
  • the cathode can be either inside or outside.
  • the at least ei ⁇ ne cathode, the metal M is, for example, coated with the metal M, or consists essentially of the metal M.
  • the overvoltage of the deposition can be reduced to 0 as soon as the Electrode consists of the metal to be deposited itself.
  • the cathode can be made of the metal M, for example, if this has a good conductivity.
  • the metal M is removed from the at least one cathode continuously or discontinuously after the electrochemical deposition.
  • the at least one cathode is preferably changed or stripped Me ⁇ tall M of the at least one cathode.
  • the anode is not particularly limited, and indeed any anode material can be used here in the second execution ⁇ form which is usable for preparing a compound for releasing the connection of the metal M.
  • the at least ei ⁇ ne anode at least one compound of the metal M or be ⁇ is the at least one anode essentially of at least one compound of the metal M, as shown in the first embodiment. 100% by weight of the Verbin ⁇ dung of the metal M, for example, one or more ores of the metal M, or mixtures thereof: -
  • the anode comprises a share of 20.
  • Suitable additives are, for example, graphite and / or binder, the binder not being limited.
  • metal scrap can also be added or used directly, and consequently, for the processing of scrap, it can, for example, also be quite complete
  • the anode comprises a
  • the at least one anode can For example, consist of a combination of iron, such as iron ore.
  • At least one membrane and / or at least one diaphragm may be provided in the electrolysis cell, so that, for example, an existing one
  • Catholyte can be divided on the cathode side, or it can also be provided no membrane and no diaphragm, so that only one electrolyte is present.
  • a cation-conducting membrane may be vorgese ⁇ hen, which is not particularly limited.
  • the charge compensation process of the invention during electrolysis can take place mainly through cations which migrate from the anode side to the cathode side, ie for example via the metal cations, such as for those shown in Figu ⁇ ren 1 to 5 embodiments.
  • sulfuric acid protons for charge transport for example, contribute ⁇ .
  • chloride-containing compounds such as HCl or NaCl can be used in the electrolyte, which then allows a chlorine production, which provides further synergies. The coupling of chlorine production with metal production will be considered separately below.
  • proton-conducting membranes can be used, game, when the compound of the metal M is not dissolved in the electrolytic cell at ⁇ but outside by an anodic connection made, and for example, the Lö ⁇ solution, which then contains metal cations, then in the cathode denraum to Deposition of the metal M is introduced. This is indicated for example in Figures 3 to 5, so the Ver ⁇ bond of the metal M is not present in the electrolysis cell. 2. It is also possible to use an anion-conducting membrane, which is also not particularly limited.
  • Anion candidatesde membranes can then, for example, in addition to hydroxide ions also other ions such as hydrogen carbonate, fluoride or sulfate hydrogen sulfate lead, in which case the compound of the metal M outside of the electrolytic cell ge ⁇ triggers and the solution is introduced including metal cations in the Ka ⁇ method space, such as this is indicated, for example, in FIGS. 3 to 5, so that the connection of the metal M is not present in the electrolysis cell.
  • the catholyte is preferably fluoride- or sulphate-containing, an enrichment of HF or sulfuric acid in the anolyte may also take place in this way.
  • a diaphragm may be provided in the electrolysis cell, which is also not particularly limited.
  • a gas separation into catholyte and anolyte Dia ⁇ Phragmén of polymer (Polysulfone) or inorganic materials (zirconia or Zirkoniumphoshat) or with orgasmic ⁇ African polymeric materials filled polymers for example in a water electrolysis, where anodic oxygen is produced, or in an anodic production of chlorine.
  • the electrical ionic conductivity include both cationic and anionic conductivity and are therefore also suitable for the migration of metal cations, so that they can be used when using an anode comprising the compound of the metal M, as shown in FIGS. 1 and 2.
  • the embodiment schematically shown in Figures 3 to 5 is possible.
  • the anode and / or cathode may rest against the diaphragm or the membrane or not, so that an electrolyte gap may or may not be present.
  • the design of the electrolyzer can be adapted to the particular metal or Güns ⁇ tigsten operation.
  • an acid for example sulfuric acid
  • types of electrolytes with or without electrolyte gaps on the anode side are conceivable.
  • electrolyte gap on the cathode side is advantageous.
  • the electrodes such as a cathode could be persuaded away ⁇ ran from a Memb or a diaphragm according to the deposition rate of the metal M.
  • the anode however, an electrolyte gap can be anode-side form, this was not present at the start.
  • an electrolyte in the electrolytic cell is not particularly limited insofar as it is aqueous at least on the anode side. It can be provided an electrolyte for the entire electrolysis cell, for example ⁇ in a mode without membrane and without diaphragm. If a diaphragm and / or a membrane is present, the electrolyte can be divided at least into the anolyte on the anode side and the catholyte on the cathode side, with the anolyte and catholyte then being the same or different.
  • the catholyte is then not particularly limited.
  • the ions of the metal M can form the strong themselves due to their high Lewis acidity so-called ⁇ cation acids under certain circumstances, such as for example Fe 3+ in Fe 2 (S0 4) 3: Fe 3+ + 6H 2 0 ⁇ "H + " + [Fe (OH) (H 2 O) 5 ] 2+
  • pH-adjusting additives it may be necessary to add pH-adjusting additives to the catholyte to avoid the undesirable formation of hydrogen at the cathode. Care should be taken here that such an additive can not be converted cathodically and preferably neither cathodically nor anodically, and in particular at the same time does not impair the solubility of the metal M to be deposited, for example by precipitation of metal cations.
  • pH-regulating additives are preferably weakly basic salts having a pH of more than 7 to less than 10 when dissolved in water, which in particular simultaneously increase the electrical conductivity of the electrolyte.
  • borates or fluorides may be mentioned, in particular of alkali metals or of the metal M itself, but this depends on the solubility of the entspre ⁇ sponding weakly basic salt of the metal M in a watery solution can.
  • the first two would be unsuitable due to the formation of sparingly soluble salts, so that preferably fluorides can be added here.
  • the use of borates is again easily possible.
  • Analogous considerations for the other metals M are familiar to the expert, so that the
  • a catholyte at the cathode of at least one weakly basic salts, and in particular ⁇ sondere fluorides, carbonates and / or borates, preferably Fluo ⁇ ride and / or borates are added.
  • one or more conductive salts can be added to the catholyte to improve the conductivity, for example a solution of a - second - compound of the metal M, for example a salt.
  • This may, for example, correspond to a salt which, upon release of the - first - compound of the measurement
  • Talls M corresponds, for example, a sulfate at a Lö ⁇ sen with sulfuric acid, or a chloride when dissolved with chlorine or HCl, or a fluoride when dissolved with HF or KHF.
  • compounds may be added to the catholyte, which are needed for the production of an alloy, for example chromium salts, if chromium steel is to be produced, etc.
  • a catholyte at the at least one cathode consists of an aqueous solution of a - second - compound of the metal M and optionally at least ei ⁇ ner further compound of an alloying component and optionally one or more weakly basic salts.
  • the - second - compound of the metal M in the aqueous solution is preferred in this ⁇ Lö from the - first - metal compound, which is converted into an aqueous solution, ver ⁇ eliminated.
  • water is removed from a catholyte at the at least one cathode. This can then be maintained the conductivity when the metal cations are deposited.
  • the method by which the water is withdrawn is not particularly limited, and includes, for example, evaporation, drying with a suitable desiccant, etc.
  • an anolyte is then not particularly limited. This can be adapted to the anode reaction and / or the compound of the metal M, which can additionally be optionally egg ⁇ ne adjustment to the effect here, too, whether the compound of the metal M included in the anode is present in the anode compartment or outside ,
  • a kla ⁇ acid preferably sulfuric acid, or a halide-containing (in particular chloride, bromide or iodide-containing), forthcoming added to chloride-containing compound used. With these, a dissolution of the connection of the metal M can be supported or a means for releasing the connection of the metal M can be provided.
  • a halogen preferably chlorine, sulfur and / or an acid, for example sulfur ⁇ acid is produced by oxidation of water, anodic.
  • the production of an acid here comprises the anodic production of protons and the subsequent production of an acid.
  • the process according to the invention preferably in aqueous media, can be carried out at temperatures below 120 ° C., preferably below 100 ° C., for example below 80 ° C.
  • This temperature is significantly reduced, in particular compared to the blast furnace temperature, so that here is a saving of energy, in particular ⁇ special of waste heat, clearly.
  • the invention it is also possible to perform several invention shown SSE process in successive electrolytic cells, for example when more than one metal M, for example, a mixed ore or electrical, to be separated off from a compound of the metal M, which has more metals M, wherein the resolution can then take place, for example, at an anode and / or with an anodically produced compound, but the deposition of the metals M can then take place at different cathodes, for example by selecting the corresponding cell voltages accordingly.
  • a solution of the metal M which then contains more metal cations for an Abschei ⁇ extension of a first metal M, may then be placed in a more suitable electrolytic cell, or it may be exchanged in the cathode of an electrolytic cell, etc.
  • the electrolysis process can then proceed, for example, as follows:
  • the cathode chamber is continuously deposited, the solution of the salt of the metal M, which is anodically or au ⁇ ßerrenz the anode compartment of the mixture with sulfuric acid it ⁇ testifies added and deposited by electrolysis on the cathode.
  • the deposited at the cathode metal eg iron, cobalt, nickel and / or manganese
  • the cathodes preferably consist of or are coated with the metal to be deposited, thereby limiting the overvoltage of the deposition to the diffusion overvoltage.
  • Sulfuric acid is used as anolyte in this exemplary embodiment, as described above, since it concentrates rather than dilutes during electrolysis.
  • the concurrent evolution of hydrogen should be minimized.
  • This can be ensured by suitable choice of the cathode, as also described above.
  • the addition of metal salt solution as in a chlor-alkali electrolysis via the anode compartment SUC ⁇ gene could, as the metal cations be generated outside of the anode chamber, but also the metal cations by dissolving an anode comprising the compound of the metal M, here ⁇ can be made.
  • polyvalent cations be ⁇ but because is difficult by a cation-conducting membrane or even block them, so this is not preferred.
  • the use of a diaphragm can also remedy the situation.
  • the operation shown here includes the Regenera ⁇ tion and even concentration of the anolyte during the electrolysis process.
  • oxygen- ⁇ -producing anode reactions such as a
  • Chlorine production which is shown below in a second exemplary embodiment. This is preferred, but other halogens such as bromine or iodine can also be produced.
  • the chlorides of the metal M can be very well electrolyzed due to their good solubility and thus high conductivity of the electrolyte.
  • the halogen can in
  • the metal chlorides are electrolyzed and recovered the pure metals, wherein the electrolyte can be continuously fed metal chloride.
  • the resulting chlorine can the release process, for example the roasting may be performed again to ⁇ .
  • Another exemplary, third embodiment without membrane represents an arrangement where the iron ore is in the immediate vicinity of the anode and anodic acid is generated.
  • the protons produced in aqueous media thereby solve the ore (for example, an oxide) and provide for a continu ous ⁇ replenishment of metal ions which can be decorated at the cathode reduced.
  • the acid formation is stoichiometric, so as much metal goes exactly in solution, as deposited at the Katho ⁇ de.
  • the system can be operated continuously.
  • iron ore comprising iron oxide and iron sulfide is dissolved in various oxidation states either as an anode material or in an anode space by means of protons or oxonium ions produced in a water electrolysis, or generally with acid.
  • iron carbonate ⁇ th can be:
  • Iron ores here have a conductivity that comes close to that of graphite, which makes the process even more attractive here.
  • the anode can in this case for example, from 20 - 100 weight% consist egg ⁇ senerzen, wherein for example, graphite may be added ⁇ beat..
  • the iron ions anodically produced can then be deposited on an iron cathode as the iron and this perio ⁇ disch removed or stripped.
  • the illustrated cathode reaction can also be coupled with various anode reactions, for example for the production of acid. be pelt so that also various ores can be processed easily.
  • anodes are used, which in an amount of 20 -100 wt. % of these ores, or mixtures thereof, e.g. Iron oxide.
  • graphite comes into consideration.
  • metal scrap can also be used directly, and consequently, scrap can be made entirely of scrap metal, in which case no oxygen is released at the anode, but the scrap is oxidized.
  • the resistance in Qm 2 / m which is specific to the minerals, should also be considered in order to be able to produce suitable anodes with sufficient conductivity, for example.
  • ge ⁇ shows that iron oxides are good oxygen generating catalysts (OER). However, these are stable only at high pH values. This instability at neutral and acidic pH and accompanying resolution, while reducing the overvoltage is present a special advantage. This is an energy-efficient resolution of the ore over ⁇ all possible.
  • a sulfidi ⁇ ULTRASONIC ore, such as iron sulfide, given anode is used as anode, wel ⁇ ches can be solved by an anodically produced acid. The actual anode reaction can then be the Wasseroxi- dation.
  • the sulfide ores are directly electrically coupled, the sulfide can be oxidized to sulfur directly at the anode. The resulting sulfur then floats on top of the aqueous anolyte solution and can be skimmed off from the electrolyte.
  • the sulfur can be used for example for the kauherstel ⁇ development, production of sulfuric acid, etc.. In the event of an oversupply, however, it can easily be dumped without causing environmental damage.
  • Such an electrolysis ⁇ cell requires very low voltages, since the anode ⁇ voltage is only +0.14 V (S 2 ⁇ (s) + 2H + + 2e- ⁇ H 2 S (g)).
  • the present invention represents a disruptive approach, which converts the previous metal-producing industry to the fundamentally new reducing agent "electrons from renewable energies.” Blast furnaces can thus become superfluous and be converted to electrolyzers with aqueous electrolytes.

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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)

Abstract

L'invention concerne un procédé pour produire un métal M et/ou un mélange et/ou un alliage de ce métal dans une cellule électrolytique comprenant au moins une anode et au moins une cathode, un composé du métal M et éventuellement au moins un autre composé d'un composant d'alliage étant mis en solution aqueuse et le métal M et/ou un mélange et/ou un alliage de ce métal étant déposé électrochimiquement sur l'au moins une cathode.
PCT/EP2018/072640 2017-09-19 2018-08-22 Production électrochimique sans co2 de métaux et d'alliages correspondants WO2019057431A1 (fr)

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DE413148C (de) * 1923-11-27 1925-05-02 Siemens & Halske Akt Ges Anode zur elektrolytischen Eisengewinnung
US1582423A (en) * 1924-04-02 1926-04-27 Zh Rikagaku Kenkyujo Process of electrodepositing iron from iron-containing minerals
US1848002A (en) * 1927-03-08 1932-03-01 Richardson Co Anode for iron plating
GB820172A (en) * 1956-05-22 1959-09-16 Nat Res Dev An electrolytic process for the purification of metals and apparatus therefor
US3580825A (en) * 1968-10-28 1971-05-25 Esb Inc Electrolytic process for purifying iron dissolved from scrap steel

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AT279554B (de) * 1968-01-22 1970-03-10 Ruthner Ind Planungs Ag Verfahren und Vorrichtung zur Herstellung von Metallsalzlösungen elektrochemisch edler Metalle
GB2025461A (en) * 1978-07-12 1980-01-23 Bnf Metals Tech Centre Recovery of copper from sulphide ores
CO4440448A1 (es) * 1993-11-22 1997-05-07 Soc Desarrollo Minero Ltda Sodemi Ltda Proceso para la disolucion electroquimica de minerales sul- forosos y/o concentrados por medio de membranas de intercam- bio ionico y diferenciales de potencia.
WO2001090445A1 (fr) * 2000-05-22 2001-11-29 Nikko Materials Company, Limited Procede de production de metal de purete superieure
PL397081A1 (pl) * 2011-11-22 2013-05-27 Nano-Tech Spólka Z Ograniczona Odpowiedzialnoscia Sposób elektrorafinacji miedzi
DE102016104237A1 (de) * 2016-03-09 2017-09-14 Thorsten Koras Elektrolytische Raffination von Rohgold

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US1582423A (en) * 1924-04-02 1926-04-27 Zh Rikagaku Kenkyujo Process of electrodepositing iron from iron-containing minerals
US1848002A (en) * 1927-03-08 1932-03-01 Richardson Co Anode for iron plating
GB820172A (en) * 1956-05-22 1959-09-16 Nat Res Dev An electrolytic process for the purification of metals and apparatus therefor
US3580825A (en) * 1968-10-28 1971-05-25 Esb Inc Electrolytic process for purifying iron dissolved from scrap steel

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