WO2015176943A1 - Verbrennung von lithium bei unterschiedlichen temperaturen, drücken und gasüberschüssen mit porösen rohren als brenner - Google Patents
Verbrennung von lithium bei unterschiedlichen temperaturen, drücken und gasüberschüssen mit porösen rohren als brenner Download PDFInfo
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- WO2015176943A1 WO2015176943A1 PCT/EP2015/059724 EP2015059724W WO2015176943A1 WO 2015176943 A1 WO2015176943 A1 WO 2015176943A1 EP 2015059724 W EP2015059724 W EP 2015059724W WO 2015176943 A1 WO2015176943 A1 WO 2015176943A1
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- burner
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Classifications
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
-
- 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
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- 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
- F23C9/00—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber
- F23C9/06—Combustion apparatus characterised by arrangements for returning combustion products or flue gases to the combustion chamber for completing combustion
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- 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
- F23C99/00—Subject-matter not provided for in other groups of this subclass
- F23C99/006—Flameless combustion stabilised within a bed of porous heat-resistant material
Definitions
- the present invention relates to a method for combusting a metal M is selected from alkali, alkaline earth ⁇ limetallen, aluminum and zinc, and alloys and / or mixtures thereof, with a fuel gas wherein the combustion by means of a pore burner, a porous tube as a burner, is carried out, an apparatus for carrying out the method and the use of a pore burner comprising a porous tube as a burner, for combustion of a metal M, which is selected from alkali, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof, with a fuel gas.
- the solid final end product of the imple ⁇ wetting of lithium is in each case, where appropriate after hydrolysis, as with nitride, the oxide or carbonate, which can then be reduced back with- means of electrolysis to lithium metal.
- ⁇ with a cycle is established in which produced by wind power, photovoltaic or other regenerative energy sources surplus ⁇ siger current, stored and at the desired time can be converted back into electricity or that chemical raw materials can be recovered.
- Lithium is usually produced by fused-salt electrolysis. For this method, efficiencies of about 42-55%, calculated from process data without Tempera ⁇ turkorrektur the normal potential. In addition to lithium, similar metals such as sodium, potassium, magnesium, calcium, aluminum and zinc can be used.
- Porenbren ⁇ ners which comprises a porous tube as a burner, in the combustion of the metal M with the fuel gas. It has been found Nurge ⁇ that can locate on the porous burner by the use of the porous burner combustion, wherein the combustion products are obtained at pore burner. For example, while at a spraying apply the reaction products in the entire reactor and solid and liquid reaction ⁇ products have to be laboriously separated from gaseous reaction products again, in particular solid and liquid reaction products in the vicinity of the pore burner are located in the combustion with the pore burner, whereby a separation This is facilitated by gaseous combustion products. In this way, the entire Verbrennungsvor ⁇ direction can be made more compact and the combustion gentler for the device by localization of the combustion process can be designed.
- the present invention relates to a method of combusting a metal M selected from alkali metals, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof, with a fuel gas, the combustion by means of a pore burner having a porous Pipe as a burner takes place.
- the present OF INVENTION ⁇ dung relates to an apparatus for combustion of a metal M is selected from alkali, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof, which comprises a pore burner, which comprises a porous tube as a burner,
- a feeding device for a fuel gas which forms ⁇ to supply fuel gas
- a heating device for providing the metal M as a liquid which is designed to, the
- the present invention relates to the use of a porous burner comprising a porous tube as a burner for burning a metal M selected from alkali metals, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof a fuel gas.
- a metal M selected from alkali metals, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof a fuel gas.
- Figure 1 shows schematically an exemplary arrangement for a device according to the invention.
- FIG. 2 schematically shows a detailed view in a further exemplary arrangement for a device according to the invention.
- FIG. 3 schematically shows a further detail view in an additional exemplary arrangement for a device according to the invention.
- FIG. 4 shows schematically an exemplary cross-section through an exemplary device according to the invention in the region of the feed device of the carrier gas to the reactor.
- FIG. 5 shows a scheme for an exemplary reaction of
- Lithium and carbon dioxide to lithium carbonate which can be ⁇ ge carried out according to the method of the invention.
- FIG. 6 shows a scheme for a further exemplary reaction of lithium and nitrogen to lithium nitride and further secondary products, which can be carried out according to the method according to the invention.
- the present invention relates, in a first aspect, to a method of combusting a metal M selected from alkali metals, alkaline earth metals, aluminum and zinc, and alloys and / or mixtures thereof with a fuel gas, the combustion being effected by means of a pore burner comprising porous tube as a burner, takes place.
- the metal M is selected according to certain embodiments from alkali metals, preferably Li, Na, K, Rb and Cs, alkaline earth metals, preferably Mg, Ca, Sr and Ba, Al and Zn, and mixtures and / or alloys 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.
- a fuel gas such gases are in accordance with certain embodiments in question, which can react or Gemi M ⁇ rule and / or alloys of the metals M in an exothermic reaction with said metal, which are not particularly limited loading.
- the fuel gas is air, Sauer ⁇ , carbon dioxide, hydrogen, water vapor, nitrogen oxides NO x, such as nitrous oxide, nitrogen, sulfur dioxide, or Ge ⁇ mix thereof.
- the method can therefore also be used for desulfurization or NOx removal.
- various products can be obtained in this case with the various metals M that can also occur in gaseous form as a solid, flues ⁇ stechnik as well.
- metal M for example, lithium, nitrogen, inter alia Metallnit ⁇ chloride, such as lithium nitride, are formed which can be transmitted later to further react Am ⁇ monia
- metal M such as lithium
- carbon dioxide for example, metal carbonate, for example lithium carbonate, carbon monoxide, metal oxide, eg lithium oxide, or metal carbide, eg lithium carbide, as well as mixtures thereof may arise, from the carbon monoxide higher value, for example ⁇ long -chain, carbon-containing products such as Me ⁇ than, ethane, etc.
- up to gasoline, diesel, but also methanol, etc. can be obtained, for example, in a Fischer-Tropsch process, while from metal carbide, such as lithium carbide, for example, acetylene can be obtained. Furthermore, for example, with nitrous oxide as a fuel gas such as metal nitride arise.
- the pore burner is not particularly limited insofar as it comprises a porous tube as a burner, to which the metal M can be supplied at at least one opening.
- the metal M is supplied only through an opening of the tube and the other end of the tube is ver closed or also consists of the material of the porous tube.
- the porous tube can in this case, for example
- Ceramic tube of alumina or magnesium oxide or a porous metal tube for example, iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zirconium and alloys of these metals, and steels such as stainless steel and chromium-nickel steel.
- the pore burner is made of a material selected from the group consisting of iron,
- steels such as stainless steel and chromium-nickel steel.
- austenitic specific chromium-nickel steels which are ⁇ tent against removal by sodium at high temperature, for example, very resis, but also materials with 32% nickel and 20% chromium, such as AC 66, Incoloy 800 or Pyrotherm G 20132 Nb , still show a relatively favorable corrosion behavior.
- the other components of the pore burner are not limited and may include the feeding device for the metal M and possibly a Zündquel ⁇ le, etc.
- the metal M is passed as a liquid in the pore burner and burned by means of the pore burner, wherein the fuel gas is optionally passed to the outer surfaces of the pore burner and burned with the metal M.
- internal mixing does not occur according to certain embodiments to avoid clogging of the pores by solid reaction products.
- the pore burner is a pore burner without internal mixing. The pores serve in the use of the pore burner according to certain embodiments, only for surface enlargement of the alloy L.
- the pore burner, the metal M is supplied as liquid in the interior of the pore burner ⁇ leads. This leads to a better distribution of the metal M in the pore burner and a more uniform exit of the metal from the pores of the porous tube, so that a more moderate ⁇ reaction between metal M and fuel gas can take place.
- the combustion of metal M and fuel gas can at ⁇ game by way of the size of the pores of the tube, the metal M used, its density - which may be related to the temperature of the metal M, with which the metal M is introduced into the porous burner pressure, , the pressure or the order / or feed rate of the fuel gas, etc. are suitably controlled.
- the metal M for example
- Lithium according to certain embodiments, therefore used liquid, so for example above the
- the melting point of lithium of 180 C The liquid metal M can in this case be pressed into the porous tube, in ⁇ example, with the aid of another, pressurized gas, which is not limited.
- the liquid metal M then passes through the pores of the tube to the surface and burns with the gas to the respective reaction product or the respective
- the fuel gas is directed to the outer surfaces of the pore burner and burned with the metal M.
- a clogging of the pores of the porous tube can be reduced or avoided, so that a cleaning of the pore burner is prevented or even a Abnut ⁇ tion can be reduced.
- the combustion of the metal M on the surface of the porous pipe tends to cross over small ones
- Particles reduced in the gas space / reaction space so that at best larger drops of reaction products, but which can be easily separated from gaseous reaction products, for example, by a cyclone for deposition can be brought to the reactor wall.
- the reactor wall can be cooled, for example with heat exchangers, which can also be connected to turbines and generators.
- the combustion takes place at a temperature which is above the melting point of the salts formed in the reaction of metal M and fuel gas.
- the salts formed during the combustion of metal M and fuel gas can in this case have a melting point which is above the melting point of the metal M, so that a supply of liquid metal M at elevated temperature may be required.
- incineration at a temperature above the melting point of the resulting salts furthermore, contamination of the pore burner by the resulting salts can be avoided, so that the pore burner can be better protected against contaminants, for example also the pores. This allows better operation and reduced cleaning of the device as well as longer periods of use without cleaning. Also, liquid reaction products on the burner can easily drain off.
- burner materials which can withstand the temperatures, such as iron, niobium, tantalum, molybdenum, tungsten, zirconium and alloys of these metals, and stainless steel are preferred.
- the combustion temperature is therefore preferably higher than the melting point of the particular reaction product or of the respective reaction products, hence the pores of the Porenbren ⁇ listeners do not clog, and a removal of the reaction products ⁇ is possible. Furthermore, depending on the reaction product some mixing between the liquid
- Metal M and the reaction product take place, so that the combustion can take place not only locally at the pore opening, but distributed over the entire surface of the tube. This can be controlled, for example, via the feed rate of the metal M.
- the metal M is added to the pore burner as an alloy of at least two metals M.
- a decrease of melting point of the metal M as well as the resulting metal salt or ent ⁇ stationary metal salts so that the process at lower temperatures and may be gently carried out for the apparatus therefore, and reduces the use of highly refractory materials in the device or can be avoided.
- combustion may be with some excess of fuel gas, for example, in a molar ratio of fuel gas
- Metal M of 1.01: 1 and more, preferably 1.05: 1 and more, more preferably 5: 1 and more, even more preferably 10: 1 and more, for example 100: 1 and more, to the exhaust temperature ⁇ temperature to stabilize in a certain temperature range.
- the fuel gas can also be used for heat dissipation to the expanding part of a turbine, etc.
- a separation of exhaust gas from solid and / or liquid reaction products in the combustion of the metal M with a fuel gas can also be carried out, wherein according to certain embodiments in a reaction step the fuel gas is burned with the metal M and exhaust gas and wei ⁇ tere 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.
- a carrier gas can additionally be added in the separation step and the carrier gas can be removed as a mixture with the exhaust gas.
- the carrier gas can also correspond to the exhaust gas, so so that an exhaust gas is, for example during combustion ent ⁇ corresponding to the supplied carrier gas, or may correspond to the fuel gas.
- the reaction products can be separated after combustion.
- 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.
- the gas that is optio ⁇ nal when feeding the metal M can also be ⁇ if the carrier gas correspond.
- 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 100 vol.%, Based on the turned ⁇ continued carbon dioxide, and is taken out as product of value. The more carbon monoxide is produced, the cleaner the carbon monoxide consider ⁇ led.
- Example ⁇ as lithium can be used as carrier gas such as nitrogen are used, so that in the exhaust gas of unreacted nitrogen may be from the combustion as "exhaust gas" adjacent to the carrier gas nitrogen before ⁇ , whereby a gas separation desired, so , can be carried out more easily and according to certain embodiments, with appropriate, preferably quantitative combustion of metal M and nitrogen using suitable, easily ascertainable parameters, may also not be necessary., For example, ammonia from the resulting nitride easily by washing or Cool down to be removed.
- the exhaust gas may correspond to the carrier gas.
- 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% by volume or more, based on the total volume of the exhaust gas, the carrier gas correspond.
- the fuel gas to 90 vol.% Or more, based on the overall volume of the exhaust gas correspond to the carrier gas, and can in some cases even to 100 vol.% Of the carrier gas entspre ⁇ chen.
- the mixture of exhaust gas and carrier gas can be at least partially recycled to the separation step as carrier gas and / or the combustion step as fuel gas.
- a 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 or more by volume, still further.%, Preferably 70 or more by volume, and more preferably 80 vol.% or more based on the total volume of carrier gas and exhaust gas.
- a recirculation of the mixture of exhaust gas and carrier gas to 90 vol.% Or more, based on the total volume of carrier Gergas 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. In this case, then, the carrier gas can be continuously circulated and removed in such an amount as it is modeled by the combustion of metal M and fuel gas.
- Example ⁇ as, for example, carbon monoxide ⁇ which can be continuously removed.
- the separation step takes place in a process according to the invention in a cyclone or a cyclone reactor.
- the cyclone reactor is in this case not particularly limited in its construction 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, as well as a discharge device for the Ge ⁇ mixture of exhaust gas and carrier gas, which after the fürmi- tion of the two gases after the burning of the metal M in the fuel gas results, can be attached.
- a cyclone reactor used in accordance with the invention may also have a different structure and possibly also comprise further regions.
- individual portions eg reaction region Separations ⁇ area, expansion chamber
- the addition of carrier gas can also take place in an area in which the reaction of the metal M and the fuel gas is advanced or already completed.
- the reaction products are largely in the center of the reactor, for example, a furnace chamber held ⁇ th, and since the combustion of the surface of the porous tube no small particles arise as in the atomization, the exhaust gas is free of solid or liquid
- the exhaust gas temperature may, according to certain embodiments, be controlled by the excess gas in the different combustion processes so that it is higher than the melting temperature of the reaction products or their mixture.
- 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. Such a grid can be additionally prevent subsequent stirring up of solid and / or liquid reaction products in the cyclone reactor.
- the reaction products of the combustion can to generate energy, preferably using at least one former ⁇ panderturbine and / or at least a gas turbine, are used in ⁇ game as a steam turbine, and / or at least one heat exchanger and / or at least a boiler, wherein according here certain embodiments, both the resulting solid and / or liquid reaction products, for example using a heat exchanger at Reak ⁇ gate, or the gaseous reaction products can be used.
- the mixture of flue gas and carrier gas can, according to certain exporting ⁇ approximately forms, for example in the reactor and / or during and / or after removal from the reactor, to heat a boiler or for heat transfer in a heat exchanger or a turbine,
- a gas turbine or an Ex ⁇ panderturbine be used.
- the mixture of the carrier gas and the exhaust gas may be under increased pressure after combustion, for example more than 1 bar, at least 2 bar, at least 5 bar or at least 20 bar.
- an apparatus for burning a metal M selected from alkali metals, alkaline earth metals, aluminum and zinc, as well as alloys and / or mixtures thereof is disclosed
- a pore burner which comprises a porous tube as a burner
- a feeding device for a metal M preferably as
- a heating device for providing the metal M as a liquid, which is adapted to liquefy the metal M.
- the pore burner can be configured as described above.
- a feeding device for metal M for example, tubes or hoses, or conveyor belts, serve, which can be heated, which can be suitably, for example ⁇ based on the state of aggregation of the metal M, determined.
- a further supply device for a gas optionally with a control device such as a valve, are attached, with which the supply of the metal M can be controlled.
- the feed device for the fuel gas can be designed as a tube or hose, etc., which may or may not be heated, wherein the feed device can be suitably determined on the basis of the state of the gas, which may also be under pressure , Also, multiple feeders for metal M or fuel gas can be provided.
- the feed device for the fuel gas is arranged to direct the fuel gas, at least partially, and preferably completely, to the upper ⁇ surface of the pore burner. This results in a verbes ⁇ serte reaction between metal M and the fuel gas is achieved.
- the pore burner is arranged in such a way that combustion reaction products and optionally unreacted metal M can be separated from the surface of the pore burner by gravity, for example by mounting the pore burner in the reactor perpendicular to the earth's surface.
- the porous combustion tubes are arranged vertically in the furnace chamber, the resulting liquid reaction product can run down the tube and then drip down into the furnace sump. On This way is also the possibly dissolved metal M,
- lithium which is not previously reacted at the pore burner burn, and the heat of reaction is delivered to the passing fuel and carrier gas.
- the porous burner made of a material selected from the group best ⁇ starting from iron, chromium, nickel, niobium, tantalum, molybdenum, Wolf ⁇ ram, zirconium, and alloys of these metals, and steels such as stainless steel and chromium nickel steel. These materials are preferred for use at higher temperatures at which the reaction with molten metal M and, if necessary, with entste ⁇ Henden liquid metal salts can vonstatten addition easier.
- the device according to the invention may further comprise a separation device of the products of the combustion of the metal M, which is designed to separate the combustion products of the metal M and the Brennga ⁇ ses, wherein the separation device is preferably a Zyk- lonreaktor.
- the separator may serve to separate exhaust gas in the combustion of the metal M with a fuel gas, and may include:
- a supply device for carrier gas which is keptbil ⁇ det to supply the reactor carrier gas.
- a discharge device for a mixture of exhaust gas and carrier gas which is designed to dissipate a mixture of the off ⁇ gas 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 fuel gas lead off ⁇ .
- the feed device for carrier gas is also not sawn Sonders limited and includes, for example pipes, Schläu ⁇ che, etc., wherein the feed for carrier gas can be appropriately determined based on the state of the carrier gas, which if desired may also be under pressure.
- 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, according to certain embodiments, have a reaction region at which the feed devices for the fuel gas, metal M and the carrier gas and the pore burner 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 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
- the cyclone reactor 6 shown in FIG. 1 comprises a reaction region 20a, a separation region 20b which lies 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.
- a feeder 1 for fuel gas for example in the form of a possibly heated tube or hose
- a feeder 2 for metal M for example in the form of a possibly heated pipe or a hose, wherein the supply of the metal M to the burner 3 burner.
- the supply of the metal M takes place according to Figure 1 with the aid of a gas in a feeder 2 ⁇ for gas, such as a pipe or hose whose supply can be controlled with a valve 2 ⁇ ⁇ .
- the metal M and the fuel gas are supplied to the reaction region 20a.
- the carrier gas ei ⁇ nem area 4 is supplied ⁇ for distributing gas, the carrier gas via nozzles 5 with which a cyclone may be formed from the then, the separation area is supplied 20b.
- FIG. 4 A detailed view of such a feed device 4 with a region 4 ⁇ for gas distribution and a nozzle 5 is exemplified in cross section in Figure 4 (representation without pore burner 3), but also more nozzles 5 may be present, for example at a suitable distance around the inner wall of area 4 to create a suitable cyclone.
- the lower component 6b which comprises the expansion ⁇ chamber 20c, solid and / or liquid reaction ⁇ products are discharged via the discharge device 7 for solid and / or liquid reaction products of the combustion of metal M with the fuel gas, while the mixture of exhaust gas and Carrier gas is discharged via the discharge device 8 for the mixture of exhaust gas and carrier gas.
- an ignition device such as an electrical ignition ⁇ device or a plasma arc may be required,
- the fuel gas of the type and state of the metal M for example, its temperature and / or physical state of the Beschaf ⁇ fenheit
- an ignition device such as an electrical ignition ⁇ device or a plasma arc
- its pressure and / or temperature and the arrangement of components in the device, such as the nature and condition of the feeders may depend.
- a high exhaust gas temperature for example, more than 200 ° C, for example, 600 ° C or more and in certain embodiments 700 ° C or more, as well as an increased (eg 5 bar or more) or high (20 bar or more) Operating pressure to achieve, 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 sufficiently little Leaves heat through, so that outside 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 erfindungsge ⁇ MAESSEN device.
- the cyclone reactor may comprise a grid which is designed such that the solid and / or liquid Reaction products can be removed during 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 by way of example in Figure 2, according to the, is the grating 6 ⁇ way of example in the cyclone reactor 6, which is shown in Figure 1 in the lower member 6b above the Abvanteinrich ⁇ tung 7 and below the discharge means. 8
- the grid preferably goal wall with sufficiently distanced from a reactor, a secure separation of solid and flüssi ⁇ gen reaction products or mixtures thereof 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 feed means for the carrier gas is not particularly limited as long as the carrier gas with the Ab ⁇ gas can be mixed from the combustion of metal M and fuel gas.
- a cyclone preferably arises, for example with the device shown in FIG.
- 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. Accordingly, suitable geometries of injection can be readily determined in a suitable way, for example, based on Strömungssimulati ⁇ ones.
- the discharge devices are not particularly limited, for example, the discharge device for the mixture of exhaust gas and carrier gas may be formed as a tube, currency ⁇ rend the discharge device for the solid and / or liquid Reaction products of the combustion of metal M may be configured with the fuel gas, for example as a rotary valve and / or as a pipe with a siphon.
- Various valves, such as pressure valves, and / or further regulators may also be provided here.
- a shown in FIG 3, for illustrative ⁇ discharge device 7, for example of the cyclone reactor 6 shown in Figure 1, may comprise a siphon 9, a valve 10 for degassing and a pressure regulator 11 in this case, but is not limited to such.
- Such Si- phon at the discharge device for the solid and / or liquid reaction products of the combustion of the metal M with the fuel gas optionally in combination with a suitable for the respective Be ⁇ operating pressure pressure regulator, for example, can be used to provide increased or high To allow operating pressure.
- the discharge device for the mixture of exhaust gas and carrier gas may according to certain embodiments also include a separator 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 total volume of carrier gas and the exhaust gas take place.
- a device according to the invention may further comprise at least one boiler and / or at least one heat exchanger and / or at least one gas turbine ⁇ turbine and / or at least one expander turbine include or is located in the reactor and / or the discharge device for the mixture of exhaust gas and carrier gas.
- the apparatus of Figure 1 which includes a cyclone reactor 6, in the reactor 6, in the discharge device 8 and / or in a device which adjoins the discharge device 8, one or more substancestau ⁇ shear and / or boilers and / or gas turbines and / or expander turbines may be provided, which are not shown.
- Heat exchange may also take place on the cyclone reactor 6 itself, for example on the outer walls in the reaction area 20a and / or the separation area 20b, but possibly also in the area of the expansion chamber 20c, the corresponding heat exchangers then also being able to be connected to turbines for generating electricity in generators.
- the exhaust gases may thus, as a mixture with carrier gas, be further used e.g. Heating a boiler for steam generation, heat dissipation in a heat exchanger, operation of a turbine, etc. are supplied.
- the reactor wall can, for example, function as a heat exchanger, while special solid heat exchangers can be required in the case of solid reaction products formed.
- a direct conduction of the mixture of exhaust gas and carrier gas to a turbine is possibly also possible, so that then no heat exchangers and / or boilers in Exhaust gas flow may be required.
- a device 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.
- 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.
- 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 present OF INVENTION ⁇ dung also relates to the use of a pore burner, comprising a porö ⁇ ses tube as a burner, for combusting a metal M is selected from alkali, alkaline earth metals, aluminum s ⁇ nium, and zinc, and alloys and / or mixtures thereof, with a fuel gas.
- the metal M used liquid, ie above the melting point, for lithium 180 C.
- the liquid metal M for example lithium
- the liquid metal M can be introduced into the pore burner and then reacts immediately, optionally after ignition to start the Reaction, with the respective fuel gas, eg air, Oxygen, carbon dioxide, sulfur dioxide, hydrogen, What ⁇ serdampf, nitrogen oxides NO x as nitrous oxide, or stick ⁇ material.
- the combustion of the metal M, such as lithium can be carried out in the embodiment shown in Figure 1 device beispiels-, with a more than stoichiometric amount of Brennga ⁇ ses to produce not too high exhaust gas temperatures.
- the fuel gas can also be added in stoichiometric or substoichiometric amount compared to the metal M.
- a carrier gas eg, nitrogen, air, carbon monoxide, carbon dioxide, and ammonia
- the hot exhaust stream may then be used to heat a boiler for heat transfer in a heat exchanger or the like.
- 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 M is for example lithium, for example, is turned ⁇ liquid, ie above the melting point of 180 ° C.
- the FLÜS ⁇ SiGe lithium is introduced into the porous burner 3 and rea ⁇ then yaws directly with the fuel gas. You may need an electric ignition or an additional pilot burner.
- Combustion of lithium is carried on the porous burner 3, be ⁇ vorzugt with the stoichiometrically required amount of carbon dioxide, where one or slightly above (eg understöchiomet- skills ratio 0.95: 1 to 1: 0.95 for the ratio of C0 2: Li) can be selected.
- one or slightly above eg understöchiomet- skills ratio 0.95: 1 to 1: 0.95 for the ratio of C0 2: Li
- lithium carbide can be produced, from which acetylene can then be obtained.
- the second step takes place in the middle part of the reactor / 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.
- 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 carrier gas and / or fuel gas by feeding 1.5 over at least 723 ° C, it can be excluded from hen liquid reaction products for combustion.
- the feeders 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 the melting point of the resulting salts, here lithium carbonate, may be.
- the cyclone is also operated with gases other than carbon dioxide, such as air or nitrogen or other gases, lithium oxide (melting point Mp 1570 ° C) or lithium nitride (Mp 813 ° C) may also be formed in the reaction products.
- the mixture of exhaust gas and carrier gas for example, passed into a boiler and used for the evaporation of water, then to drive a steam turbine with a downstream Genera ⁇ tor or others to operate technical devices (eg heat exchangers).
- the cooled off after this process mixture of exhaust gas and carrier gas can then be re ⁇ example be used as a carrier gas for generating the cyclone 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 carbon dioxide for Ver combustion with Li by exhaust gas purification, for example, from coal-fired power plants are obtained.
- 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.
- Combustion may occur with some excess fuel gas, in accordance with certain embodiments.
- the exhaust gas temperature may, according to certain embodiments, be controlled in the various combustion processes by the excess gas so that it may be higher than the melting temperature of the reaction products or their mixture (Table 1).
- 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 sits ⁇ a significantly higher proportion of carbon monoxide, as shown in Table 1. By a subsequent gas separation, carbon monoxide can be purified from carbon dioxide, and the carbon dioxide can be reused in the cycle or in the burner.
- the combustion temperature in the furnace can be lowered.
- stoichiometric combustion gas temperatures of over 3000 K can be reached, which would lead to material problems. Lowering the combustion temperature would also be possible by surplus CO2. However, this takes about 16 times higher than the stoichiometric amount have, would be present so that the Pro ⁇ duktgas CO highly diluted in the C02 excess (concentration of only about 6 Vol.%). Therefore, according to certain embodiments, it makes sense to return some of the product gas CO to the burner and to use it as a thermal ballast to lower the temperature. Before given to a certain reaction temperature is set by recycling a constant amount of mixture of exhaust gas and carrier gas as the carrier gas.
- a waste gas 100 for example from a combustion power plant such as a coal power plant, carbon dioxide is separated in a CO 2 separation 101 and then burned with lithium in step 102, CO being used as the carrier gas.
- CO being used as the carrier gas.
- L1 2 CO 3 103 a mixture of exhaust gas and carrier gas comprising CO 2 and CO may, if necessary after ei ⁇ ner separation 104, are passed through a boiler 105, with the aid of a steam turbine 106 and thus a generator 107 operated become.
- a third exemplary embodiment of apparatus can be used as fuel gas and nitrogen as the carrier gas in the ⁇ represent provided 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 supplied to the pore burner 3 and then reacts directly with the fuel gas. You may need an electric ignition or an additional pilot burner.
- the combustion of lithium takes place at the pore burner 3 with the stoichiometrically required amount of nitrogen, although a slightly higher or lower stoichiometric ratio (eg 0.95: 1 to 1: 0.95 for the ratio 2 : Li) can be selected.
- a slightly higher or lower stoichiometric ratio eg 0.95: 1 to 1: 0.95 for the ratio 2 : Li
- the mixture of the combustion products with the carrier gas, wherein ⁇ game as nitrogen, which is injected through nozzles 5 into the reactor. 6 takes place in the middle part of the reactor 6 This creates a cyclone, which causes the solid and liquid reaction products are swirled to the reactor wall and there divorced mainly from ⁇ .
- ⁇ game as nitrogen which is injected through nozzles 5 into the reactor. 6
- For combustion in pure nitrogen that has resulting lithium nitride has a melting point of 813 ° C. If the combustion temperature of the reaction products retained by means to ⁇ mixture of carrier gas and / or fuel gas by feeding 1.5 over at least 813 ° C, so one can start from the liquid reaction products for combustion.
- the feeders 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 the melting point of the resulting salts, here lithium nitride, may be. Is the cyclone with other gases than
- Nitrogen such as air or carbon dioxide or other Ga ⁇ sen operated, lithium oxide (Mp 1570 ° C) or lithium carbonate (Mp 723 ° C) may be formed in the reaction products.
- the exhaust gas is passed, for example, in a boiler and used to evaporate 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 for example be used again to generate 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 combustion, for example, by Heilzerlegung 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
- Combustion may occur with some excess fuel gas, in accordance with certain embodiments.
- a molar ratio of fuel gas to metal M of more than 1.01: 1, preferably more than 1.05: 1, more preferably 5: 1 and more, even more preferably 10: 1 and more, for example 100: 1 and more to that
- the exhaust gas temperature may, according to certain embodiments, be controlled in the various combustion processes by the excess gas so that it may be higher than the melting temperature of the reaction products or their mixture (Table 2).
- a corresponding reaction procedure is also shown by way of example in FIG.
- nitrogen is separated and then burned at step 202 with lithium in an air separation ⁇ interpretation, with nitrogen, for example likewise from the air separation 201, as a carrier gas is used.
- nitrogen for example likewise from the air separation 201
- From the lithium nitride 203 may by Hyd ⁇ rolyse 209 ammonia 210 are obtained, said LiOH is created 211, which is converted with carbon dioxide to lithium carbonate 212 may be.
- 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.
- Heat exchanger or to supply a boiler.
- the entire combustion device can be made more compact and the combustion can be designed more gently for the device by locating the combustion process.
- the device for example a reactor such as a furnace
- the combustion and separation process can be adapted to the respective conditions of the subsequent step.
- the possibility of distinguishing fuel gas and carrier gas to establish a cyclone makes it possible, in certain embodiments, to recirculate exhaust gases after the heat has been released. Recirculation is easily possible with this construction. Also 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)
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- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2016149495A RU2647187C1 (ru) | 2014-05-20 | 2015-05-04 | Сжигание лития при различных температурах, давлениях и избытках газа с использованием пористых труб в качестве горелок |
CN201580039635.5A CN106537035A (zh) | 2014-05-20 | 2015-05-04 | 用多孔管作为燃烧器在不同温度、压力和气体过量下燃烧锂 |
EP15723658.9A EP3123078A1 (de) | 2014-05-20 | 2015-05-04 | Verbrennung von lithium bei unterschiedlichen temperaturen, drücken und gasüberschüssen mit porösen rohren als brenner |
US15/311,258 US20170082284A1 (en) | 2014-05-20 | 2015-05-04 | Combustion Of Lithium At Different Temperatures And Pres-sures And With Gas Surpluses Using Porous Tubes As Burners |
KR1020167035513A KR20170010805A (ko) | 2014-05-20 | 2015-05-04 | 다공성 튜브들을 버너들로서 사용한, 상이한 온도들 및 압력들에서의 그리고 가스 과잉들을 이용한 리튬의 연소 |
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DE102014209529.8A DE102014209529A1 (de) | 2014-05-20 | 2014-05-20 | Verbrennung von Lithium bei unterschiedlichen Temperaturen, Drücken und Gasüberschüssen mit porösen Rohren als Brenner |
DE102014209529.8 | 2014-05-20 |
Publications (1)
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WO2015176943A1 true WO2015176943A1 (de) | 2015-11-26 |
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PCT/EP2015/059724 WO2015176943A1 (de) | 2014-05-20 | 2015-05-04 | Verbrennung von lithium bei unterschiedlichen temperaturen, drücken und gasüberschüssen mit porösen rohren als brenner |
Country Status (7)
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US (1) | US20170082284A1 (de) |
EP (1) | EP3123078A1 (de) |
KR (1) | KR20170010805A (de) |
CN (1) | CN106537035A (de) |
DE (1) | DE102014209529A1 (de) |
RU (1) | RU2647187C1 (de) |
WO (1) | WO2015176943A1 (de) |
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DE102014222919A1 (de) | 2014-11-11 | 2016-05-12 | Siemens Aktiengesellschaft | Verbrennung von elektropositivem Metall in einer Flüssigkeit |
WO2018065078A1 (de) | 2016-10-04 | 2018-04-12 | Siemens Aktiengesellschaft | Verfahren und anordnung zur energiegewinnung |
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Also Published As
Publication number | Publication date |
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EP3123078A1 (de) | 2017-02-01 |
DE102014209529A1 (de) | 2015-11-26 |
KR20170010805A (ko) | 2017-02-01 |
US20170082284A1 (en) | 2017-03-23 |
CN106537035A (zh) | 2017-03-22 |
RU2647187C1 (ru) | 2018-03-14 |
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