EP3083500A1 - Procédé et dispositif de séparation de gaz résiduaire lors de la combustion de certains métaux - Google Patents

Procédé et dispositif de séparation de gaz résiduaire lors de la combustion de certains métaux

Info

Publication number
EP3083500A1
EP3083500A1 EP15708128.2A EP15708128A EP3083500A1 EP 3083500 A1 EP3083500 A1 EP 3083500A1 EP 15708128 A EP15708128 A EP 15708128A EP 3083500 A1 EP3083500 A1 EP 3083500A1
Authority
EP
European Patent Office
Prior art keywords
gas
carrier gas
metal
exhaust gas
mixture
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Withdrawn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
EP15708128.2A
Other languages
German (de)
English (en)
Inventor
Walter Preidel
Manfred Baldauf
Günter Schmid
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 EP3083500A1 publication Critical patent/EP3083500A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C01D15/02—Oxides; Hydroxides
    • 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
    • C01B21/0607—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 alkali metals
    • C01B21/061—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 alkali metals with lithium
    • 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
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
    • F23B30/00—Combustion apparatus with driven means for agitating the burning fuel; Combustion apparatus with driven means for advancing the burning fuel through the combustion chamber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
    • F23B80/00—Combustion apparatus characterised by means creating a distinct flow path for flue gases or for non-combusted gases given off by the fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C3/00—Combustion apparatus characterised by the shape of the combustion chamber
    • F23C3/006—Combustion apparatus characterised by the shape of the combustion chamber the chamber being arranged for cyclonic combustion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00—Arrangements of devices for treating smoke or fumes
    • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
    • F23J15/027—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using cyclone separators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J3/00—Removing solid residues from passages or chambers beyond the fire, e.g. from flues by soot blowers
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2217/00—Intercepting solids
    • F23J2217/30—Intercepting solids by screens
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2217/00—Intercepting solids
    • F23J2217/40—Intercepting solids by cyclones

Definitions

  • the present invention relates to a method for the separation of exhaust gas from solid and / or liquid reaction products in the combustion of a metal M, which is selected from alkali metals, alkaline earth metals, Al and Zn and mixtures thereof, with a fuel gas, wherein in a reaction step ⁇ the Fuel gas is burned with the metal M and Ab ⁇ gas and other solid and / or liquid reaction products are formed, and in a separation step, the exhaust gas is separated from the solid and / or liquid reaction products, in which in the separation step in addition a carrier gas is zugege ⁇ ben and the carrier gas is beau ⁇ leads as a mixture with the exhaust gas, and a device for carrying out the method.
  • a metal M which is selected from alkali metals, alkaline earth metals, Al and Zn and mixtures thereof
  • a fuel gas wherein in a reaction step ⁇ the Fuel gas is burned with the metal M and Ab ⁇ gas and other solid and / or liquid reaction products are formed, and in a separation step, the exhaust
  • Lithium is usually Herge ⁇ poses with fused salt electrolysis. For this process, efficiencies of approximately 42-55% are calculated, calculated from process data without temperature correction of the normal potential. In addition to lithium, similar metals such as sodium, potassium, magnesium, calcium, aluminum and zinc can be used.
  • the supply of a carrier gas can be used to efficiently dissipate the heat produced in the combustion so that it is efficient for generating energy, for example electrical energy via a gas turbine, and efficiently removing the heat from the Re ⁇ Actor can be achieved, so that the material of the reactor, for example, the reactor wall, is spared or a correspondingly simpler reactor construction is possible.
  • the present invention relates to a process for separating exhaust gas from solid and / or liquid reaction products in the combustion of a metal M selected from alkali metals, alkaline earth metals, Al and Zn and mixtures thereof with a fuel gas, wherein a reaction step, the fuel gas with the metal M is ver ⁇ burned and exhaust gas and other solid and / or liquid reaction products formed; and
  • the exhaust gas is separated from the solid and / or liquid reaction products
  • the present OF INVENTION ⁇ dung relates to a device for the separation of exhaust gas from the combustion of a metal M, selected from alkali metals, alkaline earth metals, Al and Zn and mixtures thereof, with a fuel gas, comprising: a burner for burning the metal M with the
  • a fuel gas supply means adapted to supply fuel gas to the burner
  • a feeding device for metal M which is keptbil ⁇ det to supply the burner metal M;
  • a supply device for carrier gas which is designed to supply carrier gas to the reactor.
  • a discharge gas mixture discharge means and carrier gas adapted to discharge a mixture of the exhaust gas from the combustion of metal M with the fuel gas and the carrier gas;
  • Fuel gas which is adapted to dissipate solid and / or liq ⁇ sige reaction products of the combustion of metal M with the fuel gas.
  • FIG. 1 shows schematically an exemplary arrangement for a device according to the invention.
  • FIG. 2 shows schematically a detail view in a further exemplary arrangement for a device according to the invention.
  • FIG. 3 shows schematically a further detail view in egg ⁇ ner additional exemplary arrangement for a device according to the invention.
  • FIG 4 schematically illustrates an exemplary cross-sectional view of an exemplary inventive Vorrich ⁇ tung in the region of the supply of the Crowga- ses to the reactor.
  • FIG. 5 shows a scheme for an exemplary reaction of lithium and carbon dioxide to lithium carbonate, which can be carried out according to the method of the invention.
  • FIG. 6 shows a schematic of another exemplary Re ⁇ action of lithium and nitrogen to lithium nitride and other secondary products, which can be performed according to the inventions to the invention method.
  • the present invention relates, in a first aspect, to a process for separating exhaust gas from solid and / or liquid reaction products in the combustion of a metal M selected from alkali metals, alkaline earth metals, Al and Zn and mixtures thereof with a fuel gas, in one Reaction step, the fuel gas with the metal M ver ⁇ burned and exhaust gas and other solid and / or liquid reaction products are formed, and in a separation step, the exhaust gas is separated from the solid and / or liquid reaction products, in which a carrier gas is additionally added in the separation step and the carrier gas as a mixture is discharged with the exhaust gas.
  • the carrier gas may also correspond to the exhaust gas, so that, for example, during combustion, an exhaust gas is produced which corresponds to the supplied carrier gas or else corresponds to the fuel gas.
  • the metal M is, according to certain embodiments, selected from alkali metals, preferably Li, Na, K, Rb and Cs, alkaline earth metals, preferably Mg, Ca, Sr and Ba, Al and Zn, as well as mixtures thereof.
  • the metal M is selected from Li, Na, K, Mg, Ca, Al and Zn, more preferably Li and Mg, and more preferably the metal M is lithium.
  • such gases come into question, which can react with said metal or mixtures of metals in an exothermic reaction, these are not particularly limited.
  • the fuel gas, air, oxygen, carbon monoxide, Kohlendio ⁇ dioxide, hydrogen, water vapor, nitrogen oxides NO x monoxide as nitrous include nitrogen, sulfur dioxide, or mixtures of the same ⁇ .
  • the method can therefore also be used for desulfurization or NOx removal.
  • different products can be obtained with the different metals, which can be obtained as a solid, liquid and also in gaseous form.
  • metal M for example, at a reaction of metal M, at ⁇ play, lithium, nitrogen, inter alia Metallnit ⁇ chloride, such as lithium nitride, are formed, which can then be further reacted later ammonium monia, whereas at a conversion of metal M, such as lithium with carbon dioxide, for example, metal carbonate such as lithium carbonate, coal ⁇ monoxide, metal oxide such as lithium oxide, or Metallcar- bid, for example, lithium carbide, and also produces mixtures thereof, wherein, from the carbon monoxide higher carbon ⁇ containing products such as methane, ethane, methanol etc.
  • metal M such as lithium with carbon dioxide
  • metal carbonate such as lithium carbonate
  • coal ⁇ monoxide coal ⁇ monoxide
  • metal oxide such as lithium oxide
  • Metallcar- bid for example, lithium carbide
  • metal carbide for example, lithium carbide
  • metal carbide for example, lithium carbide
  • ⁇ play as acetylene can be obtained, for example in a Fischer-Tropsch driving while metal carbide, for example, lithium carbide, can be obtained at ⁇ play as acetylene.
  • nitrous oxide as a fuel gas such as metal nitride arise.
  • the carrier gas according to the invention is not particularly limited, and may correspond to the fuel gas, but also be different from this.
  • the carrier gas are, for example air, Koh ⁇ monoxide, carbon dioxide, oxygen, methane, hydrogen, water vapor, nitrogen, nitrous oxide, mixtures of two or more of these gases, etc. for use.
  • various gases, such as methane are used to Wär ⁇ metransport and the reaction heat of the reaction of metal M able to remove the fuel gas from the reactor.
  • the various carrier gases can be suitably adapted to the reaction of the fuel gas with the metal M, for example, in order to achieve synergy effects if necessary.
  • lithium in which carbon monoxide, can be used as carrier gas, for example carbon monoxide and optionally circulated, after the discharging as ⁇ the, at least partially, as are returned carrier gas.
  • the carrier gas is adapted to the exhaust gas, so that possibly a portion of the carrier gas removed as value product who ⁇ can, for example, for a subsequent Fischer-Tropsch synthesis, while it is generated by the combustion of carbon dioxide with metal M again, so that in the balance carbon dioxide is at least partially converted to carbon monoxide, preferably to 90 vol.% or more, more preferably 95 vol.% or more, even more preferably 99 vol.% or more and particularly preferably 10 vol.%, Based on the turned ⁇ continued carbon dioxide, and is taken out as product of value. ever More carbon monoxide is generated, the cleaner is the select ⁇ led carbon monoxide.
  • the exhaust gas may be at least 10% by volume, preferably 50% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, and even more preferably 80 vol.% Or more, based on the total volume of the exhaust gas, corresponding to the carrier gas
  • the fuel gas can be at least 10% by volume, preferably 50% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, and even more preferably 80 vol.% Or more, based on the total volume of the exhaust gas, corresponding to the carrier gas
  • the mixture of exhaust gas and carrier gas is at least partially recycled to the separation step as carrier gas and / or the combustion step as fuel gas.
  • Recirculation of the mixture of flue gas and carrier gas may in ⁇ play, in an amount of 10 vol.% Or more, preferably. 50% by volume or more, more preferably 60 vol.% Or more.% Even more preferably 70 or more by volume, and even more preferably 80% by volume or more, based on the total volume of carrier gas and exhaust gas, take place.
  • recycling the mixture of exhaust gas and carrier gas to 90 vol.% Or more, based on the total volume of carrier gas and exhaust gas done.
  • a reaction between fuel gas and metal M can take place in such a way that the carrier gas is formed as exhaust gas, for example with carbon dioxide as fuel gas and carbon monoxide as carrier gas, so that then the mixture of carrier gas and exhaust gas substantially, preferably 90 Vol.% And more, more preferably 95 vol.% And more, even more preferably 99 vol.% And more, and particularly preferably 100 vol.%, Based on the mixture of exhaust gas and carrier gas, consists of the carrier gas.
  • the carrier gas are continu ously ⁇ circulated and removed in such an amount as it is modeled by the combustion of metal M and fuel gas.
  • the separation step takes place in a process according to the invention in a cyclone reactor.
  • the cyclone reactor is not particularly limited in its structure and may, for example, have a shape as they have ordinary cyclone reactors.
  • a cyclone reactor can have a reaction region at which the feed devices for the fuel gas, metal M and the carrier gas (which may also be previously combined and then fed together to the reaction region) can be attached, for example in the form of a rotationally symmetrical upper part .
  • a separation region which is configured conically, for example,
  • a discharge device for solid and / or liquid reaction products of the combustion of metal M with the fuel gas for example in the form of a rotary valve, and a discharge device for the GE mixture of exhaust gas and carrier gas, which results after fürmi ⁇ tion of the two gases after the burning of the metal M in the fuel gas, can be attached include.
  • a cyclone reactor used in accordance with the invention may also have a different structure and optionally also comprise further regions).
  • individual portions eg reaction region Separations ⁇ area, expansion chamber
  • reaction region Separations ⁇ area, expansion chamber can also be combined in one component of an exemplary cyclone reactor and / or extend over a plurality of components of a cyclone reactor.
  • the cyclone reactor comprises a grid through which the solid and / or liquid reaction products can be removed with the combustion gas during the combustion of the metal M.
  • the mixture of exhaust gas and carrier gas may according to certain embodiments, for example in the reactor and / or at and / or after discharge from the reactor, for heating a boiler or for heat transfer in a heat exchanger or a turbine, for example a gas turbine, can be used.
  • the mixture of the carrier gas and the exhaust gas may be under increased pressure after combustion.
  • an apparatus for separation of exhaust gas from the combustion of a metal M selected from alkaline metals, according to another aspect of the invention, alkali metal earth ⁇ , Al and Zn, discloses a fuel gas, comprising:
  • a burner for burning the metal M with the fuel gas which is adapted to the metal M with the
  • a fuel gas supply means adapted to supply fuel gas to the burner
  • a metal feed M adapted to supply metal M to the burner
  • a discharge gas mixture discharge means and carrier gas adapted to discharge a mixture of the exhaust gas from the combustion of metal M with the fuel gas and the carrier gas;
  • a discharge device for solid and / or liquid reaction products of the combustion of metal M with the fuel gas which is designed to solid and / or liquid reaction products of the combustion of metal M with the
  • the burner according to the invention is not particularly limited and can be configured for example as a nozzle in which the fuel gas is mixed with the metal M and then ignited, if necessary, by an igniter. Also, the burner may be provided in or on the reactor.
  • the feeding means are not particularly limited and, for example, pipes, hoses, conveyor belts, etc., which suited the basis of the physical appearance of the Me ⁇ talls or the state of the gas, if necessary, may also be under pressure, can be determined.
  • the reactor particularly limited insofar as combustion of the fuel gas with the metal M can take place in it.
  • the reactor may be a cyclone reactor, as illustrated by way of example in FIG. 1 and in a detailed view in a further embodiment in FIG.
  • the cyclone reactor can be a reaction region on which are mounted the feed means for the fuel gas, metal M and the carrier gas Kgs ⁇ NEN accordance with certain embodiments, for example in the form of a rotationally symmetric shell,
  • a separation region which is configured conically, for example,
  • a discharge device for solid and / or liquid reaction products of the combustion of metal M with the fuel gas for example in the form of a rotary valve, and a discharge device for the Ge ⁇ mixture of exhaust gas and carrier gas, which is after fürmi ⁇ Schung of the two gases after burning the metal M in the fuel gas results, can be attached include.
  • a cyclone reactor used in accordance with the invention may also have a different structure and optionally also comprise further regions).
  • individual portions eg reaction region Separations ⁇ area, expansion chamber
  • FIG. 1 An exemplary cyclone reactor is shown in FIG.
  • the cyclone reactor 6 shown in FIG. 1 comprises a reaction region 20a, a separation region 20b which is located both together with the reaction region 20a in the upper component 6a and together with the expansion chamber 20c in the lower component 6b, as well as a flash chamber 20c.
  • Cyclone reactor lead in the upper part of a feeder 1 for fuel gas, for example in the form of a possibly heated pipe or hose, and a feed device 2 for metal M, for example in the form of a possibly heated pipe or a hose, wherein the two feeders in the nozzle 3 are combined and then fed together to the reaction area 20c.
  • a nozzle 3 is suitable for For example, when using liquid metal M, which can then be atomized by means of the nozzle.
  • the metal M can also be atomized in the form of solid particles. Other types of atomization or mixing of metal M and fuel gas are possible.
  • the carrier gas is supplied to a region 4 ⁇ for gas distribution, from which then the carrier gas via Dü ⁇ sen 5, with which a cyclone can be formed, fed to the separation region 20b.
  • a detailed view of such a feed device 4 with a region 4 ⁇ for gas distribution and a nozzle 5 is shown in cross-section by way of example in FIG 4, but more nozzles 5 may be present, for example, at a suitable distance around the inner wall of the area 4 to a suitable Create cyclone.
  • an ignition device such as an electric ignition device or a plasma arc, or an additional pilot burner may be required, this depends on the type and condition of the metal M, such as its temperature
  • the nature of the fuel gas for example, its pressure and / or temperature
  • the arrangement of components in the device such as the nature and condition of the feeders, from ⁇ hang.
  • the inner material of the reactor made of high temperature alloys, for example, in extreme cases, from the material Haynes 214.
  • a thermal insulation can be arranged, which is sufficient allows little heat through, so that the outside of a steel wall, which may also be air or water cooled, absorbs the pressure load. From the ⁇ gas can then be fed to the further process step with the increased or high operating pressure.
  • the reactor for example a cyclone reactor, may also comprise heating and / or cooling devices which are connected to the reaction region, the separation region and / or the expansion chamber as well as to the various supply and / or discharge devices, if necessary the burner, and / or possibly the ignition device are present.
  • other components such as pumps for generating a pressure or a vacuum, etc. may be present in a device according to the invention.
  • the cyclone reactor may comprise a grid which is designed such that the solid and / or liquid reaction products can be removed during the combustion of the metal M with the fuel gas through the grid.
  • a grid may also be present in other reactors which may be provided in the device according to the invention.
  • Such a grating is shown as an example in FIG 2, according to the, is the grating 6 ⁇ way of example in the cyclone reactor 6, which is shown in FIG 1 in the lower member 6b above the discharge device 7 and below the discharge means. 8
  • the grid preferably with a sufficiently large distance from the reactor wall, a safe separation of solid and liquid reaction products or their mixture can be ensured. As a result, the already separated solid or liquid combustion products are no longer stirred up by the cyclone.
  • the geometry of the supply system is not particularly be ⁇ limits, provided the carrier gas with the exhaust gas from the Burn ⁇ voltage of metal M and fuel gas can be mixed.
  • PREFERRED Trains t here a cyclone, for example, arises with the ⁇ represent provided in FIG 1 device.
  • a cyclone can also be generated by other arrangements of the feeders to each other.
  • the supply means of the carrier gas is also present at the top of the reactor in the vicinity of the feeders for metal M and fuel.
  • suitable injection geometries can be easily determined in a suitable manner, for example by means of flow simulations.
  • the discharge devices are not particularly limited, wherein, for example, the discharge device for the mixture of exhaust gas and carrier gas can be formed as a tube, while the discharge device for ⁇ the solid and / or liquid reaction products of the combustion of metal M with the fuel gas, for example as Rotary valve or can be configured as a pipe with a siphon.
  • various valves, such as pressure valves, and / or other controller can be provided.
  • An exemplary discharge device 7, for example the cyclone reactor 6 shown in FIG. 1, may in this case include a siphon 9, a degassing valve 10 and a pressure regulator 11, but is not limited to such a device.
  • Such a siphon at the discharge device for the solid and / or liquid reaction products of the combustion of metal M with the fuel gas optionally in conjunction with a suitable for the respective operating pressure form pressure regulator, can be used for example to allow increased or high operating pressure.
  • the discharge device for the mixture of exhaust gas and carrier gas may according to certain embodiments also contain a separation device for the exhaust gas and the carrier gas and / or individual components of the exhaust gas.
  • the discharge device for a mixture of exhaust gas and carrier gas can such be to ⁇ transfer device connected for carrier gas and / or the feed device for the fuel gas with that the mixture of exhaust gas and carrier gas at least partially to the reactor as a carrier gas and / or the burner as Fuel gas is supplied.
  • the amount of the recirculated gas may be 10% by volume or more, preferably 50% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, and even more preferably 80% by volume or more, based on the total volume of carrier gas and exhaust gas amount.
  • According to certain shapes can exporting approximately ⁇ a recirculation of the mixture of flue gas and carrier gas to 90 vol.% Or more, based on the Intelvolu ⁇ men of carrier gas and the exhaust gas take place.
  • a device may further comprise at least one boiler and / or at least one heat exchanger, which is located in the reactor and / or the discharge device for the mixture of exhaust gas and carrier gas.
  • the device of FIG. 1 which comprises a cyclone reactor 6, one or more heat exchangers and / or boilers may be provided in the reactor 6, in the discharge device 8 and / or in a device adjoining the discharge device 8, which are not shown.
  • a heat from ⁇ exchange can even take place at the cyclone reactor 6, for example on the outside walls in the reaction region 20a and / or the separation region 20b, but possibly also in the area of the expansion chamber 20c.
  • the exhaust gases can thus, as a mixture with carrier gas, a further use, for example, heating a boiler for steam generation, heat dissipation in a heat exchanger, etc. are supplied.
  • a device according to the invention may comprise a removal device in the discharge device for the mixture of exhaust gas and carrier gas, which is designed for returning the mixture of exhaust gas and carrier gas to the feed device for carrier gas and / or the fuel gas supply device by connecting the discharge device for the mixture of exhaust gas and carrier gas with the feed device for carrier gas and / or the feeder for fuel gas to take part of the mixture of Ab ⁇ gas and carrier gas.
  • Such a part can at ⁇ game instance more than 1 vol.%, Preferably 5.% Vol.% And more, and further preferably 10 or more by volume, based on the total ⁇ volume of the mixture of flue gas and carrier gas, respectively.
  • Availability checked ⁇ supply such as when carbon monoxide is discharged, and is then reacted in a Fischer-Tropsch process to higher quality hydrocarbons.
  • the discharged solids can be further converted into recyclables.
  • So made of a metal nitride with nitrogen Burn ⁇ voltage may be implemented by hydrolysed ⁇ se with water to form ammonia and caustic, for example, the resulting liquor can then also serve as a scavenger for carbon dioxide and / or sulfur dioxide.
  • the metal M for example lithium
  • the metal M is used liquid, ie above the melting point, for lithium 180 C.
  • the liquid metal M e.g. Lithium can be atomized into fine particles in a nozzle and then reacts immediately, optionally after ignition to start the reaction, with the respective fuel gas, e.g. Air, oxygen, carbon monoxide, carbon dioxide,
  • carbon dioxide can be used as the fuel gas and carbon monoxide in the apparatus shown in FIG. 1 as the carrier gas.
  • the metal used is, for example, lithium, for example liquid, ie above the melting point of 180.degree.
  • the liquid li Thium can be atomized with the nozzle 3 to fine particles and then reacts directly with the fuel gas. You may need an electric ignition or an additional pilot burner.
  • the second step takes place in the central part of the reaction tors / furnace 6 in the area 4 ⁇ of the mixture Verbrennungspro ⁇ -products with the carrier gas carbon monoxide, which is injected through nozzles 5 into the reactor. 6
  • an excess of Trä ⁇ gergas is used to ensure sufficient removal of heat generated by the combustion.
  • the temperature in the reactor 6 can be suitably adjusted.
  • the resulting lithium carbonate has a melting point of 723 ° C. If the combustion temperature of the reaction products retained by means to ⁇ mixture of gas through the nozzles 3.5 of at least 723 ° C, so one can start from the liquid reaction products for combustion.
  • the nozzles can be used here in the highly exothermic reaction for cooling, so that the system does not excessively heat up, with the lower temperature ⁇ temperature limit of the melting point of the resulting salts, here
  • Lithium carbonate can be. If the cyclone is also operated with gases other than carbon dioxide, such as air, nitrogen or carbon monoxide or other gases, lithium oxide (melting point Mp 1570 ° C) or lithium nitride (Mp 813 ° C) may also be formed in the reaction products. After separation of the liquid and solid reaction products, which can be improved by a grating ⁇ 6 ⁇ , the mixture of exhaust gas and carrier gas, for example, passed into a boiler and used for Ver ⁇ steaming of water, to then drive a steam turbine with a downstream generator or other technical devices (eg heat exchangers). The cooled after this process mixture of exhaust gas and carrier gas can then, for example, again as a carrier gas for generating the
  • Cyclones are used in the oven.
  • the residual heat of the exhaust gas is used after the evaporation process in the boiler, and it must only the stoichiometrically necessary amount of Kohlendi ⁇ oxide for combustion with Li be obtained by exhaust gas purification, for example of coal power plants.
  • Table 1 shows the relationship between exhaust gas temperature and stoichiometric excess for the combustion of lithium in pure carbon dioxide, which was calculated with non-temperature-dependent specific heat.
  • carbon monoxide With recirculation of the exhaust gas cooled by the subsequent process step, carbon monoxide can be accumulated in the exhaust gas. It is according to certain embodiments possible to remove a portion of the exhaust gas, and thus to obtain a gas mixture of carbon monoxide and carbon dioxide, which has a significantly higher proportion of carbon dioxide, as indicated in Table 1. A subsequent gas separation ⁇ the carbon monoxide can be purged of carbon dioxide, and the carbon dioxide can be used in the circuit or in Bren ⁇ ner.
  • a specific reaction temperature is preferably set by recycling a constant amount of mixture of exhaust gas and carrier gas as carrier gas.
  • a corresponding reaction procedure is also shown by way of example in FIG.
  • a waste gas 100 for example, from a combustion power plant such as a coal power plant
  • carbon dioxide is separated in a C0 2 ⁇ separation 101 and then burned step 102 with lithium, wherein CO is used as a carrier gas.
  • a third exemplary embodiment of apparatus can be used as fuel gas and nitrogen as the carrier gas in the Darge ⁇ presented in Fig. 1
  • the metal used is, for example, lithium, for example liquid, ie above the melting point of 180.degree.
  • the liquid lithium can be atomized with the nozzle 3 to fine particles and then reacts directly with the fuel gas.
  • a elekt ⁇ innovative ignition or an additional pilot burner may have lent required.
  • the combustion of lithium takes place in the burner first in the nozzle 3 or in the vicinity of the nozzle 3 with the stoichiometrically required amount of nitrogen, with a slightly over or under stoichiometric ratio (eg 0.95: 1 to 1: 0 , 95 for the ratio N 2 : Li) can be selected.
  • a slightly over or under stoichiometric ratio eg 0.95: 1 to 1: 0 , 95 for the ratio N 2 : Li
  • the nozzles can be used here in the highly exothermic reaction for cooling, so that the system does not heat up too much, the lower temperature limit of melting the ent ⁇ standing salts, here lithium nitride, may be.
  • the cyclone is operated with gases other than nitrogen, such as air or carbon dioxide or other gases, lithium oxide (mp 1570 ° C.) or lithium carbonate (mp 723 ° C.) may also be formed in the reaction products.
  • the exhaust gas is passed, for example, in a boiler and used for the evaporation of water to then drive a turbine with downstream generator or other technical devices (eg Heat exchanger) to operate.
  • the cooled after this process exhaust gas can be used in ⁇ example, again for generating the cyclone in the reactor 6.
  • the residual heat of the exhaust gas is used after the evaporation process in the boiler, and it must only the stoichiometrically necessary amount of nitrogen for Ver ⁇ combustion, for example by Lucaszerlegung be recovered.
  • Table 2 shows the relationship between exhaust gas temperature and stoichiometric excess for the combustion of lithium in pure nitrogen, with the calculation of non-temperature-dependent specific heat. Table 2: Operation of the furnace with nitrogen as fuel gas and as carrier gas
  • a corresponding reaction procedure is also shown by way of example in FIG.
  • nitrogen was separated in a Lucaszerle ⁇ supply and then burned step 202 with Li thium ⁇ with nitrogen, for example likewise from the air separation 201, as a carrier gas is used.
  • L1 2 3 203 and the mixture of exhaust gas and carrier gas comprising 2 204 can be passed through a boiler 205, by means of which a steam turbine 206 and thus a Genera ⁇ tor 207 are operated.
  • ammonia can be obtained by hy- rolyse, said LiOH is created 211, which can be converted ⁇ interspersed with carbon dioxide to lithium carbonate 212th
  • nitrogen can act as a carrier gas, which can also be obtained from the first exhaust gas, or the first exhaust gas itself, if it is circulated, for example.
  • the device By the construction of the device according to the invention and the use of the method according to the invention, it is possible to separate the solid or liquid reaction products or their mixture from the exhaust gases in a combustion of metal M with a fuel gas and thus a use in, for example, a boiler and / or a Feed heat exchanger. Furthermore, the device can be operated with increased operating pressure, and thus the combustion and separation / separation process can be adapted to the respective conditions of the subsequent step.
  • the possibility of distinguishing fuel gas and carrier gas to establish the cyclone enables the recirculation of exhaust gases after the heat release. Recirculation is easily possible with this construction. Gas mixtures are possible as fuel and carrier gas ⁇ . By recycling the exhaust gas after the process steps or the energy and material can be saved.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Treating Waste Gases (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé de séparation d'un gaz résiduaire vis-à-vis de produits de réaction solides et/ou liquides lors de la combustion d'un métal M, choisi parmi les métaux alcalins, les métaux alcalino-terreux, Al et Zn et leurs mélanges, avec un gaz combustible. Dans une étape de réaction, le gaz combustible est brûlé avec le métal M et un gaz résiduaire ainsi que d'autres produits de réaction solides et/ou liquides sont générés et, dans une étape de séparation, le gaz résiduaire est séparé des produits de réaction solides et/ou liquides, dans lequel on ajoute en outre un gaz porteur à l'étape de séparation et le gaz porteur est évacué sous forme de mélange avec le gaz résiduaire. L'invention concerne en outre un dispositif pour la mise en œuvre du procédé.
EP15708128.2A 2014-02-19 2015-02-11 Procédé et dispositif de séparation de gaz résiduaire lors de la combustion de certains métaux Withdrawn EP3083500A1 (fr)

Applications Claiming Priority (2)

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DE102014203039.0A DE102014203039A1 (de) 2014-02-19 2014-02-19 Verfahren und Vorrichtung zur Trennung von Abgas bei der Verbrennung bestimmter Metalle
PCT/EP2015/052834 WO2015124474A1 (fr) 2014-02-19 2015-02-11 Procédé et dispositif de séparation de gaz résiduaire lors de la combustion de certains métaux

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EP3083500A1 true EP3083500A1 (fr) 2016-10-26

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US (1) US20170008765A1 (fr)
EP (1) EP3083500A1 (fr)
KR (1) KR101858075B1 (fr)
CN (1) CN106233070A (fr)
DE (1) DE102014203039A1 (fr)
RU (1) RU2655318C2 (fr)
WO (1) WO2015124474A1 (fr)

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DE102014209527A1 (de) 2014-05-20 2015-11-26 Siemens Aktiengesellschaft Verfahren zum Verbrennen einer Legierung eines elektropositiven Metalls
DE102014209529A1 (de) * 2014-05-20 2015-11-26 Siemens Aktiengesellschaft Verbrennung von Lithium bei unterschiedlichen Temperaturen, Drücken und Gasüberschüssen mit porösen Rohren als Brenner
DE102014219274A1 (de) 2014-09-24 2016-03-24 Siemens Aktiengesellschaft Kraftwerk zur Herstellung von Energie und Ammoniak
DE102014219276A1 (de) 2014-09-24 2016-03-24 Siemens Aktiengesellschaft Gas und Dampfkraftwerksanlage (GUD) auf der Basis von elektropositiven Metallen mit optional angeschlossenem Fischer-Tropsch Prozess
DE102014222919A1 (de) 2014-11-11 2016-05-12 Siemens Aktiengesellschaft Verbrennung von elektropositivem Metall in einer Flüssigkeit
DE102015116897A1 (de) * 2015-10-05 2017-04-06 Ventilatorenfabrik Oelde Gmbh Verfahren und Vorrichtung zum Entstauben von Abluft
WO2018065078A1 (fr) 2016-10-04 2018-04-12 Siemens Aktiengesellschaft Procédé et ensemble de récupération d'énergie
DE102018210304A1 (de) * 2018-06-25 2020-01-02 Siemens Aktiengesellschaft Hochstromtaugliches Verfahren zur Herstellung von Ammoniak

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Publication number Publication date
RU2016133748A (ru) 2018-03-22
RU2016133748A3 (fr) 2018-03-22
DE102014203039A1 (de) 2015-08-20
WO2015124474A1 (fr) 2015-08-27
RU2655318C2 (ru) 2018-05-25
KR101858075B1 (ko) 2018-05-15
CN106233070A (zh) 2016-12-14
KR20160123376A (ko) 2016-10-25
US20170008765A1 (en) 2017-01-12

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