WO2015082289A1 - Installation de traitement pour la combustion continue d'un métal électropositif - Google Patents

Installation de traitement pour la combustion continue d'un métal électropositif Download PDF

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Publication number
WO2015082289A1
WO2015082289A1 PCT/EP2014/075746 EP2014075746W WO2015082289A1 WO 2015082289 A1 WO2015082289 A1 WO 2015082289A1 EP 2014075746 W EP2014075746 W EP 2014075746W WO 2015082289 A1 WO2015082289 A1 WO 2015082289A1
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WIPO (PCT)
Prior art keywords
electropositive metal
metal
electropositive
lithium
thermal energy
Prior art date
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PCT/EP2014/075746
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German (de)
English (en)
Inventor
Helmut Eckert
Renate Elena Kellermann
Wiebke SARFERT-GAST
Günter Schmid
Dan Taroata
Original Assignee
Siemens Aktiengesellschaft
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Publication of WO2015082289A1 publication Critical patent/WO2015082289A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0612—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with alkaline-earth metals, beryllium or magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
    • C01B21/0722—Preparation by direct nitridation of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D13/00—Compounds of sodium or potassium not provided for elsewhere
    • 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
    • C01F11/02—Oxides or hydroxides
    • 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
    • C01F11/18—Carbonates
    • 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
    • C01F11/18—Carbonates
    • C01F11/186—Strontium or barium carbonate
    • C01F11/188—Barium carbonate
    • 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
    • C01F5/02—Magnesia
    • C01F5/04—Magnesia by oxidation of metallic magnesium
    • 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
    • C01F5/14—Magnesium hydroxide
    • 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
    • C01F5/24—Magnesium carbonates
    • 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
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • C01F7/422—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation with a gaseous oxidator at a high temperature
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
    • F23B90/00—Combustion methods not related to a particular type of apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
    • F23B2900/00—Special features of, or arrangements for combustion apparatus using solid fuels; Combustion processes therefor
    • F23B2900/00003—Combustion devices specially adapted for burning metal fuels, e.g. Al or Mg

Definitions

  • the present invention relates to a method of conti nuous ⁇ burning an electropositive metal for generating thermal energy, and preferably the same chemical raw materials, and an apparatus for continuously burning a loan electropositive metal for generating thermal energy.
  • DE 10 2010 041 033 A1 shows how a complete energy cycle with electropositive metals can be represented.
  • lithium which serves both as Ener ⁇ energy carrier as well as energy storage is used. It is believed that the findings can be transferred to other electro-positive metals such as sodium, potassium or magnesium, calcium, barium or aluminum and zinc.
  • Lithium meets the criteria for such a fully recyclable energy source.
  • lithium oxide or its salts are electrochemically reversible to lithium.
  • hitherto no industrially utilizable processes have been known.
  • This lithium is used in the overall cycle as the energy source and energy storage and is therefore not consumed, but only changes its oxidation state during the cycle.
  • the amount of energy that can be stored at the same time scales with the amount of lithium used.
  • DE 10 2010 041033 AI it is shown that a power plant operation can be realized by means of lithium as a metallic coal ⁇ set. On a thermodynamic energy scale, lithium is so high that it is highly exothermic, not only in air, but also in pure nitrogen, hydrogen and carbon dioxide.
  • the combustion of lithium into carbon dioxide is an energy-efficient way to significantly reduce the CO 2 emissions of a fossil power plant.
  • the advantage here is that both the thermal energy from the combustion process of Li in CO 2 and the reaction ⁇ product (CO) contribute to energy or are useful. So the carbon atom leaves for example in methanol TIALLY ⁇ to the power plant.
  • ammonia can also be produced under similar power plant conditions, one of the most important raw materials of the fertilizer industry. This is the case with the combustion of lithium in nitrogen (for example, from air decomposition in power plant concepts such as
  • Lithium ⁇ nitride reacts exothermically with water to ammonia.
  • lithium as well as magnesium, potassium, sodium, calcium, barium
  • electropositive metal for example, lithium, in a burner room requirement.
  • the above-mentioned reactions of lithium with the indicated gases are known from the laboratory scale, combustion of electropositive metal in air, a carbon dioxide, Nitrogen, water vapor, or oxygen atmosphere or in gas mixtures in a continuous power plant process with a continuous supply of electropositive metal as a fuel and in the form of spray or particles not yet realized. Investigations into the ignition and ignition temperature for a power plant-relevant process for energy conversion are not known in the literature.
  • Lithium fires are to be prevented or how they are to be extinguished in case of fire.
  • the process used for this purpose includes a reaction chamber, in which lithium filled and liquefied at 400 ° C is vice ⁇ sets. Gas mixtures of oxygen, nitrogen and What ⁇ serdampf were in the chamber via a gas inlet through the liquid lithium led (Gil, TK, Kazimi, MS, Plasma Fusion Center MIT, 1986). However, here too no deeper analysis of the combustion process to lower ⁇ investigation of the reaction mechanisms and the resultant reaction products was carried out.
  • the lithium in order for the combustion processes to be used to provide thermal energy for power production, the lithium, as with coal or petroleum burners, must be introduced into the oxidant as a high surface area powder or spray. tion medium to maintain a sufficient flow of energy are introduced.
  • a process for producing lithium particles is described in the patent DE 10 2011 052 947 AI.
  • the ⁇ Patent specification DE 10 2011 052 947 Al is directed here to the Her ⁇ position of products such as metal oxides, metal hydrides or metal by the reaction of lithium ((in particulate form) with a reactive gas is oxygen, water, or
  • DE 102 04 680 A1 describes a process for the preparation of alkyllithium compounds by atomization of lithium metal, in which metallic lithium in the form of particles is reacted with an alkali metal halide.
  • a combustion process is not covered in the document DE 102 04 680 AI.
  • the production of lithium particles takes place by the atomization of lithium melt in an inert atmosphere or in a vacuum, using single-substance pressure nozzles and preferably two-component nozzles.
  • the present invention relates to a method for continuously burning an electro-positive metal to generate thermal energy
  • Process chamber with a process gas generating thermal energy
  • chemical raw materials are simultaneously produced during the combustion.
  • the invention further relates to an apparatus for continuously burning an electropositive metal for generating thermal energy with the following components:
  • Figure 1 Schematic overview of the process flow and a
  • Figure 2 Schematic view of a piston pump as an example of a conveyor of the present invention
  • Figure 3 Schematic view of an injector as an example of a conveyor of the present invention
  • Figure 4 Schematic view of a screw compressor as
  • Figure 5 Schematic view of an extruder as an example of a conveyor of the present invention
  • Figure 6 Schematic view of a nozzle as an example of a
  • FIG. 8 Schematic view of a nozzle as an example of a sputtering device of the present invention
  • Figure 9 Schematic view of an exemplary process ⁇ chamber of the present invention
  • Figure 10 Schematic view of an exemplary apparatus of the present invention
  • Figure 11 Schematic view of an exemplary apparatus of the present invention
  • Figure 12 Schematic view of an exemplary apparatus of the present invention
  • the present invention describes an apparatus / Pro ⁇ zessstrom, which allows an electropositive metal such as to burn in a continuous process, the energy source lithium, and the process performed by means of this device, method of continuous combustion of the electropositive metal. Furthermore, the invention relates to a device / process plant, it enables light to process electro-positive metals such as alkali and alkaline earth metals ⁇ in a continuous process, for example, a spray, and then burn them in a process chamber. As electropositive metals are in this context
  • an electropositive metal is a metal which with respect to the standard hydrogen electrode at 25 ° C has a Elektrodenpo ⁇ tential of ⁇ -0.75V.
  • Preferred electropositive metals are alkali or alkaline earth metals or Al or Zn as well Mixtures and alloys thereof, with Li, Na, K, Mg and mixtures and alloys thereof being more preferred, and more preferably the electropositive metal is Li and its alloys, particularly preferably Li.
  • Lithium is particularly versatile in reacting with various ones Process gases as well as under safety aspects preferred.
  • the device / process system assumes the following after ⁇ running part functions
  • melting or pulverizing the electropositive metal i. Transition from the solid to the liquid state or process of surface enlargement of the electropositive metal to increase its reactivity;
  • melting of the electropositive metal is preferred according to certain embodiments.
  • the process plant according to the invention for the combustion of lithium consists of the process units:
  • Feeder supply of the electropositive metal.
  • Dosing unit Dosing the electropositive metal.
  • Melting device or pulverizer Melting or pulverizing the electropositive metal.
  • Conveyor also called process unit for continuous pressure build-up: transport melt and build up pressure.
  • atomizing device for example nozzle / nozzle tool:
  • Process chamber possibly ignition and combustion of the particles produced, for example in a reaction gas.
  • the feed unit, the metering unit and the melting device can also be combined in the context of a metering device, with which the electropositive metal is metered, wherein it is melted at the same time.
  • other parts of the system can be combined in certain embodiments, for example only the dosing unit and the melting device, the melting device and the conveyor, the dosing unit, the melting device and the conveyor, etc., so that their functions are taken over in a single combined component and no clear demarcation between the individual components occurs.
  • melting and / or metering may occur during promotion of the electropositive metal.
  • the melting device and the conveyor are coupled together.
  • FIG. 1 A schematic overview of the process flow is shown in FIG. 1.
  • the present process (process) P comprises the following steps in this order:
  • Process chamber with a process gas generating thermal energy
  • the method steps i to vi can be carried out.
  • the present invention thus relates, in one aspect, to a method of continuously burning an electropositive metal to generate thermal energy
  • Process chamber with a process gas generating thermal energy According to certain embodiments, the pressurization in step iv) at a pressure of 0.01 to
  • the electropositive metal can also, in step v) with the process gas sprayed ⁇ the.
  • the electropositive metal is ignited after sputtering in step v). In particular, an ignition of the electropositive metal has not been realized on an industrial scale.
  • the molten in step iii) electropolished ⁇ sitive metal in the steps iv) and v) may further preferably be heated to a temperature above the melting point of the electro ⁇ positive metal.
  • the electro-positive metal can also be used in some areas in steps iv) and / or v), ie in parts of the conveyor
  • the sputtering device are heated to a temperature below the melting point of the electropositive metal, wherein it can then be heated in the further course in these steps iv) and / or v) to a temperature above the melting point of the electropositive metal.
  • the thermal energy generated in step vi) may, according to certain embodiments, be used to generate electrical energy
  • Energy and / or used to melt the electropositive metal may also be used instead or in addition to heat the electropositive metal in steps iv) and v).
  • solids are carbonate and / or nitride compounds such as lithium carbonate L1 2 CO 3 and / or lithium nitride L1 3 N, but also oxides or hydrides such as L1 2 O or LiH or hydroxides such as LiOH, but also combustion products pure from the process gas such Carbon C or its reaction product lithium carbide.
  • the present invention thus also relates to an apparatus for continuously burning an electropositive metal for generating thermal energy with the following components:
  • Conveyor is coupled and adapted to atomize the electropositive metal
  • the process gas is not further limited in the present invention as long as it can be burned with the electropositive metal to generate thermal energy. This can be easily estimated by reaction enthalpies.
  • the electropositive metal is brought in step vi) with the process gas to reac ⁇ tion, wherein the process gas is air, carbon dioxide, Nitrogen, water vapor, hydrogen, oxygen or
  • the inventive method is preferably carried out in a device which is operated with a power greater than 1 kW, preferably greater than 100 kW.
  • the amount of supplied to the combustion electro-positive metal for example, the injected lithium ⁇ amount,> lOg / s and the thermal power achieved thereby be> 100 KW.
  • the reaction temperature in the reactor system / the process chamber is preferably> 500 ° C. Adiabatic reaction temperatures up to 4000K can be achieved.
  • the feed device 1 has the task of the electropositive metal, such as the fuel and energy sources
  • the dosing unit 2 has the task of the electropositive metal, such as the fuel and energy carrier "lithium” for the combustion process continuously
  • the electropositive metal for example lithium
  • the starting material can be present in the form of powder, granules, pellets or bulk material (for example in the form of blocks or in barrels).
  • lithium for example in the form of pellets, granules or powder with a typical particle size in the range of about 0.01 to 100 mm is present, it may, for example, a
  • dosing or vibrating chutes or similar dosing units which are commonly used for dosing solids, are added to the process plant.
  • the type of dosing unit 2 is not particularly limited here.
  • the metering unit Since electropositive metals, such as lithium as well as other suitable alkali and alkaline earth metals such as Magne ⁇ sium and sodium, oxidize in air.
  • the metering unit is encapsulated air-free or airtight.
  • the dosing unit for protection to ⁇ addition with respect to the electropositive metal, such as lithium, inert behaving gases such as argon or CO and / or aliphatic hydrocarbons such as methane, ethane, propane and / or volatile oils such as pentane, hexane, octane , aromatic hydrocarbons or mixtures thereof are flooded.
  • the electropositive metal is melted or pulverized in a melting device or in a pulverizer 3. Preference is given to melting using a melting device.
  • a melting device 3 are any components into consideration, with which an electropositive metal can be melted.
  • the electropositive metal may be in particulate form in a heated flow tube melted and thus simply the conveyor 4, in which a pressure build-up, as a melt, for example by means of Pum ⁇ pen supplied.
  • the treatment of particulate electro-positive metal, such as lithium with the help of a conveyor, such as a heated conveyor belt, a continuous furnace or a rotating screw conveyor and a heated cylinder, which is able to congress the electropositive metal ⁇ melt and transport.
  • an electropositive metal such as lithium is usually stored and transported in barrels with a capacity of 100 liters and more.
  • electropositive metal eg lithium metal
  • the use of the present in large quantities in barrels or containers metal is therefore preferred.
  • the solid metal is melted in this case, for example, in a continuous furnace to supply it in the form of melt the conveyor 4.
  • the waste heat of the combustion ⁇ process can be used in a device according to the invention for melting the electropositive metal. This is particularly attractive for the alkali metals or higher alkaline earth metals (especially Mg, Ca, Sr, Ba), such as lithium, sodium, as they melt easily.
  • a powdering device 3 can be provided, in which the electropositive metal is pulverized to fine dust, which can then be burnt after atomization with the process gas, for example also with the aid of an ignition device. Powdering of the electropositive metal, for example lithium, is preferably carried out using a protective gas, since the electropositive metal reacts easily, for example in air, and thus an inert
  • the electropositive metal is preferably also not introduced with a particle size of less than 10 mm in the inventive device or the method according to the invention by the feeder ⁇ device 1.
  • the electropositive metal in the form of particles having a particle size in the range to 10 mm, preferably up to 1 mm, more preferably up to 100 ym and particularly preferably up to 10 ym under protective gas may optionally be dispensed with an independent Pulverisier Road 3, but this is not preferred, and it takes place within the system, for example within the feed - Device 1, the metering unit 2, the conveyor 4 and / or the atomizer 5, a further pulverization instead, so that these components can thus take over the function of the Pulverisier worn 3 with.
  • pulverization is preferably carried out with metals such as Zn and Mg.
  • the conveyor 4 is for the continuous transport of the melt provided by the melting device 3 of the electropositive metal, for example
  • the conveyor 4 may for example be designed as a conveyor coupled with a system for pressure build-up, but also as an integrated component in which the promotion takes place under simultaneous pressurization.
  • the conveyor may include heating elements 100 configured to be electropositive metal to a temperature above the
  • the delivery device 4 comprises a piston pump, as illustrated by way of example in FIG.
  • the piston pump consists of a possibly heated cylinder 41a and an axially bewegli ⁇ chen piston 41b, for example, a reciprocating piston, which pressurizes the molten metal MM with pressure, combined with an inlet valve and a nozzle outlet as an example of Zerstäube Nur 5, with which the Spray S is generated.
  • two or more piston pumps can be operated in alternating cycles, wherein the nozzle outlet opens into a common process chamber 6.
  • Other known types of piston pumps, which are also suitable for the pressure build-up of lithium melts are, for example RadialkoIbenpumpen
  • the working pistons are arranged radially and perpendicular to the rotating shaft.
  • the lifting movement is triggered, for example, via the eccentrically mounted pump shaft.
  • the inlet of the melt takes place either from the inside via a hollow pumping shaft or is applied from the outside.
  • injector 42 instead of a piston, the molten metal MM, for example lithium melt, is pressurized in a so-called injector 42, as shown by way of example in FIG.
  • the molten metal MM which is present for example in a cylinder 42 a, by a gas flow 42 b with pressure (for example 3-5 bar) is applied to press them through the Zerstäubeeinrich- device 5, for example a nozzle to produce the spray S.
  • a gas flow 42 b with pressure for example 3-5 bar
  • pressure for example 3-5 bar
  • gas come, especially in the case of lithium, argon and CO or aliphatic hydrocarbons such as methane, ethane, propane or depending on the field of application volatile alkanes and aromatics for use, since they do not react with lithium.
  • the screw compressor 43 for example a screw pump, has the task of conveying the molten metal MM in a continuous process and building up the pressure required for spraying the molten metal MM, and is shown by way of example in FIG.
  • the technology of the two intermeshing, rotating spindles used here, for example 43b comes usual way in the compression of gases such as air and liquid ⁇ possibilities for application.
  • the medium to be compressed is continuously displaced by the helical toothing of two spindles 43b within the cylinder 43a, as the working volume of the gas channels decreases along the axis towards the outlet end.
  • the profiles of the two helical spindles 43b are usually different, with one spindle having a concave and the other a convex profile.
  • the length of the spindles typically extends over 5 to 10 spiral turns.
  • the screw pump is used to build up pressure.
  • the screw compressor 43 is used according to the invention to build up pressure in the molten metal MM in a continuous process in order to press it through the atomizing device 5, for example a nozzle tool, for particle or droplet production.
  • Typical pressures that are required to process an electro-positive metal such as lithium as spray S are in the range of 0.01-100 bar, Favor 1 - 10 bar.
  • the screw compressor 43 is optionally equipped with one or more heating elements 100.
  • the pressure in an extruder system / an extruder 44 is created which is illustrated at ⁇ way of example in FIG. 5 In contrast to the embodiments AC, the extruder 44 is adjacent to the
  • Dosing unit 2 and the melting device 3 take over, and thus can be dispensed with a separate upstream metering unit 2 and a separate melting device 3 for preparing the molten metal MM.
  • the extruder 44 is thus a particular embodiment of a component within the continuous incinerator / apparatus.
  • An extruder 44 essentially consists of a possibly heatable cylinder 44a, in the interior of which one or two rotating screws 44b do the work.
  • the extrusion process is typically used in the processing of plastic melts, with the plastics (thermoplastics) to be processed as fine-grained granules or
  • Powder are added.
  • the molding takes place at the exit of the extruder, by the plastic melt through a
  • Nozzle tool is pressed. In this way, For example, cables, hoses, films produced in a continuous process.
  • the extruder 44 In contrast to the screw pump, the extruder 44 also assumes the task of melting the mate ⁇ rial here. For this reason, the screws 44b are longer than the screw pump and typically include more than 10 and up to 100 spiral circuits.
  • Plastics in which the abovementioned extrusion process is usually used are usually viscous and have viscosities in the range> 100 Pas compared to the melt of the electropositive metal MM, for example a lithium metal melt with a melt viscosity of about 0.5 mPas (for comparison: water at room temperature has 1 mPas), rather than viscous.
  • the pressure in the melt depends essentially on the type of extruder 44 and its screw geometry.
  • Known designs are single and twin-screw extruders (also twin-screw extruder).
  • the teeth of two screws 44b engage each other, with closely intermeshing, counterrotating screws 44b favor the pressure build-up and therefore for processing and pressure build-up of low-viscosity molten metals, such as lithium, which is the preferred design.
  • the tempering of the cylinder 44a also plays a role in the pressure build-up.
  • the viscosity as temperature-dependent and pressure-dependent material properties can in this case 44 stunning ⁇ influence on the heating zones / heating elements 100 of the extruder system.
  • he became the father of friction ⁇ carries the material to heat and thus to
  • the extruder 44 has at least 3, typically via 5-7 separately controllable heating zones / heating elements 100, which a gradual and thus controlled melting and pressure build-up of the electropositive metal, in the case of lithium in a temperature range of room temperature (eg. 25 ° C) to about 450 ° C, allow.
  • Typical pressures that are required to process the electropositive metal such as lithium as spray S are in the range of 0.01-100 bar, preferably 1-10 bar.
  • the design of the screw 44b influences the melting behavior of the electropositive metal and the compression or build-up of pressure in the melt and thus the extrusion and spray process.
  • Common designs such as those used in plastics processing, are, for example, 3-zone screws, short compression screws, long compression screws, degassing screws and screw conveyors.
  • a detailed description of the plastic extruder technology can be found, for example, in Schenkel, G., Kunststoff-Extrudertechnik, Carl Hanser Verlag, Kunststoff, Vienna 1963.
  • a 2-zone screw is for example for the processing of fine-grained or powdered electropositive metal, for example, lithium, suitable.
  • the extruder 44 is filled with material and this melted directly on ⁇ .
  • the pressure builds up. In order to build up the pressure efficiently, it is advantageous if in this area the working space in the direction of the outlet decreases continuously. This is done for example through a steady Ver ⁇ réelleung the channel depth.
  • the profiles of the two screws 44b may be identical or as in the screw pump in a convex and concave design.
  • the design of the screw design depends on the size of the plant / equipment and the required process speeds and mass flow rates (for example throughput of electropositive metal or lithium mass flow rate: from lg / s to 50 t / h).
  • the Zerstäube desk 5 for example a nozzle tool / a nozzle 51 as a single-fluid nozzle / single-fluid pressure nozzle, a two-fluid or pneumatic nozzle or a mechanical nozzle is preferably directly connected to the conveyor 4 and has an object, the melt of the electropositive Me ⁇ talls MM or the pulverized electropositive metal into a fine particulate spray S having particle sizes up to and including 100 ym, preferably up to 10 ym and more preferably up to
  • a nozzle 51 located at the atomizer 5, for example, a nozzle 51, according to certain Embodiments of a fastening device 45, as shown in Figures 6 to 8.
  • Atomizing device 5 or nozzle 51 with internal gas supply Embodiments for nozzles 51 without internal gas supply (so-called single-substance nozzles) can be found by way of example in FIGS. 6 and 7 and with internal gas supply in FIG.
  • the nozzle diameter tapers toward the nozzle outlet.
  • the bore diameter of the nozzle 51 is typically in the range of 0.5 to 3 mm.
  • the molten metal MM leaves the nozzle 51 at sufficient speed and pressures in the range of 0.01-100 bar, preferably 1 - 10 bar, forming fine
  • a process gas inlet 52 e.g. additional nozzles (for example in the form of a ring nozzle, which is formed annularly around the nozzle, or in FIG.
  • Supplied process gas PG promotes the formation of droplets and also serves as a process gas (PG (reaction gas)) for combustion with the electropositive metal, for example lithium .
  • PG reaction gas
  • the process gas at a certain distance from the outlet of the atomizer 5, example ⁇ as the nozzle outlet is supplied to prevent clogging of the Zerstäube Road 5, for example the nozzle 51, for example at a distance of more than 1 cm, more than 1 dm or more than 1 m, for instance more than 5 m.
  • the nozzle 51 may be provided with a perforated grid 53 to further promote the formation of droplets.
  • the process gas PG is supplied via a gas nozzle in the interior of the tool nozzle 51, in order to favor the atomization of the molten metal MM.
  • process gases come in ⁇ example in the case of lithium, for example, N 2 , CO 2 , H 2 O, air in question.
  • This design is a two-fluid nozzle. These have the advantage that the atomization by the process gas PG takes place, which is also used as a reaction gas (oxidant) for the combustion and thus no subsequent supply of process gas PG is necessary. So that no mixing of the process gases PG and the "fuel electropositive metal" takes place within the nozzle, which would lead to an undesired premature conversion of the electropositive metal to carbonate, oxide, nitride, the supply line for the internal gas supply is preferably so ⁇ sets in that the desired combustion takes place after ignition.
  • swirlers incorporated in the nozzle 51 may generate flow turbulences, thereby promoting the formation of fine droplets.
  • the generated droplet size of the spray S is on the one hand dependent on the geometry and temperature of the atomizer 5 and on the other hand on the viscosity of the melt and the pressure with which it is pressed through the nozzle. Therefore, the Zerstäube driving 5, for example, a
  • Nozzle 51 can be heated in certain embodiments.
  • Typical orifices have a diameter in the range of 0.5 to 3 mm.
  • Process chamber 6
  • the process chamber 6 (combustion ⁇ reactor) is preferably hermetically encapsulated, for example by a reactor wall 61.
  • the supply of the process gases PG either directly to the Zerstäube overlooked 5, as described above, or the process gases are introduced into the process chamber 6.
  • process gases PG for the combustion of the electropositive metal such as lithium, for example, the gases oxygen 0 2 , water vapor H 2 O, carbon dioxide CO 2 or nitrogen 2 are used, which can react strongly exothermic with the electropositive metal. 2 as flame ⁇ temperatures up to 4000 K and 2 were calculated up to 2000K, for example, in the reaction of lithium with CO.
  • the start of combustion occurs directly in response to the process gas PG, according to certain embodiments.
  • This type of autoignition takes place under certain conditions, which depend inter alia on the particle size of the spray S, the Tempe ⁇ temperature, pressure and the process gas PG.
  • ignition temperatures For the reaction of lithium with nitrogen, for example, ignition temperatures of 170 ° C to 600 ° C are reported in the Lite ⁇ temperature.
  • values in the range of 400 to 640 ° C can be found.
  • moisture for example in the form of water vapor, shifts the ignition to lower temperatures and has an accelerating effect (Rhein, RA:
  • the process chamber 6 is equipped with an ignition device 7 according to preferred embodiments. This can e.g. via a discharge spark or plasma excitation.
  • ignition devices 7 e.g. Magneto, electronic
  • the ignition can be initiated by adding steam. Once the combustion process has been ignited, it will continue to run by itself, provided that the electropositive metal, eg, lithium, and process gas PG are continuously supplied to the combustion process. Alternatively, the electropositive metal which can be injected ⁇ upper half of the ignition temperature, a
  • Other gaseous reac ⁇ tion products for example, formed in the reaction with water or C0 2, for example, are H 2 and CO.
  • the process chamber is designed in accordance with certain embodiments so that resulting burn-off products 64 can be disposed of via a possibly interchangeable grid floor 63 during operation. Resulting gaseous products can be extracted via an outlet 62 and collected for further follow-up reactions.
  • the CO formed during combustion in C0 2 can be used as starting material for the production of methanol or hydrocarbons.
  • the combustion products 64 may be removed continuously by means of a discharge device within the process chamber, for example, which is adapted to remove a combustion ⁇ product of the electropositive metal with the process gas kon ⁇ continuously from the process chamber, for example a conveyor belt or similar.
  • a discharge device within the process chamber, for example, which is adapted to remove a combustion ⁇ product of the electropositive metal with the process gas kon ⁇ continuously from the process chamber, for example a conveyor belt or similar.
  • the outlet 62 by means of which continuously gaseous products of the combustion can be removed, is to be understood as a discharge device.
  • the thermal energy generated in the process chamber is used according to certain embodiments, eg analogous to a coal-fired power plant primarily for power generation.
  • steam can be generated, which is a Gastur- bine, which converts the thermal into electrical energy.
  • all compounds formed during the combustion of the electropositive metal, for example lithium can be further utilized and further processed, or they are recycled by means of electrolysis into the electropositive metal, for example lithium.
  • the loss produced by the combustion heat which does not benefit due to Entro ⁇ pie bin binen of electricity, be utilized as heat for the heating of the starting material, the electropositive metal can.
  • the device according to the invention further has a transport system with which the thermal energy is conducted to the melting device 3 and / or to the conveying device 4 for heating the electropositive metal.
  • Embodiment 1 (FIG. 10) is a special embodiment for processing powdered and particulate metals, here lithium, in which the extruder 44 takes over the process steps - melting, conveying and pressure.
  • Extruders 44 are constructed as set forth above, wherein the process chamber 6 has an ignition device 7.
  • a special feature in this embodiment is that the extruder 44 and the supply of the metal pellets MP as well as the dosage device 2 in an inert gas, such as argon, ge ⁇ filled chamber 20 are provided to reactions of the electropositive metal in these components with the Environment as far as possible to exclude.
  • Embodiment 2 according to Figure 11 of the screw compressor shown above are 43 connected to the above dargestell ⁇ th process chamber 6, wherein the supply to the screw compressor, the metering and melting in a
  • inert gas SG for example argon
  • the process chamber 6 has an ignition device 7.
  • Embodiment 3 shown in FIG. 12 the above-described screw compressor 43 is connected to the above-described process chamber 6 having an ignition device 7.
  • the supply to the screw compressor 43 takes place as follows: Via a conveyor belt 11 as an example of a feed device 1, solid electropositive metal, in this case lithium, in barrels of a continuous
  • Furnace 31 which is filled with inert gas SG for pressure equalization and to prevent premature reaction of the metal supplied. From this continuous furnace ⁇ plant 31, the molten metal MM is supplied via a valve to the screw compressor 43. On the speed of the conveyor 11, the valve before the screw compressor 43, etc. Here, the metering can be controlled, so that the combination of conveyor belt 11, a continuous furnace ⁇ system 31 and valve after melting the dosing unit 2 comprises.
  • Metal in particular lithium, and the inventive method:
  • process gases such as C0 2 , N 2 , H 2 , air, water.
  • the system / device takes over all the processes required for the combustion of the electropositive metal, such as: providing material, melting, conveying, pressure build-up, sputtering, possibly igniting and burning the lithium.
  • the process is scalable from small material throughputs of a few 10 g / h up to several 100 kg / h or to the 100 tons / h (comparison coal-fired power plant 13000 t coal per day).
  • the systems are relatively compact and can be connected directly to oxyfuel power plants without special precautions.
  • the CO 2 produced in oxyfuel power plants can be used as a reaction gas for combustion.
  • the thermal energy generated in the system can be any thermal energy generated in the system.

Abstract

L'invention concerne un procédé pour la combustion continue d'un métal électropositif pour la génération d'une énergie thermique et un dispositif de combustion continue d'un métal électropositif pour la génération d'une énergie thermique.
PCT/EP2014/075746 2013-12-03 2014-11-27 Installation de traitement pour la combustion continue d'un métal électropositif WO2015082289A1 (fr)

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DE102013224709.5A DE102013224709A1 (de) 2013-12-03 2013-12-03 Prozessanlage zur kontinuierlichen Verbrennung eines elektropositiven Metalls
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DE102014209527A1 (de) * 2014-05-20 2015-11-26 Siemens Aktiengesellschaft Verfahren zum Verbrennen einer Legierung eines elektropositiven Metalls
DE102014210402A1 (de) 2014-06-03 2015-12-03 Siemens Aktiengesellschaft Pumpenfreie Metall-Verdüsung und -Verbrennung mittels Unterdruckerzeugung und geeignete Materialflusskontrolle
DE102014219275A1 (de) 2014-09-24 2016-03-24 Siemens Aktiengesellschaft Zündung von Flammen eines elektropositiven Metalls durch Plasmatisierung des Reaktionsgases

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DE102008031437A1 (de) 2008-07-04 2010-01-07 Siemens Aktiengesellschaft Mobiler Energieträger und Energiespeicher
KR101285223B1 (ko) * 2011-09-08 2013-07-11 연세대학교 산학협력단 물 플라즈마를 이용한 금속 분말 점화방법, 소형 연소장치 및 연소방법

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DE102009014026A1 (de) * 2008-12-03 2010-06-10 Ernest Stangl Verfahren zur Erzeugung thermischer Energie
US20110033355A1 (en) * 2009-08-10 2011-02-10 Smith David R Method and apparatus to sequester co2 gas
US20130178677A1 (en) * 2010-09-20 2013-07-11 Siemens Aktiengesellschaft Method and a system for converting carbon dioxide into chemical starting materials
DE102011052947A1 (de) * 2011-08-24 2013-02-28 Karlsruher Institut Für Technologie (Kit) Verfahren zur Herstellung hochreiner Pulver und Extrusionsvorrichtung hierzu

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