EP3066045A1 - Conversion de carbonate métallique en chlorure métallique - Google Patents

Conversion de carbonate métallique en chlorure métallique

Info

Publication number
EP3066045A1
EP3066045A1 EP15706702.6A EP15706702A EP3066045A1 EP 3066045 A1 EP3066045 A1 EP 3066045A1 EP 15706702 A EP15706702 A EP 15706702A EP 3066045 A1 EP3066045 A1 EP 3066045A1
Authority
EP
European Patent Office
Prior art keywords
metal
reactor
phosgene
diphosgene
triphosgene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15706702.6A
Other languages
German (de)
English (en)
Inventor
Günter Schmid
Ralf Krause
Dan Taroata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3066045A1 publication Critical patent/EP3066045A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B9/00—General methods of preparing halides
    • C01B9/02—Chlorides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/085—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/14—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moving in free vortex flow apparatus
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/60—Preparation of carbonates or bicarbonates in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/26—Magnesium halides
    • C01F5/30—Chlorides
    • C01F5/32—Preparation of anhydrous magnesium chloride by chlorinating magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • C01F7/58—Preparation of anhydrous aluminium chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • C01F7/58—Preparation of anhydrous aluminium chloride
    • C01F7/60—Preparation of anhydrous aluminium chloride from oxygen-containing aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00752—Feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a method for the manufacture ⁇ development of metal chloride M x + Cl x ⁇ is reacted with the metal carbonate as a solid with phosgene, diphosgene and / or triphosgene to metal chloride M x + Cl x ⁇ wherein the metal M ⁇ is selected from the group of alkali metals, alkaline earth metals, Al and Zn, preferably Li and Mg, particularly preferably Li, and x corresponds to the valence of the metal cation, as well as an on ⁇ device for performing the method.
  • WO2012 / 038330 and WO2013 / 156476 it is described how flue gases / waste gases can be treated with the electropositive metals lithium or magnesium in order to obtain valuable substances and high-grade thermal energy and thereby to reduce the pollution of the atmosphere.
  • CO 2 reacts with lithium to valuable substances such as carbon monoxide or acetylene, which can be further converted to methanol or other valuable substances.
  • the released thermal energy can be used to drive the methanol-C0 2 separation or even a steam generator.
  • the treatments of flue gas / offgas may also include desulfurization due to the high solubility of lithium sulfur based salts and the low solubility of lithium carbonate:
  • Li 2 S 2 0s or Li 2 S0 3 are also very soluble. This means that all the sulfur compounds remain in solution, whereas Li 2 C0 3 (solubility 13 g / 1) as a low ⁇ impact is formed and can be obtained as a very pure product for recycle (s. W02010 / 000681).
  • the good solubility of lithium sulphate is in contrast to that of CaSC.sub.2 (2 g / l), which is prepared in a prior art desulphurisation process. All these process sequences end with a slightly wet, fairly pure lithium carbonate.
  • the reduction of lithium carbonate to metallic lithium can be carried out, for example, by reaction of the carbonate with the chloride and the subsequent the electrolysis of a eutectic mixture of potassium
  • US 20130001097 A1 is to allow lithium carbonate to react with chlorine gas to obtain anhydrous Li ⁇ thiumchlorid.
  • the preparation of anhydrous lithium chloride from powdered lithium carbonate in a fluidized bed reactor is described in WO2014 / 005878.
  • a fast reaction sequence can be ensured by the expiring exothermic reactions, which can lead to a high throughput, and also the freediving energy can be used, for example power plant ⁇ technically.
  • the present invention relates to a process for the preparation of metal chloride M x + Cl x ⁇ , in which metal carbonate is reacted as a solid with phosgene, diphosgene and / or triphosgene to form metal chloride M x + Cl x ⁇ , wherein the metal M is selected from Group of alkali metals, alkaline earth metals, Al and Zn, preferably Li and Mg, more preferably Li, and x corresponds to the valency of the metal cation.
  • the present OF INVENTION ⁇ dung relates to a device for the implementation of metal carbonate as a solid with phosgene, diphosgene and / or triphosgene to metal tallchlorid M x + Cl x ⁇ , where the metal M is selected from the group of alkali metals, alkaline earth metals, Al and Zn, before ⁇ given to Li and Mg, more preferably Li, and x corresponds to the valence of the metal cation, comprising
  • a first reactor for reacting metal carbonate and phosgene, diphosgene and / or triphosgene
  • a first feed device for metal carbonate which is designed to introduce metal carbonate as a solid in the ers ⁇ th reactor
  • a second feeder for phosgene, diphosgene and / or triphosgene which is designed to introduce phosgene, diphosgene and / or triphosgene into the first reactor
  • a first metal chloride discharge means adapted to remove metal chloride from the first reactor
  • a second discharge device for gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene which is adapted to remove gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene from the first reactor.
  • the invention in another aspect relates to an apparatus for the conversion of metal carbonate as a solid with phosgene, diphosgene and / or triphosgene to metal chloride M x + Cl x ⁇ , where the metal M is selected from the group of alkali metals, alkaline earth metals, Al and Zn, preferably Li and Mg, more preferably Li, and x corresponds to the valence of the metal cation, wherein as starting material in addition metal M is added, comprising a first reactor for the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene;
  • a first feed device for metal carbonate which is designed to introduce metal carbonate as a solid in the ers ⁇ th reactor;
  • a second chlorine supply means adapted to introduce chlorine into the first reactor
  • a first metal chloride discharge means adapted to remove metal chloride from the first reactor
  • At least a seventh feeding device for carbon monoxide and / or phosgene, diphosgene and / or tri-phosgene which is designed to carbon monoxide and / or
  • phosgene diphosgene and / or triphosgene into the first reactor; and a second discharge device for gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene, which is designed to remove gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene from the first reactor,
  • FIG. 1 shows schematically a grate reactor which can be used in a method according to the invention and a device according to the invention.
  • Figure 2 schematically shows a detailed view of exporting approximately ⁇ example of a rust reactor which may be used in a ⁇ he inventive method and apparatus according to the invention.
  • FIG. 3 schematically shows a cyclone reactor which can be used in a method according to the invention and a device according to the invention.
  • FIG. 4 shows schematically a further cyclone reactor which can be used in a method according to the invention and a device according to the invention.
  • FIG. 5 shows schematically an embodiment of the present invention.
  • Figure 6 shows schematically a further embodiment of the present invention.
  • FIG. 7 shows schematically yet another among others.
  • FIG. 8 also illustrates another embodiment of the present invention.
  • FIG. 9 shows schematically an embodiment of the present invention, which additionally comprises an electrolytic device.
  • FIG. 10 illustrates a further embodiment of the present invention, which additionally comprises an electrolysis device.
  • FIG. 11 shows schematically an embodiment of the present invention which additionally comprises an electrolysis device, a second electrolysis device and a third reactor.
  • Figure 12 also constitutes a furtherandsbei ⁇ game of the present invention, which additionally comprises an electrolysis device and a second electrolyzer.
  • FIG. 13 shows schematically an exemplary embodiment of the present invention, which additionally comprises a second reactor.
  • Figure 14 shows schematically an embodiment of the present invention, which additionally comprises an electrolysis device and a second reactor.
  • Figure 15 shows schematically a further embodiment of the present invention, which additionally comprises an electrolysis device and a second reactor.
  • FIG. 16 illustrates another embodiment of the invention
  • present invention which additionally comprises an electrolysis device and a second reactor.
  • Figure 17 also constitutes a furtherandsbei ⁇ game of the present invention, which additionally comprises an electrolysis device and a second reactor.
  • the present invention relates in a first aspect to a process for preparing metal chloride M x + Cl x ⁇ , in which metal carbonate is reacted as a solid with phosgene, diphosgene and / or triphosgene to form metal chloride M x + Cl x ⁇ , where x is the valency of the metal cation ( eg 1 for Li, 2 for Mg, 3 for Al).
  • the metal M is selected from the group of alkali metals, preferably Li, Na, K, Rb, Cs, alkaline earth metals, preferably Mg, Ca, Sr, Ba, and Al and Zn.
  • the metal is Li or Mg, and preferably is Li.
  • phosgene, diphosgene and / or triphosgene can hereby be produced in an external reactor or in situ according to certain embodiments.
  • the phosgene, diphosgene and / or triphosgene are generated in an extra reactor before being fed to the reaction with metal carbonate in a first reactor. In this case, the energy already generated there in the production of phosgene, diphosgene and / or triphosgene can be adequately removed.
  • phosgene without diphosgene and / or triphosgene is used in the process according to the invention and in the device according to the invention.
  • phosgene thus also includes diphosgene and / or triphosgene, unless it is otherwise apparent from the context.
  • the phosgene, diphosgene and / or triphosgene can be prepared in situ, for example from carbon monoxide and chlorine, by feeding carbon monoxide and chlorine to a first reactor which also reacts with metal carbonate. It may be advantageous that carbon monoxide and chlorine are easier handhab ⁇ cash or are better available.
  • the amounts of added phosgene, diphosgene and / or triphosgene and / or carbon monoxide and chlorine can be determined on the basis of simple stoichiometric and procedural considerations Amount adjusted to supplied metal carbonate suitably ⁇ the.
  • metal M is additionally added as a starting material.
  • the metal M is used together with the metal carbonate, so that already a reaction of metal with metal carbonate beaufin ⁇ det before, for example, chlorine is added. It is also possible that chlorine and carbon monoxide are produced in other ways than by the carbon monoxide from such a reaction of metal M with metal carbonate in situ, ie in an arbitrary manner, for example by carbon monoxide ⁇ is used in addition. This can also be added in addition to a supply of metal M, for example, unless otherwise re ⁇ cient carbon monoxide may be provided by the reaction of metal carbonate with the metal M, to meet the needs of the CO reaction reaction is complete.
  • carbon monoxide as well as phosgene, diphosgene and / or triphosgene itself can be additionally supplied, unless otherwise re ⁇ cient carbon monoxide may be provided by the reaction of metal carbonate to metal M.
  • the additionally added metal M may also be a metal that is different from the metal ion of the metal carbonate. So, for example when using lithium carbonate as the metal carbonate Li ⁇ thium, sodium, potassium, calcium and / or magnesium are added. In general, such a metal may be added which does not harm later in the electrolysis of the metal chloride. According to certain embodiments, such a metal, which is different from that of the metal carbonate, may also be advantageous if, for example, a eutectic mixture can be formed for the electrolysis of the metal chloride. According to certain embodiments, the metal M corresponds to that of the metal carbonate.
  • the lithium oxide can react further with the CO and Cl 2 or phosgene to form lithium chloride:
  • phosgene From phosgene or alternatively from carbon monoxide and chlorine directly also diphosgene and / or triphosgene can be produced.
  • the phosgene can then with lithium carbonate, as above beschrie ⁇ ben, or with lithium oxide react further:
  • the phosgene, diphosgene and / or triphosgene may thus arise in-situ directly upon injection of lithium to lithium carbonate ⁇ nat in conjunction with a chlorine atmosphere.
  • reaction enthalpies may be so high that, as shown above, they are sufficient for use in power plants (similar to a waste incineration plant).
  • Analogous equations result for the further usable metals M, where M is selected from the group of alkali metals, preferably Li, Na, K, Rb, Cs, alkaline earth metals ⁇ , preferably Mg, Ca, Sr, Ba, and Al and Zn.
  • the metal is Li, K or Mg, and it is preferably Li or K, more preferably Li.
  • the metal M if it is added, in a weight ratio metal / Metallcar- carbonate adjusted that enough carbon monoxide for a reaction, preferably completely, gebil ⁇ det is formed with supplied chlorine, in which case also phosgene, diphosgene and / or triphosgene may be supplied, or that is generated in an additional supply of carbon monoxide as much Kohlenmo ⁇ monoxide that the total amount of carbon monoxide for a reaction, preferably completely, with sufficient chlorine supplied.
  • the amounts of produced carbon monoxide, optionally added ⁇ experiencedem carbon monoxide fed chlorine and optionally fed phosgene, diphosgene and / or triphosgene can be readily determined based on stoichiometric considerations and process technology on the basis of the supplied amounts of metal carbonate and metal ge ⁇ suitable.
  • metal M which is produced for example by electrolysis of a metal chloride using excess energy from renewable energy sources, including a higher proportion of metal M may conces- sets, for example, at times at which no ⁇ excess energy from renewable energy is present, so that in addition can be generated from the additional thermal energy generated in the process according to the invention.
  • the metal M represents a kind of energy storage, which is generated using surplus energy from renewable energies and then gives off the energy when it is needed.
  • the metal M in the process according to the invention can be used together with the metal carbonate.
  • the method can thus be simplified and thus also the apparatus for carrying out the method.
  • the energy release can be suitably optimized by mixing metal M and metal carbonate.
  • the metal M can be used in various forms, for example as a solid, for example in the form of particles, and / or as a liquid in the form of a melt, wherein it can also be atomized in the case of particles or liquid.
  • the phosgene after cooling can be gaseous, liquid or, if necessary, be added as a solution in a suitable solvent or in other form, be ⁇ vorzugt however, gaseous or liquid, most preferably in gaseous form is added.
  • Diphosgene and / or triphosgene can be added in liquid form or as a solid, but also as a gas. If chlorine and possibly carbon monoxide are added for the in situ production of phosgene, diphosgene and / or triphosgene, these can be added in a suitable form, preferably in gaseous form.
  • the program will introduce ge ⁇ Switzerlandss certain embodiments, no further substances into the circulation, which then separated again ⁇ to have.
  • diphosgene and / or triphosgene gaseous products may result, such as CO 2, CO, etc.
  • Kgs ⁇ NEN discharged for example via a discharge device into the atmosphere and / or as products of value stored and / or allowed to react further.
  • excess CO with hydrogen to alkanes, alkenes, koholen ⁇ Al, etc. are implemented.
  • the possibly supplied carbon monoxide can come from any source.
  • the carbon monoxide required can for example be prepared by the following reaction ⁇ to:
  • the inventive method only exothermic reactions take place in the first reactor, while the endothermic part ⁇ reactions are conducted electrochemically, such as a taking place according to certain embodiments of electrolysis of the metal chloride to metal M and chlorine.
  • the electrochemical production of carbon monoxide in ⁇ example by electrolysis is not particularly limited loading, and may for example consist Y. Hori,
  • Electrochemical C02 reduction on metal electrodes in: C. Vayenas, et al. (Eds.), Modern Aspects of Electrochemistry, Springer, New York, 2008, pp. 89-189, which document is referred to the electrolysis of carbon dioxide.
  • Suitable electrolysis equipment / electrolytic cells for performing an electrolysis of carbon dioxide, umfas ⁇ send appropriate anodes, cathodes, if necessary, membranes, etc. may be suitably selected us are also not limited in its kind.
  • the electrolyte aqueous systems with KHCO 3 or ähnli ⁇ chen salts can be used.
  • the electrolyte must be highly conductive to have a low voltage drop and at the same time to provide a good solubility of CO2 besit ⁇ zen must be enough CO2 to the electrode to reduce disposal. This is difficult due to the low solubility of CO2 in water ( ⁇ 3g CO2 per liter at 1 bar and 20 ° C).
  • the cathode space and the anode space are not involved in the electrolysis of carbon dioxide.
  • the carbon dioxide may be present in the electrolyte in dissolved and / or gaseous form. From an environmental point of view, it is preferred in certain embodiments that the electrolyte is also present as an aqueous solution.
  • the electrolyte is not particularly limited as long as it allows (possibly physical) dissolution of the carbon dioxide.
  • it may comprise KCl, K 2 SO 4 , KHCO 3 or mixtures thereof.
  • all combinations of cations and anions can serve as conductive salts, which allow the required current densities for a CO 2 electrolysis.
  • the electrolysis can be carried out according to certain embodiments with a C0 2 - edu Vietnameselysator as a cathode and / or an oxidation catalyst as an anode.
  • the cathode-side reaction depends on material of the cathode, and is not limited insofar as CO is generated. Examples of suitable cathode materials are gold, silver, zinc,
  • the anode material is not particularly be ⁇ limits and includes all anode materials that can be used in electrolysis of water, crizspielswei- se anodes based on platinum, ruthenium or graphite.
  • the cathode-side electrolyte and the anode-side electrolyte may be identical.
  • an electrolysis cell for the electrolysis of carbon dioxide can do without membrane.
  • the electrolytic cell in such embodiments has a membrane, but this is associated with additional expense in terms of the membrane as well as the applied voltage.
  • the electrolysis cell for the carbon dioxide electrolysis has a membrane which separates the cathode space and the anode space of the electrolysis cell, to prevent mixing of the electrolyte.
  • the membrane here is not particularly limited as long as it separates the Ka ⁇ Thode space and the anode space. In particular, it essentially prevents a transfer of carbon dioxide or its dissolved form to the anode.
  • a preferred membrane is an ion exchange membrane, for example polymer based.
  • a preferred material of an ion exchange membrane is a sulfonated tetrafluoroethylene polymer, such as Nafion ®, for example, Nafion ® 115.
  • polymeric membranes and ceramic membranes can be used, for example, in
  • the electrolyte for the electrolysis of carbon dioxide is not limited be ⁇ Sonders, as long as it allows a (possibly physical) solu- sen of the carbon dioxide.
  • KCl KCl
  • KBr KI, K 3 PO 4, K 2 SO 4, KHCO 3 or mixtures thereof. It is not excluded that more than one compound is present in the electrolyte or the electrolyte solution. In principle, all combinations of cations and anions can serve as conductive salts, which allow the required current densities.
  • the electrolyte comprises an ionic component such as a salt.
  • an ionic component such as a salt.
  • this has a low viscosity at room temperature.
  • Materials ⁇ ser type are referred to as an ionic liquid.
  • ioni ⁇ specific liquids certain embodiments according organic salts having a melting point below 300 ° C, preferably below 100 ° C, more preferably referred to below 50 ° C, which according to certain electrolyte from ⁇ guide shapes, optionally in addition to the above- mentioned KCl, K2 SO 4 , KHCO 3 or mixtures thereof, can be added.
  • Exemplary are ionic liquids based on:
  • These anions may be halides, or complex halides such as BF 4 - or PF 6 - , carboxylates, sulfates, triflates, bis (trifluoromethanesulfone) imides, carbonate or bicarbonate, etc.
  • the metal chloride in the presence circuit is converted to the reaction of metal carbonate and metal M with the chlorinating agent back to metal M, before Trains t ⁇ by electrolysis.
  • the reaction can also be carried out in other suitable ways. For lithium results, for example the following reaction ⁇ equation:
  • the preferred electrolysis is not specifically be restricted ⁇ and may for example a melt flow electrolysis of a compound of the formula M x + Cl x ⁇ or an electrolysis ei ⁇ ner aqueous solution of the Compound of the formula M x + Cl x ⁇ include.
  • a eutectic salt mixture with the Ver ⁇ compound of the formula M may be x + Cl x ⁇ testifies replaced by the addition of suitable additives, which is then electrolyzed.
  • the metal M is obtained as a mixture with other metals and thus may have to be separated from these ist ⁇ .
  • a metal M that can be separated for example, later, as a sparingly soluble lithium in the electrolysis of LiCl, so that such a disadvantage is not necessarily ⁇ ent.
  • additional thermal energy can be obtained in the novel reaction of metal carbonate and optionally metal M with Phos ⁇ gen, diphosgene and / or triphosgene used in electric power and / or for preheating, if appropriate, metal M and / or the metal carbonate can be.
  • the electrical energy for the electrolysis of metal chloride as described above provides Darge ⁇ , or be used in the electrolysis of carbon dioxide, so this is supplied can.
  • the energy for the electrolytic reaction of M x + Cl x "provided to M and Cl 2 as well as possibly for the electrolytic To ⁇ reduction of CO 2 to CO essentially of excess energy from renewable energy sources and / or conventional power plants, so for example, more than 30%, preferably more than 70%, more preferably greater than 80% and be ⁇ Sonder preferably more than 90%, based on the energy needs of the electrolysis.
  • surplus energy from erneuerba ⁇ ren energies for this purpose is, for example, then the It will be made available if more electricity is supplied by renewable and / or conventional energy sources than is consumed by consumers, in particular the energy that is surplus in excess of renewable energy sources such as solar, wind, hydro, geothermal , Biofuels (biomass) or similar, and which are not local, regionally d / or überregio ⁇ nal at the time of generation of consumers can be removed. It is not excluded that energy is also obtained from other sources, for example from conventional power sources and / or from the energy generated above in the implementation of metal carbonate and optionally metal M with phosgene, diphosgene and / or triphosgene. According to particularly preferred embodiments, the energy used to
  • Electrolysis of the compound of the formula M x + Cl x ⁇ is used, and / or for the electrolytic conversion of CO 2 to CO, 100% from renewable energy sources, wherein for operating the electrolysis device and energy that does not directly with the electrolysis of the compound Formula M x + Cl x ⁇ or the electrolysis of CO 2 is associated, as in For example, for lighting purposes or for the operation of pumps, etc. can also come from other energy sources, but also from renewable energy sources.
  • the generated metal M is at least partially, for example, more than 20 wt%, more than 50 wt%, or more than 80 wt%, more than 90 wt%, or more than 95 wt% with carbon dioxide to metal carbonate ⁇ set, so that a metal cycle is created.
  • Complete conversion (100% by weight) of the produced metal M with carbon dioxide to metal carbonate is also conceivable. This may for example depend on the demand for the metal M in the market or also the availability of energy, for example surplus energy from renewable energies.
  • the metal M to metal carbonate reacted ⁇ the, for example by metal nitride is first prepared, which then reacts by hydrolysis with carbon dioxide to metal ⁇ carbonate even after a first otherwise reacting with carbon dioxide.
  • both a direct reaction of the metal M with carbon dioxide and a first otherwise word ⁇ term conversion of the metal M, for example with nitrogen, and subsequent reaction to take place with carbon dioxide where weight in here more than 20 ⁇ .%, More than 50 percent by .%, or more than 80% by weight, more than 90% by weight or more than 95% by weight of the metal M can be reacted.
  • a fully continuous ⁇ reaction is (100 wt.%) Of the metal produced to M Me ⁇ tallcarbonat conceivable.
  • the individual steps ie the reaction of metal carbonate and optionally metal M with phosgene, diphosgene and / or triphosgene, the conversion of the metal chloride to metal M and chlorine, possibly the production of CO, for example the electrolytic Implementation of CO 2 to CO, as well as the implementation of the metal M with carbon dioxide at different times, for example on different days, months or seasons, for example, depending on availability of surplus energy from renewable energy, as well as take place in various locations, with the individual generated compounds, metal chloride, metal M, chlorine and metal carbonate and optionally carbon monoxide then transported here ge ⁇ suitable manner, for example by train, trucks, ships, För ⁇ coarse change, pipes, etc.
  • phosgene, diphosgene and / or triphosgene may be generated from the generated chlorine or chlorine again be used as such, optionally together with carbon monoxide, in an additional set of metal M ⁇ to the metal carbonate in its implementation, and thus stored or transported who ⁇ the.
  • the method and apparatus for producing the metal tallcarbonats metal M and carbon dioxide are not particular ⁇ limited and it may, for example, combustion of the metal M, if appropriate with melting and / or pre-heating of the metal M, in a carbon dioxide-containing atmosphere, optionally Un ⁇ ter ignition of the metal M include, where also for the individual processes that require energy, such as excess energy from renewable energy, but also possibly energy from an exothermic combustion of the metal M can be used with the carbon dioxide. Also, in the reaction of metal M and carbon dioxide or kohlendioxidhal- tiger atmosphere, which may also include for example air, stick ⁇ cloth, etc., various, possibly gaseous products of value such as acetylene, CO, hydrogen, oxygen, Ammo ⁇ niak, etc. incurred, which can be further implemented or stored as such and / or used. It may also be possible that the metal carbonate is obtained in a mixture with other solids, from which it may be separated.
  • the reaction of metal carbonate and optionally metal M with phosgene, diphosgene and / or triphosgene takes place in a rust reactor or a mechanically moving fixed bed reactor or in a cyclone reactor.
  • the grate reactor, mechanically agitated fixed bed reactor and the cyclone reactor are in this case according to the invention is not particular limited ⁇ DERS.
  • the reaction is carried out in a grate reactor in which the phosgene, diphosgene and / or triphosgene and / or chlorine and optionally carbon monoxide is added with the addition of metal M as gas in cocurrent with the metal carbonate and optionally metal M. and / or the chlorination medium is preheated.
  • FIG. 11 An exemplary grate reactor is shown in FIG. Via a feeder 11 for metal carbonate, the metal carbonate is introduced into the grate reactor, so that on the grate 13, a metal carbonate bed 12 is formed, wherein the
  • Supply of metal carbonate also possibly with metal M, ⁇ example, by a common opening or by separate Publ ⁇ openings or feeders, can be done.
  • the supply 14 for the phosgene, diphosgene and / or triphosgene takes place.
  • the feed 14 of the phosgene, diphosgene and / or triphosgene can take place over the entire grate 13, but it is not excluded that the feed 14 of the phosgene, diphosgene and / or triphosgene can also be present only in partial regions of the grate 13.
  • the converted and / or optionally unreacted solid metal chloride is a Abvantein ⁇ device 15 for solid fuel comprising discharged, for example by a chute 16.
  • Gaseous products of the reaction of the metal carbonate and the phosgene, Diphosgens and / or triphosgene can via a discharge device 17 for gaseous products the implementation of metal carbonate and phosgene, diphosgene and / or triphosgene be removed.
  • a grate reactor may include one or more cooling devices and / or heat exchangers. Heat exchangers can be provided, for example, in the reaction chamber, which convert the heat generated into steam, which can then be used, for example, to operate generators.
  • Grids are designed to convert solids with long residence times re ⁇ established, and an example is grate furnaces as described in Loo, Sjaak van; Koppej an, Jaap: Handbook of Biomass Combustion. London: Earthscan, pp. 134-144, 2008 are exemplified.
  • the principle of grate firing is well known and well developed. As also shown in Figure 1 at ⁇ way of example, an are fed involved in the reaction solids at the upper end of the grate. 13
  • the grate Since the solid has to be transported out of the reaction space via the grate 13 in order to ensure continuous operation of the reactor, the grate, according to certain embodiments, consists of moving parts which enable the transport of the solid. In FIG. 2, this is
  • the grid 13 is constructed from individual stae ⁇ ben 13a, 13b, of which by way of example, every second bar 13 is horizontally movable, whereas the other rods 13b are laid.
  • all the movable rods may for example have a ⁇ the Common men drive and are thereby moved in phase.
  • Another option is to meet the bars in groups share ⁇ or even individually to control, making the implementation process very carefully monitored and complete reaction can be guaranteed as DE 10137520 Al Darge ⁇ represents is.
  • An adapted pattern of movement of the grate bars may be a control and equalization of the thickness of the layer lying on the grate fuel / solid as the solid ⁇ material flow 18 comprising metal carbonate, optionally metal M
  • the film thickness can be monitored at ⁇ play with corresponding sensors and / or cameras and / or it may be a controlled delivery of the phosgene, Diphosgens and / or triphosgene and / or chlorine and possibly carbon monoxide over the entire bed area.
  • FIG. 2 also shows a discharge of the exemplary reacted process gas via the discharge device 17 in the co-current, which can be done by way of example, although a plurality of removal devices 17 can also be provided or the removal of the converted process gas can take place differently.
  • the removal of the excess, possibly partially unreacted process gas is carried out, for example, according to certain embodiments at the end of the solids discharge from the reactor chamber.
  • An exemplary process is the reaction of lithium carbonate as metal carbonate with phosgene, diphosgene and / or trihydric phosgene in a rust reactor.
  • Lithium can be used as metal M to produce carbon monoxide when using chlorine gas.
  • Lithium can be introduced into the reactor, for example, in liquid, nebulized form (eg, solid lithium, which is heated to a temperature> 180 ° C and is atomized) of solid lithium particles are mixed at ⁇ or form.
  • the reacted metal carbonate can be cooled to the discharge device according to certain embodiments.
  • metal such as lithium
  • the reaction takes place in a cyclone reactor, which is cooled according to certain embodiments, and / or in which, if appropriate, the metal M is introduced at different positions in the reaction zone.
  • Exemplary cyclone reactors are Darge ⁇ represents in Figures 3 and 4, wherein the cyclone reactors case in Figures 3 and 4 are partly bau Sammlungt except that the cyclone reactor shown in Figure 3 a supply means 11 comprises for metal carbonate, while in Figure 4 shown cyclone reactor has a separate feeder IIa for metal carbonate and a separate feed IIb for metal M.
  • Both illustrated cyclone reactors also have a feed 14 for phosgene, diphosgene and / or triphosgene and in the case of Figure 4 also represents chlorine and possibly carbon monoxide, a laxative ⁇ device 15 for solid fuel comprising metal chloride and a discharge device 17 for gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene
  • a reaction zone 21 for example in the form of a rotationally symmetrical upper part a separation zone 22, which is for example conical, as shown in the figure, a flash chamber 23 and a rotary valve 24 as an example of a solids discharge device , as they are present for example in a cyclone separator.
  • a reaction zone 21 for example in the form of a rotationally symmetrical upper part
  • a separation zone 22 which is for example conical
  • a flash chamber 23 and a rotary valve 24 as an example of a solids discharge device , as they are present for example in a cycl
  • the cyclone reactor according to the invention can also be constructed differently.
  • a plurality of removal devices 17 may be provided, or the removal of the reacted process gas may be carried out differently.
  • the discharged solid in addition to metal chloride other substances such as unreacted starting materials or include other.
  • the cyclone reactor may comprise one or more cooling elements / cooling devices and / or heat exchangers, which are not shown, wherein in the heat ⁇ exchangers, for example, steam can be generated, which can be used to generate electricity in generators.
  • a cyclone reactor for the reaction of L1 2 CO 3 with phosgene, diphosgene and / or triphosgene may be used to LiCl, by way of example in the form of a Zyklonabschei ⁇ id. This is the lithium carbonate and the phosgene, diphosgene and / or triphosgene
  • a rotationally symmetric shell as a reaction region 21 is blown tangentially and so swirled together and brought into rotation. Since the desired reaction of the two educts is exothermic to Li ⁇ thiumchlorid, additional cooling is required, which can be done for example by one or more saucetau ⁇ shear.
  • the L1 2 CO 3 pure lithium can be mixed, whereby carbon monoxide can be formed, which can be reacted with chlorine to phosgene, diphosgene and / or triphosgene, so that here chlorine gas and optionally carbon monoxide in addition to or instead of phosgene, diphosgene and / or triphosgene can be supplied.
  • the lithium can be introduced into the reactor, for example either in solid form, for example as lithium particles, or as flüssi ⁇ ges, atomized lithium. For better control of the reaction process, it is conceivable to introduce the lithium at various positions in the reaction region, as shown in Figure 4.
  • the walls of the cyclone reactor may be cooled to dissipate excess heat, which may be reused to generate steam for operation of generators.
  • the present invention also relates to a device in which the method according to the invention can be carried out.
  • the present invention relates to an apparatus for reacting metal carbonate as a solid with phosgene, diphosgene and / or triphosgene to metal chloride M x Cl x ⁇ , wherein the metal M is selected from the group of alkali metals, alkaline earth metals, Al and Zn, preferably Li and Mg, more preferably Li, and x corresponds to the valence of the metal ⁇ cation, comprising
  • a first metal carbonate feeder adapted to introduce metal carbonate as a solid into the first reactor
  • a second feeder for phosgene, diphosgene and / or triphosgene which is designed to introduce phosgene, diphosgene and / or triphosgene into the first reactor;
  • a first discharge device for metal chloride which is formed ⁇ to remove metal chloride from the first reactor nen;
  • a second discharge device for gaseous products of Um ⁇ tion of metal chloride and phosgene, diphosgene and / or triphosgene which is adapted to remove gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene from the first reactor.
  • such apparatus may further comprise a third metal M feed means adapted to introduce metal M into the first reactor.
  • the present OF INVENTION ⁇ dung relates to a device for the implementation of metal carbonate as a solid with phosgene, diphosgene and / or triphosgene to metal tallchlorid M x + Cl x ⁇ , where the metal M is selected from the group of alkali metals, alkaline earth metals, Al and Zn, before ⁇ given to Li and Mg, more preferably Li, and x corresponds to the valency of the metal cation, wherein as starting material Me ⁇ tall M is additionally added, comprising
  • a first reactor for reacting metal carbonate and the chlorinating agent; a first metal carbonate feeder adapted to introduce metal carbonate as a solid into the first reactor;
  • a seventh chlorine supply means adapted to introduce chlorine into the first reactor
  • a first discharge device for metal chloride which is formed from ⁇ to remove metal chloride from the first reactor to entfer ⁇ nen;
  • optionally at least one eighth feed mechanism for carbon monoxide and / or phosgene, diphosgene and / or triphosgene which is adapted to introduce carbon monoxide and / or phosgene, diphos ⁇ gene and / or triphosgene in the first reactor;
  • a second discharge device for gaseous products of the reaction of metal chloride and phosgene, diphosgene and / or
  • Triphosgene designed to remove gaseous products of the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene from the first reactor
  • the device of the invention may further comprise a second electrolysis unit to produce carbon monoxide from carbon dioxide, is fed from the carbon monoxide ⁇ a delivery apparatus of a eighth optional supply means for carbon monoxide.
  • the second electrolysis unit for generating carbon monoxide from carbon dioxide next to it may comprise a feed for carbon dioxide and a feed for water and a discharge device for oxygen or the like.
  • Solids or other substances are removed from the first reactor, for example, unreacted metal carbonate and / or metal M and further reaction products of metal carbonate and / or metal M with the chlorinating agent.
  • the first reactor is for reacting metal carbonate and the chlorinating agent
  • Rust reactor or a mechanically moving fixed bed reactor or a cyclone reactor.
  • the supply of metal M and metal carbonate into the first reactor can take place via a common opening in the first reactor.
  • the apparatus according to the invention may further comprise a metal chloride electrolyzer adapted to electrolyze metal chloride to metal M and chlorine, a fourth metal chloride supply means connected to the first metal chloride discharge means and adapted to form the metal chloride out of the electrolysis device to ⁇ include a third discharge device for metal M, which is adapted to remove the metal M from the electrolysis ⁇ means and comprise a fourth discharge device for chlorine, which is adapted to remove chlorine from the electrolysis device , Also, for example, an additional removal device may be present, which is designed to further reaction products of the electrolysis of metal chloride, for example, in the implementation of a solu ⁇ tion of metal chloride, in which case a solvent such as water, etc.
  • the structure of the electrolytically is se appreciated this is not particularly limited and may commonly used electrolysis facilities, such as the fusion electrolysis or electrolysis of solutions, preferably for fusion electrolysis, umfas ⁇ sen.
  • the device according to the invention may also further comprise, according to certain embodiments, a second reactor for reacting metal M with carbon dioxide to metal carbonate, which is adapted to react metal M with carbon dioxide, a fifth metal M feed means adapted thereto is to feed the metal M to the second reactor, comprising a sixth feed means for carbon dioxide, which is configured to supply carbon dioxide ⁇ the second reactor include a fifth discharge device for metal carbonate, which is connected to the first supply means and is adapted to the
  • Remove metal carbonate from the second reactor, and at least a sixth discharge device for the other products of the implementation of metal M and carbon dioxide include, which is adapted to remove the other products of the reaction of metal M and carbon dioxide from the second reactor.
  • a plurality of removal devices for the other products of the reaction of metal M and carbon dioxide can be included.
  • the second reactor is not particularly limited and may be, for example, a combustion reactor.
  • the fifth removal device for metal carbonate in addition to the metal carbonate, other solids or other substances such as unreacted metal M and / or other reaction products of the reaction of metal M and carbon dioxide are removed.
  • a device comprises an electrolysis device for metal chloride, which is designed to electrolyze metal chloride to metal M and chlorine; a fourth supply means of metal chloride, which is connected to the first discharge device for metal chloride and is adapted to supply the metal chloride of the electrolysis ⁇ direction;
  • a third discharge device for metal M which is ⁇ forms to remove metal M from the electrolysis device
  • a fourth discharge means for chlorine adapted to remove chlorine from the electrolyzer
  • a second reactor for converting metal M with carbon dioxide to metal carbonate which is adapted to react metal M with carbon dioxide;
  • a sixth carbon dioxide supply means adapted to supply carbon dioxide to the second reactor;
  • a fifth metal carbonate discharge means connected to the first supply means and adapted to remove the metal carbonate from the second reactor;
  • At least one sixth discharge device for the other products of the reaction of metal M and carbon dioxide as ⁇ formed to dissipate the other products of the reaction of tall Me ⁇ M and carbon dioxide from the second reactor; in which the third discharge device is connected to the fifth supply device.
  • the third discharge device is additionally connected to the third supply device. In this way, moreover, metal M can be recycled, so that no or less addition of metal M to the process according to the invention is required.
  • further metal M is supplied through a wide ⁇ re, separate third feed or via the same third feed to the first reactor.
  • a erfindungsge ⁇ Permitted apparatus further comprises a second electrolyzer for the electrolysis of carbon dioxide, which is adapted to electrolyze carbon dioxide;
  • a ninth discharge device for carbon monoxide which is designed to remove carbon monoxide from the second electrolysis ⁇ device;
  • a tenth feeder for carbon dioxide which is formed from ⁇ to supply carbon dioxide to the second electrolysis device;
  • a tenth discharge device for oxygen which is ⁇ forms to remove oxygen from the second electrolysis device
  • optionally one and third reactor for the conversion of chlorine and carbon monoxide which is designed to convert chlorine and Kohlenmo ⁇ noxide to phosgene, diphosgene and / or triphosgene and is connected to the second feeder for phosgene, diphosgene and / or triphosgene;
  • a ninth feeder for carbon monoxide which is connected to the ninth discharge device for carbon monoxide and adapted to feed carbon monoxide to the first reactor in order ⁇ reduction of metal carbonate and phosgene, diphosgene and / or triphosgene or the third reactor for reaction of chlorine and carbon monoxide.
  • a erfindungsge ⁇ Permitted device comprises a third reactor for the reaction of chlorine and carbon monoxide, which is adapted, chlorine and carbon monoxide to phosgene, diphosgene and / or triphosgene umzu- and connected to the second feeder for phosgene, diphosgene and / or triphosgene. From this reactor, the phosgene, diphosgene and / or triphosgene can then be fed to the first reactor for the reaction of metal carbonate and phosgene, diphosgene and / or triphosgene. In such embodiments, the preparation of the phosgene,
  • first and / or second reactor and / or the electrolysis devices may also include additional facilities such as one or more cooling devices, heaters, heat exchangers, pumps, etc.
  • additional facilities such as one or more cooling devices, heaters, heat exchangers, pumps, etc.
  • Such devices can also be provided at the various supply and discharge devices.
  • the manner of the supply and discharge devices is not particularly limited and can be suitably selected or provided, for example, as an opening, grate, grid, chute, etc.
  • the connection between the various supply and discharge devices, as above and below described by way of example, can be seen in a suitable manner ⁇ before, for example, by conveyor belts, pipes, etc., but also in terms of bearings and suitable transport options.
  • first reactor and the electrolysis device, the second reactor, the third reactor and / or the second electrolysis device may also be present at different locations, so that they do not necessarily have to be connected to pipes, conveyor belts or the like, but the connection via transport options how ships, goods transport by train, truck, etc. can take place.
  • This has the advantage that the energy-requiring steps, game wise, can vonstatten addition to Standor ⁇ ⁇ th at one or both electrolysis steps where excess energy is regularly present, for example, while the exothermic
  • Processes or process steps can be performed in places where excess energy rarely or never is present, so that takes place in this way a kind of "energy ⁇ transport".
  • FIGS. 5 to 17 Examples of devices according to the invention are shown schematically in FIGS. 5 to 17.
  • heat exchangers and / or cooling devices, etc., as well as further devices at the various supply and / or discharge devices as well as the electrolysis device E may be provided in the first and / or optionally second reactor.
  • FIG. 5 shows a first exemplary embodiment is provided ⁇ , in the metal carbonate via a first Zuglassein ⁇ device 1 for metal carbonate to the first reactor R for implementation-be supplied to metal chloride of metal carbonate as a solid with phosgene, diphosgene and / or triphosgene.
  • phosgene, diphosgene and / or triphosgene are fed to the first reactor R via a second feed device 2 for phosgene, diphosgene and / or triphosgene.
  • metal chloride via a first discharge means 1 ⁇ for metal chloride and gaseous products of Um ⁇ tion of metal carbonate and phosgene, diphosgene and / or triphosgene via a second discharge means 2 ⁇ for gaseous products of the reaction of metal carbonate and phosgene , Diphosgene and / or triphosgene.
  • a second exemplary embodiment is provided in Figure 6 ⁇ , in the additional metal M via a third feed Device 3 for metal M are supplied to the first reactor R via a separate opening in comparison to the feed device 1 for metal carbonate.
  • a third feed Device 3 for metal M are supplied to the first reactor R via a separate opening in comparison to the feed device 1 for metal carbonate.
  • the metal carbonate and the metal M can also be supplied through a common opening.
  • a third exemplary embodiment is shown in FIG. 7, in which a seventh chlorine supply device 7 is provided instead of the second phosgene, diphosgene and / or triphosgene feed device 2 in comparison with the second exemplary embodiment, the chlorine then being supplied with carbon monoxide from the Reaction of metal carbonate and metal M reacts to phosgene, diphosgene and / or triphosgene.
  • a seventh chlorine supply device 7 is provided instead of the second phosgene, diphosgene and / or triphosgene feed device 2 in comparison with the second exemplary embodiment, the chlorine then being supplied with carbon monoxide from the Reaction of metal carbonate and metal M reacts to phosgene, diphosgene and / or triphosgene.
  • an eighth supply device 8 for carbon monoxide and / or phosgene, diphosgene and / or triphosgene, through which phosgene, diphosgene and / or triphosgene and / or carbon monoxide are supplied is not sufficient Carbon dioxide and / or phosgene, diphosgene and / or triphosgene for the conversion of metal carbonate are present, wherein the feed can also be made via two se ⁇ parate eighth feed 8.
  • a fifth exemplary embodiment which is illustrated in Figure 9, corresponding to the first exemplary embodiment, wherein the discharged through the first discharge device 1 ⁇ for metal chloride metal chloride is fed via a fourth To ⁇ transfer device 4 for metal chloride electrolysis device E and is electrolyzed there. From the electrolysis E then metal M via a third discharge means 3 ⁇ for metal and chlorine via a fourth discharge means 4 ⁇ for chlorine dissipated.
  • the first reactor R additionally metal M as in the second exemplary embodiment and optionally chlorine as in the third exemplary embodiment and optionally phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment is supplied.
  • metal chloride is additionally supplied to the electrolysis device E from a source other than the first reactor R.
  • a sixth exemplary embodiment which is shown in Figure 10 corresponds to the fifth exemplary From ⁇ guide die, said metal M as in the second beispielhaf ⁇ th embodiment via a third feeder 3, chlorine as in the third exemplary embodiment of a seventh feeder 7 and Phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment via an eighth feed 8 are supplied, but no second feeder 2 is provided for phosgene, diphosgene and / or triphosgene.
  • the fourth discharge device 4 ⁇ is connected to the seventh feed device 7, so that chlorine is recycled, it is not excluded that chlorine is also fed from ei ⁇ ner further source the first reactor R and / or the electrolyzer E is removed without recycling ,
  • a seventh exemplary embodiment is shown in FIG. 11, in which, in addition to the sixth exemplary embodiment, a second electrolysis device ⁇ ⁇ for electrolyzing carbon dioxide, which is designed to electrolyzate carbon dioxide, is a ninth carbon monoxide removal device 9 ⁇ , which is designed to Carbon ⁇ monoxide from the second electrolyzer ab ⁇ dissipate, a tenth feeder 10 for carbon dioxide, which is adapted to supply carbon dioxide of the second Elektrolyseeinrich ⁇ tion, a tenth discharge 10 ⁇ for oxygen, which is adapted to oxygen from the second electrolyzer ⁇ ⁇ dissipate, a third reactor R xx for the reaction of chlorine and carbon monoxide, which is to temporarilybil ⁇ det, chlorine and carbon monoxide react to form phosgene, diphosgene and / or triphosgene and a ninth feeder 9 for carbon monoxide, which is connected to the ninth Abriosgene, diphosgene and / or triphosgene and a ninth feeder 9 for
  • the third reactor R xx is connected to the second feed device 2 for phosgene, diphosgene and / or triphosgene, so that phosgene, diphosgene and / or triphosgene from the third reactor R xx are fed to the first reactor R. It is not excluded in such an embodiment that additionally metal M, chlorine and / or carbon monoxide, phosgene, diphosgene and / or triphosgene are fed to the first reactor.
  • FIG. 8 An eighth exemplary embodiment is shown schematically in FIG.
  • a second electrolysis means E ⁇ for electrolyzing carbon dioxide which is adapted to electrolyze carbon dioxide
  • a ninth carbon monoxide removal means 9 ⁇ which is adapted to remove carbon monoxide from the second electrolyzer ⁇ ⁇
  • a tenth feeder 10 for carbon dioxide which is adapted to supply carbon dioxide to the second electrolysis device
  • a tenth discharge device 10 ⁇ for oxygen which is designed to remove oxygen from the second electrolysis ⁇ device ⁇ ⁇
  • a ninth feed 9 for carbon monoxide which is connected to the ninth removal device 9 ⁇ for carbon monoxide and is adapted to supply carbon monoxide mon ⁇ the first reactor R, present, in contrast to the sixth exemplary embodiment, in turn, no third feed 3 for metal M and no eighth feeder 8 are present.
  • a ninth exemplary embodiment is outlined in Figure 13, and corresponds to first turn of the first exporting ⁇ approximate shape, the via the first feed device 1 for metal carbonate to the first reactor R supplied metal carbonate from a second reactor R x for the reaction of metal M with carbon dioxide to metal carbonate derived from which it is discharged through a fifth discharge means 5 ⁇ for metal carbonate, which is connected to the first feeder 1 for metal carbonate.
  • To the second reactor R x are fed metal via a fifth feed 5 for metal and Kohlendi ⁇ oxide via a sixth feeder 6 for carbon dioxide and also other products of the implementation of metal M and carbon dioxide via a sixth removal means 6 ⁇ for the other products of the implementation of Metal M and carbon dioxide dissipated.
  • the first reactor R additionally metal M as in the second exemplary embodiment and optionally chlorine as in the third exemplary embodiment and optionally phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment is supplied. It is also not been Schlos ⁇ sen that the first reactor R x metal carbonate is additionally supplied from a ande ⁇ ren source as the second reactor R.
  • production of phosgene, diphosgene and / or triphosgene as in the seventh exemplary embodiment and / or supply of carbon monoxide as in the eighth exemplary embodiment may be present, and the same as set forth in the seventh and / or eighth exemplary embodiments may also be applied such embodiments is true.
  • the illustrated in Figure 14 exemplary tenth exporting ⁇ approximate shape initially corresponds to the fifth exemplary training guide die, said via the first feed device 1 for metal carbonate to the first reactor R supplied metal carbonate from a second reactor R x for the reaction of metal M with carbon dioxide comes to metal carbonate from which it by a fifth discharge device 5 ⁇ for metal carbonate which first with the Feeding device 1 is connected to metal carbonate, is discharged.
  • metal M are fed via a fifth feed device 5 for metal M and carbon dioxide via a sixth feed device 6 for carbon dioxide and also other products of the reaction of
  • the metal M to be converted in the second reactor R x originates, at least partially, from the electrolysis device E, in which case the fifth feed device 5 for metal M is connected to the third discharge device 3 ⁇ for metal M.
  • the first reactor R additionally metal M as in the second exemplary embodiment and optionally chlorine as in the third exemplary embodiment and optionally phosgene, diphosgene and / or triphosgene and / or carbon monoxide as supplied in the fourth exemplary embodiment.
  • first reactor R metal carbonate from a source other than the second reactor R x and / or metal chloride of the electrolysis E from a source other than the first reactor R and / or metal M the second reactor R x from another Source be supplied as the electrolysis E additionally.
  • a preparation of phosgene, diphosgene and / or triphosgene as in the seventh exemplary embodiment and / or a supply of carbon monoxide as in the eighth exemplary embodiment can be present, with the method set forth for the seventh and / or eighth at ⁇ play embodiment also in Such embodiments are true.
  • FIG. 15 exemplary eleventh execution ⁇ form corresponds to the tenth embodiment, wherein metal M As in the second exemplary embodiment via a third feed device 3, chlorine as in the third exemplary embodiment via a seventh feed 7 and phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment ⁇ form via an eighth feed 8 fed However, no second feeding device 2 for phosgene, diphosgene and / or triphosgene is provided.
  • the fourth discharge device 4 ⁇ is connected to the seventh feed device 7, so that chlorine is recycled, with no out ⁇ closed is that chlorine is also fed from a further source to the first reactor R and / or the electrolytic device E is taken without recycling , Likewise, a preparation of phosgene, diphosgene and / or triphosgen gene as in the seventh exemplary embodiment
  • a twelfth exemplary embodiment is shown in FIG. 16, which for the most part corresponds to the tenth exemplary embodiment, but wherein part of the metal M from the electrolysis device E is fed to the first reactor R, ie the third discharge device 3 ⁇ additionally with a third feed device 3 connected is.
  • chlorine may be supplied as in the third exemplary embodiment and optionally phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment.
  • first reactor R metal carbonate from a source other than the second reactor R x and / or metal chloride of the electrolysis E from a source other than the first reactor R and / or metal M the second reactor R x and / or the first reactor R from a source other than the electrolyzer E are additionally supplied.
  • a production of phosgene, diphosgene and / or triphosgene as in the seventh exemplary embodiment and / or a supply of carbon monoxide as in the eighth exemplary embodiment, and the one set forth for the seventh and / or eighth exemplary embodiment also applies in such embodiments.
  • FIG. 17 exemplary thirteenth exporting ⁇ approximate shape corresponding to the twelfth embodiment, with chlorine as in the third exemplary embodiment of a seventh feeder 7 and phosgene, diphosgene and / or triphosgene and / or carbon monoxide as in the fourth exemplary embodiment, an eighth feed mechanism 8, but no second feeding device 2 is provided for phosgene, diphosgene and / or triphosgene.
  • the fourth discharge device 4 ⁇ is connected to the seventh feed device 7, so that chlorine is recycled, it is not excluded that chlorine is also supplied from a further source to the first reactor R and / or the electrolyzer E is removed without recycling.
  • the first reactor R metal carbonate from a source other than the second reactor R x and / or metal chloride of the electrolysis E from a source other than the first reactor R and / or metal M the second reactor R x and / or the first reactor R from a source other than the electrolyzer E are additionally supplied.
  • the present invention relates to a method and apparatus in which metal carbonate such as lithium carbonate ⁇ , is reacted with phosgene, diphosgene and / or triphosgene, wherein contamination and costly dehydra- sticians intimide can be avoided.
  • the phosgene, diphosgene and / or triphosgene is provided according to certain embodiments from an electrolysis of the metal chloride, for example lithium chloride, and a successful conversion of the chlorine to phosgene, diphosgene and / or triphosgene.
  • the thereby obtained metal ⁇ example, lithium may then in accordance with certain embodiments, with carbon dioxide to metal carbonate such as lithium carbonate ⁇ be burned.
  • the metal chloride preparation is used by the direct chlorination of metal carbonate using the originating from the electrolysis of chlorine for the production of phosgene, diphosgene and / or triphosgene.
  • All process steps that require energy can be performed using electrochemical techniques. These can be operated, for example, from about ⁇ surplus energy power generation, particularly but not exclusively by means of renewable energy.
  • the purely thermal processes are exothermic, so that they run very fast and can also be used by power plants, because the temperature levels are very high. The number of species involved in the overall cycle can be kept to a minimum.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Toxicology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un procédé de production de chlorure métallique Mx+Clx - dans lequel un carbonate métallique (1) est converti sous forme solide en chlorure métallique Mx+Clx ‑ (1') au moyen de phosgène, de diphosgène et/ou de triphosgène (2). Le métal M est choisi dans le groupe comprenant les métaux alcalins, les métaux alcalino-terreux, l'Al et le Zn, de préférence le Li et le Mg, de façon particulièrement préférée le Li, et x correspond à la valence du cation métallique. L'invention concerne en outre un dispositif (R) servant à mettre en œuvre le procédé.
EP15706702.6A 2014-02-13 2015-02-09 Conversion de carbonate métallique en chlorure métallique Withdrawn EP3066045A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014202591.5A DE102014202591A1 (de) 2014-02-13 2014-02-13 Umwandlung von Metallcarbonat in Metallchlorid
PCT/EP2015/052640 WO2015121196A1 (fr) 2014-02-13 2015-02-09 Conversion de carbonate métallique en chlorure métallique

Publications (1)

Publication Number Publication Date
EP3066045A1 true EP3066045A1 (fr) 2016-09-14

Family

ID=52595274

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15706702.6A Withdrawn EP3066045A1 (fr) 2014-02-13 2015-02-09 Conversion de carbonate métallique en chlorure métallique

Country Status (7)

Country Link
US (1) US10280090B2 (fr)
EP (1) EP3066045A1 (fr)
KR (1) KR101862342B1 (fr)
CN (1) CN105992748B (fr)
DE (1) DE102014202591A1 (fr)
RU (1) RU2664510C2 (fr)
WO (1) WO2015121196A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014202593A1 (de) 2014-02-13 2015-08-13 Siemens Aktiengesellschaft Umwandlung von Metallcarbonat in Metallchlorid
DE102014202591A1 (de) 2014-02-13 2015-08-13 Siemens Aktiengesellschaft Umwandlung von Metallcarbonat in Metallchlorid
WO2018065078A1 (fr) 2016-10-04 2018-04-12 Siemens Aktiengesellschaft Procédé et ensemble de récupération d'énergie
EP3544726A4 (fr) * 2016-11-22 2020-06-03 Hepatochem, Inc. Dispositif de photochimie
CN113800549A (zh) * 2020-06-17 2021-12-17 南风化工集团股份有限公司 一种从沉淀硫酸钡废渣中提取氯化钡的方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB561651A (en) * 1941-11-24 1944-05-30 Motrac Motormaher & Traktoren Process and apparatus for the manufacture of metals of the alkaline earth series
US3488143A (en) * 1966-06-08 1970-01-06 Cabot Corp Metal halides production in fluid bed
US4096234A (en) 1977-03-23 1978-06-20 Aluminum Company Of America Production of anhydrous aluminum chloride from clay using catalyst and recycling of silicon chloride
JPS603004B2 (ja) 1978-07-27 1985-01-25 ミネラル プロセス ライセンシング コ−ポレイシヨン ビ−ヴイ 無水塩化マグネシウムの製造方法
JPH02243510A (ja) * 1989-03-16 1990-09-27 Osaka Titanium Co Ltd 塩化マグネシウムの製造方法
CA2012009C (fr) * 1989-03-16 1999-01-19 Tadashi Ogasawara Procede pour la production electrolytique du magnesium
DE19514663A1 (de) 1995-04-20 1996-10-24 Kronos Titan Gmbh Metallchloridgenerator
US6048507A (en) 1997-12-09 2000-04-11 Limtech Process for the purification of lithium carbonate
CA2340528A1 (fr) 2000-03-13 2001-09-13 Olivo Giuseppe Sivilotti Methode et appareil d'alimentation de piles electrolytiques
DE10137520B4 (de) 2001-08-01 2004-05-13 Martin GmbH für Umwelt- und Energietechnik Rostfeuerung
EP1434892B1 (fr) 2001-10-03 2005-09-07 Umicore Procede de production de chlorure pour la separation et la recuperation de zinc
AU2003208834A1 (en) * 2002-02-27 2003-09-09 Basf Aktiengesellschaft Reactor and method for producing phosgene
DE102005003612B3 (de) 2005-01-26 2006-06-14 Forschungszentrum Jülich GmbH Verfahren zur Herstellung einer dünnen, gasdichten und Protonen leitenden Keramikschicht sowie Verwendung derselben
EP1874688A1 (fr) 2005-04-18 2008-01-09 Jan Procida Méthode de production sous une forme pure de sels halogénés de métaux alcalins et/ou alcalino-terreux obtenus par traitement hydrolytique de déchets organiques halogénés
RU2288217C1 (ru) 2005-06-27 2006-11-27 Открытое Акционерное Общество "Каустик" Способ получения перхлорированных метиловых эфиров угольной и хлоругольной кислот
US9315382B2 (en) * 2006-03-23 2016-04-19 Keystone Metals Recovery Inc. Metal chlorides and metals obtained from metal oxide containing materials
US20100051470A1 (en) * 2006-11-02 2010-03-04 Santoku Corporation Process for producing metallic lithium
DE102008031437A1 (de) 2008-07-04 2010-01-07 Siemens Aktiengesellschaft Mobiler Energieträger und Energiespeicher
DE102010041033A1 (de) * 2010-09-20 2012-03-22 Siemens Aktiengesellschaft Stoffverwertung mit elektropositivem Metall
US8728425B2 (en) 2012-04-17 2014-05-20 Siemens Aktiengesellschaft Method and an apparatus for performing an energy efficient desulphurization and decarbonisation of a flue gas
EP2850218A1 (fr) 2012-07-05 2015-03-25 Siemens Aktiengesellschaft Procédé d'obtention d'un métal électropositif à partir d'un carbonate de métal
US9624589B2 (en) * 2013-03-13 2017-04-18 University Of Delaware System and process for electrochemical conversion of carbon dioxide to carbon monoxide
DE102014202593A1 (de) 2014-02-13 2015-08-13 Siemens Aktiengesellschaft Umwandlung von Metallcarbonat in Metallchlorid
DE102014202591A1 (de) 2014-02-13 2015-08-13 Siemens Aktiengesellschaft Umwandlung von Metallcarbonat in Metallchlorid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2015121196A1 *

Also Published As

Publication number Publication date
KR101862342B1 (ko) 2018-05-29
RU2016130847A3 (fr) 2018-03-16
CN105992748A (zh) 2016-10-05
WO2015121196A1 (fr) 2015-08-20
US10280090B2 (en) 2019-05-07
RU2664510C2 (ru) 2018-08-20
DE102014202591A1 (de) 2015-08-13
RU2016130847A (ru) 2018-03-16
CN105992748B (zh) 2019-01-25
US20170001875A1 (en) 2017-01-05
KR20160111442A (ko) 2016-09-26

Similar Documents

Publication Publication Date Title
KR102590935B1 (ko) 다양한 금속의 하이드록사이드와 옥사이드 및 이들의 유도체를 제조하는 방법
WO2015121196A1 (fr) Conversion de carbonate métallique en chlorure métallique
Li et al. Electrochemical methods contribute to the recycling and regeneration path of lithium-ion batteries
Buzatu et al. Recovery of zinc and manganese from spent batteries by reductive leaching in acidic media
CN108367933A (zh) 用于处理含锂材料的方法
ITRM20100551A1 (it) Impianto e processo per il trattamento di pile e accumulatori esausti
CN113302168A (zh) 涉及酸和碱的反应方案；包括空间上变化的化学组成梯度的反应器；以及相关的系统和方法
EP2707517A1 (fr) Procédé permettant d'obtenir des métaux et des métaux des terres rares à partir de ferrailles
Li et al. A closed-loop ammonium salt system for recovery of high-purity lead tetroxide product from spent lead-acid battery paste
WO2021069470A1 (fr) Procédé et dispositif d'électrolyse pour la production de chlore, de monoxyde de carbone et éventuellement d'hydrogène
WO2013152942A1 (fr) Système de méthanisation basé sur une centrale électrique
EP3080042B1 (fr) Conversion de carbonate de métal en chlorure de métal
EP2877614A1 (fr) Procédé de préparation d'un métal alcalin
WO2019091653A1 (fr) Préparation et séparation de phosgène par électrolyse combinées co2 et chlorure
EP3079795B1 (fr) Séquestration de dioxyde de carbone par liaison sous la forme de carbonate alcalin
WO2019057431A1 (fr) Production électrochimique sans co2 de métaux et d'alliages correspondants
DE102020003440B4 (de) Verfahren zur thermochemischen Herstellung von Titan
WO2024056401A1 (fr) Production d'hydrogène et d'hydroxyde de lithium solide
DE2033109C (de) Verfahren zur Herstellung von Schwefelhexafluorid
EP3635801A1 (fr) Procédé permettant de faire fonctionner un dispositif de stockage d'énergie électrique et dispositif permettant la mise en oeuvre du procédé
DE2927279A1 (de) Verfahren zur herstellung von synthetischer, wasserfreier soda und chlor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160608

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SIEMENS AKTIENGESELLSCHAFT

17Q First examination report despatched

Effective date: 20181210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190424