WO2018065078A1 - Method and arrangement for generating power - Google Patents

Method and arrangement for generating power Download PDF

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Publication number
WO2018065078A1
WO2018065078A1 PCT/EP2016/082865 EP2016082865W WO2018065078A1 WO 2018065078 A1 WO2018065078 A1 WO 2018065078A1 EP 2016082865 W EP2016082865 W EP 2016082865W WO 2018065078 A1 WO2018065078 A1 WO 2018065078A1
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WO
WIPO (PCT)
Prior art keywords
melting chamber
gas
metal
outer
inner wall
Prior art date
Application number
PCT/EP2016/082865
Other languages
German (de)
French (fr)
Inventor
Pascal Maas
Viktor Scherer
Martin Schiemann
Günter Schmid
Dan Taroata
Original Assignee
Siemens Aktiengesellschaft
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
Priority to DE102016219183.7 priority Critical
Priority to DE102016219183 priority
Priority to DE102016223851.5 priority
Priority to DE102016223851 priority
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2018065078A1 publication Critical patent/WO2018065078A1/en

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C99/00Subject-matter not provided for in other groups of this subclass

Abstract

The invention relates to a method for the combustion of a fuel gas in a melting chamber, in which a metal M, which is selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and/or mixtures of same, undergoes combustion with the fuel gas; to a melting chamber in which the method can take place; and to a melt firing system comprising such a melting chamber.

Description

description

Method and arrangement for energy production The invention relates to a method for burning a

Fuel gas in a Schmelzkämmer, in which method a metal M, which is selected from alkali metals, Erdalkalime ¬ cal, Al and Zn, and alloys and / or mixtures thereof, is burned with the fuel gas, a Schmelzkämmer, in which the process can be carried out , as well as a Schmelzfeuerung with such Schmelzkämmer.

The present description is based, in whole or in part, on articles which are known from DE102014202591, DE102014203039, DE102014210402, DE102014209529, DE102014219276, US Pat.

DE102014219274, DE102014219275, DE102014222919,

DE102008031437 are known, reference. Their disclosure is therefore in each case added to this description by reference and thus forms part of the disclosure of the present application.

In DE102008031437 is described and added at least in this context of the present description by reference, as can be represented with alkali metals fully recirculated energy cycles. These are in W02012 / 038330 and W02013 / 156476 detail out processing ¬ tet, and at least in this respect the present descrip ¬ exercise is added either together with at least the part of DE102014219274 in which it was described how such a plant might look like.

In DE102014203039 is described and is added at least within this scope of the present description by reference, as emerging lithium nitride can be separated by means of a cyclone after combustion. As part of the

Among other things, disclosure of the present invention illustrates the combustion of lithium in a melt chamber vessel. The melting chamber firing is also used in the combustion of fossil fuels. For example, in the Ake T, Beittel R, Lisauskas R, Riley D., Slag Tap Firing System for a Low Emission Boiler. Netl.doe.gov 2008. "and also included in the present specification by reference, coal firing is known, as is the case with the" Black JB, NETL Cost and Performance Baseline for Fossil Energy Plants Volume 3a: Low Rank Coal to Electricity: IGCC Gases 2011. " Known, as well as Refe ¬ rence included article a Flugstromvergaser is known.

The present invention describes the Ver ¬ combustion of metals in a corresponding combustion chamber, such as a 100MW combustion chamber, and further discloses the feasibility of the invention with results here, for example, on experimental results on a small scale, in particular single particle reactions, burner concepts with metal atomization in the field of 30kW th (thermal) and based on it simulations of a large-scale plant.

The invention is based inter alia on the fact that over the years a large number of energy production devices have been proposed which operate with heat generated in the oxidation of, for example, metallic lithium, as can be seen, for example, in US Pat. No. 3,328,957, the disclosure of which, at least in this regard, is attached to this description.

In such a system, for example, water and lithium are reacted with each other to produce lithium hydroxide, hydrogen and steam. Elsewhere in the system of witnessed by the reaction between lithium and water ER- hydrogen with oxygen to form zusätzli ¬ chem vapor is combined. The steam is then used to drive a turbine or the like, so as to obtain a power generation source. The invention is also based on an inventive manner on the fact that electropositive metals such as lithium can also be used in addition to the extraction of basic chemicals. Examples include the reaction with nitrogen to lithium nitride and subsequent hydrolysis to ammonia, or the reaction with carbon dioxide to lithium oxide and carbon monoxide. The solid end product of the reaction of lithium is depending ¬ weils the oxide or carbonate, then the rolyse again by means of elec- can be reduced to lithium metal.

Thus, a circuit can be established with respect to the electropositive metal in which current, e.g. Excess electricity, for example, from renewable energy sources such as wind and / or photovoltaic (PV), stored and the desired

Time can be converted back into electricity and / or chemical raw materials can be obtained.

However, there remains a need for efficient implementation of electropositive metals as well as efficient separation of combustion products, particularly when performing such a process in the area of high thermal performance. In the context of the present invention, a reactor concept for the combustion of metals is presented in which the thermal power can be in the range of a few 100 kW to 500 MW or even 1 GW. According to a first aspect, the present invention relates to a method for combusting a fuel gas in a

Melting chamber, in which method a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, is burned with the fuel gas, wherein the metal M and a primary gas comprising the fuel gas from above into an outside area the melting chamber are introduced between an outer wall and an inner wall of the melting chamber, wherein the metal M and / or the primary gas is introduced substantially tangentially to the outer and / or inner wall at an angle φ to the vertical in the outer region of the melting chamber, wherein the vertical extends substantially parallel to the outer wall and the inner wall.

In addition, the present invention relates to a Schmelzkämmer, comprising:

an outer area between an outer wall and an inner wall of the melting chambers;

an inner area within the inner wall of the melting chamber;

a bottom portion located below both the outside and inside of the melting chamber, including a substantially inwardly inclined bottom connected to the outside wall;

a drain for a melt, which is located centrally in Bodenbe ¬ rich and is connected to the inclined floor; a plurality of nozzles above and in an upper area of the outside of the melting chambers, respectively, which are formed, a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, in the outside of the melting chamber to bring in;

a plurality of primary gas inlets at an upper portion of the outer region of the melt comber which are to ausgebil ¬ det comprising introducing a primary gas, a fuel gas into the outer ¬ range of the melting chamber;

at least one gas outlet at an upper end of the interior of the melting chambers;

wherein the plurality of primary gas inlets and / or the plurality of nozzles are configured such that the primary gas and / or the metal M are substantially tangent to the outer and / or inner wall at an angle φ to the vertical in the outer region of the melting chamber between the outer wall and the inner wall of the melting chamber, wherein the vertical extends substantially parallel to the outer wall and the inner wall. In addition, a melting chamber furnace is disclosed, comprising the inventive melting chamber and a boiler, which is mounted above the melting chamber and which is connected thereto.

Further aspects of the present invention can be found in the dependent claims and the detailed description and the attached figures.

Description of the figures

The accompanying drawings are intended to illustrate embodiments of the present invention and to provide further understanding thereof. In the context of the description, they serve to explain concepts and principles of the invention. Other embodiments and many of the stated advantages will become apparent with reference to the drawings. The elements of the drawings are not necessarily shown to scale to each other. Identical, functionally identical and identically acting elements, features and components are in the figures of the drawings, unless otherwise stated, each provided with the same reference numerals. FIG. 1 shows the dependence of the particle size distribution on the nozzle diameter during an atomization of lithium with the aid of a single-fluid spin-pressure nozzle.

FIG. 2 shows the dependence of the particle size distribution on the atomization gas velocity during the atomization of a lithium melt with the aid of a two-substance nozzle.

FIG. 3 schematically shows a detail of a melting chamber according to the invention with exemplary gas flows.

FIG. 4 schematically shows a 1/8 section of a melting chamber according to the invention. FIG. 5 schematically shows a 1/8 section of a melting chamber according to the invention from the top view (xy plane). 6 shows a section through the xz plane ei ¬ ner melting chamber according to the invention schematically.

FIGS. 7 and 8 show diagrammatically the principle of the use of melting scavengers (FIG. 7) or melting scavengers with an inner cone (FIG. 8) in a melting chamber according to the invention.

FIG. 9 shows results of a simulation with a reaction gas excess of 1.3 and an introduction angle of 30 ° in a melting chamber according to the invention - as shown in FIG. 6, the temperatures in K being indicated in the xz sectional plane.

FIG. 10 shows results of the temperature distribution on the walls of a melting chamber according to the invention - as shown in FIG.

FIG. 11 shows the axial velocity v ax in the z direction (z axis upward) in the xz plane, as shown in FIG. 6, in m / s in the simulation with a reaction gas excess of 1.3 and 1 Introduction angle of 30 ° are ent ¬ taken.

The figure 12 is analogous to Figure 11, the results of the rapid Dialen velocity V r in the x-direction (x-axis to the right) in the xz plane - as shown in Figure 6 - in m / s in the Si ¬ mulation a reaction gas excess of 1.3 and an introduction angle of 30 ° shown. Figure 13 shows analogously to Figure 11, the results of the tangentia ¬ len speed v tan in y-direction (y-axis in the Zei ¬ chenebene in) in the xz plane - as shown in Figure 6 - in m / s in the simulation with a reaction gas excess of 1.3 and an introduction angle of 30 °.

The figures 14 to 16 are exemplary particle trajectories of exemplary introduced metal particles with the relative degree of conversion X rel in the simulation with a Reakti ¬ onsgasüberschuss of 1.3 and an inlet angle of 30 ° (Figure 14), 15 ° (Figure 15) and 0 ° (FIG. 16) in a melt chamber cutout shown according to FIG.

Figure 17 shows the results of the turbulent intensity I structure of a simulation with a reaction gas excess of 1.3 and an inlet angle of 30 ° with the xz plane of an OF INVENTION ¬ to the invention the melting chamber - as shown in FIG. 6

Figures 18 and 19 show the dependence of the conversion ¬ rate (Figure 18) and the outlet temperature of the gas and the product particles / gobs at the outlet (Figure 19) from the Einleitwinkel of the metal droplets and the primary gas, and the ratio of lambda (λ) between the actual Gas mass flow and at least necessary reaction gas mass flow for a complete reaction of the metal drops. (Lambda = reaction gas / minimum reaction gas). definitions

Used herein ¬ tech niche and scientific terms have as otherwise defined the same meaning as commonly understood by a person skilled in the art of the invention commonly.

In the context of the present invention, electropositive metals are understood in particular to be the alkali metals and alkaline earth metals as well as aluminum and zinc. Are preferred as electropositive sitive metals Li, Na, K, Mg, Ca, Sr, Ba, Al and Zn and Mi ¬ mixtures and / or alloys thereof, more preferably Li, Na, K, Mg, Ca, Sr and Ba as well as Mixtures and / or alloys thereof. A Schmelzkammerfeuerung, also called briefly Schmelzfeuerung, is a device for burning fuels, are achieved in the so high temperatures that at least one resulting product, which at room temperature

Solid, remains liquid and thus can be used as liquid abgezo ¬ gen.

In a first aspect, the present invention relates to a method of combusting a fuel gas in a melting chamber, in which method a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof is burned with the fuel gas wherein the metal M and a primary gas comprising the fuel gas are introduced from above into an outer region of the melting chamber between an outer wall and an inner wall of the melting chamber, wherein the metal M and / or the primary gas substantially tangential to the outer and / or inner wall at an angle φ are introduced to the vertical in the outer area of the melting chamber, wherein the vertical extends substantially parallel to the outer wall and the inner wall.

The vertical runs in the melting chamber from top to bottom, towards the bottom. The tangent to the outer and / or inner wall is obtained in contrast as a horizontal tangent to the respective wall, so a corresponding curve of the outer and / or inner wall which for example, at Hohlzylin ¬ countries as the outer and / or inner wall of a tangent to a Circle represents. Besides circular hollow cylinders, the outer and / or inner wall may also be shaped differently, for example with an oval cross section, can be a horizontal tangent to the outer and / or inner wall ge ¬ sets in that a thus has at least one curve. According to certain embodiments, the outer and / or inner wall of a circular hollow cylinder, preferably concentric ¬ specific hollow cylinder are formed. The inner wall and the outer wall are each connected to themselves, so they each connect in a horizontal direction, so that the outer area is created between the two walls. The inner wall is in this case within the outer wall, so that the outer area between the two walls extends in the vertical direction.

The melting chamber itself is not particularly limited, so far as they ¬ having an outer wall and an inner wall, intermediate see which an outer region can be formed. The outer wall and inner wall are substantially parallel to the ground, so that the metal M and the fuel gas can be introduced from above. According to certain execution ¬ form the outer wall and the inner wall are laid out concentrically with each other. According to certain embodiments, the outer wall and the inner wall are substantially round or round in a plan view from above, and thus each have the shape of a substantially round or round hollow cylinder. Thus, in this case, the inner wall of a lower Durchmes- ser than the outer wall where the two are in this case before ¬ Trains t concentrically to form an external region formed between two walls in certain segments with a certain angle to the center of the hollow cylinder is substantially has the same volume, so that the temperature distribution can take place uniformly during combustion.

The wall thicknesses of the outer wall and the inner wall are not particularly limited insofar as they can withstand the gas pressure in the melting chamber.

Also, the material of the outer wall and the inner wall is not particularly limited insofar as it can withstand the temperatures of the combustion of metal M and fuel gas. For example, the inner and outer walls, as well as the other components of the melting chambers, such as the components described in connection with the melting chamber according to the invention, for example the inwardly inclined bottom, the melt outlet, the plurality of nozzles, the A large number of primary and secondary gas inlets, the gas outlet, the melt catchers and / or the tapering cones, and / or the boiler described in connection with the inventive melting chamber furnace, of iron, steel, for example Fe-Cr steel, Fe -Ni-Cr steel, stainless steel, etc. exist, and these may for example be adapted to the metal M and the fuel gas. Also, the different components may consist of the same material or of different ones.

According to certain embodiments, the metal M is selected from Li, Na, K, Mg, Ca, Sr, Ba, Al and Zn and / or mixtures and / or alloys thereof, more preferably Li, Na, K, Mg, Ca, Sr and Ba and / or mixtures and / or alloys thereof.

In addition to lithium, so too is the use of similar metals such as sodium, potassium; Magnesium, calcium; Aluminum and zinc possible.

Furthermore, the fuel gas is not particularly limited, as far as it can be burned with the metal M. For example, air, CO2, water and / or N 2 are suitable as fuel gas, or else mixtures. It can therefore also contain more than one fuel gas. According to certain embodiments, the fuel gas comprises CO2 and / or N 2 . According to certain embodiments , the fuel gas consists essentially of CO 2 and / or N 2 . According to the invention, the combustion of metals M, for example

electropositive metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium or to a limited extent also aluminum or zinc in addition to air in carbon dioxide (CO 2), water (H 2 0) and / or nitrogen possible, with For example, the combustion of Na and / or K preferably with CO2 and / or H 2 0 is carried out. In this case, in particular the che ¬ mixing basic materials carbon monoxide (CO) and / or hydrogen (H 2 ) are formed, as well as, for example, corresponding carbonates, nitrides, etc.

In addition, the primary gas may contain a gas component or a plurality of gas components, which, for example, allows a heat transfer from the reaction. Thus, the primary gas may include at least one further Gaskom ¬ component for heat transfer in addition to the fuel gas continues, a so-called heat transfer gas which can transport the heat produced during combustion me and can act as a moderator. For example, when CO 2 is used as fuel gas CO can serve as a gas component for heat transfer. CO 2 can, for example ¬ from a plant for carbon dioxide separation and / or coal combustion, a coal power plant, etc. come, but it is also not excluded that the primary gas consists only of the fuel gas.

In the method according to the invention, it is thus possible for the heat produced during the combustion of fuel gas and metal M to pass to a heat transfer gas, which then via a gas outlet, possibly together with a product gas and / or unused fuel gas and / or a further gas such as a secondary gas can be discharged into a boiler. The product gas and / or unused fuel gas and / or the further gas, such as a secondary gas, can also absorb heat from the reaction of fuel gas and metal M. The energy contained in the boiler in the gas or gases, for example Wärmeener ¬ energy can then for the extraction of energy, such as district heating and / or electrical energy can be used. It is also possible for product gases to form which can be used further chemically and / or serve as desired products, for example alcohols, such as methanol and / or ethanol, ethene, ethyne, ammonia, etc. The mixture of heat transfer gas, if appropriate together with a product gas and / or unconsumed combustion gas. Gas and / or another gas such as a secondary gas is hereinafter also referred to as product gas mixture. However, heat arising in the reaction can also or additionally already beforehand, for example within the

Melting chamber - are at least partially removed, in ¬ example via heat exchangers, which in the outer and / or inner wall and / or other components of the melt chamber, such as the inwardly inclined bottom, the flow for the melt, the gas outlet, the melt catchers and / or the upwardly tapering cone may be provided, and / or may be separately provided within the melting chamber.

According to certain embodiments, the angle φ is in a range of about 5 ° to about 60 °, preferably about 7 ° to about 45 °, more preferably about 8 ° to about 35 °, even more preferably about 15 ° to about 30 °, especially about 17.5 to about

 21.5 °, for example at about 22 ° to about 23 °, e.g. about 22.5 °. If the angle φ is too small, insufficient reaction of fuel gas and metal M may occur, and it may also be difficult to make a product of combustion of fuel gas and metal M suitable in the art

Separate melting chamber. Again, if the angle φ is too large, the reaction rate between metal M and fuel gas may be too low before the fuel gas and / or the metal M come into contact with the inner and / or outer wall, which may result in a decreased reaction.

By the supply of the primary gas and / or the metal M at a certain angle φ a kind of rotational flow can be achieved, wherein the particles and / or drops of the metal M perform a kind of lateral movement within the melting chamber, so the trajectory thereof also a tangential, Has horizontal component next to the downward flow component. Due to the rotational flow, a turbulent mixing of metal M and primary gas can be achieved. In addition, a kind of vortex or swirling can be produced, and particles can be passed through inertia to externa ¬ ßere wall. It has been shown that by increasing the injection ¬ angle or angle φ in the tangential direction of the

Swirling can increase, which can lead to a better separation of product particles and a smaller extent of the reaction of the particles, since a collision with the wall rather occurs.

According to certain embodiments, the combustion takes place in such a way that a substantially homogeneous temperature distribution during combustion is ensured. This can ¬ example, by suitable timing supply of fuel gas and Me ¬ M tall be ensured.

According to certain embodiments, the metal M and the primary gas are locally introduced together into the melting chamber. According to certain embodiments, the supply of metal M and primary gas takes place in the same direction Rich ¬ . According to certain embodiments, the supply streams of metal M and primary gas do not intersect when fed from different feed points but are introduced in the same direction. According to certain embodiments, the metal M and the primary gas are introduced locally to ¬ together in the same direction in the melting chamber. In addition, the metal M and the primary gas are timely put together in the melting chamber to ensure a reaction of metal M and fuel gas.

The supply or introduction of metal M and primary gas are not particularly limited and can be carried out in a suitable manner. For example, a common supply with ¬ means of a two fluid nozzle can be made, or it may be a feed about one-material nozzles, for example, one-material nozzles, for example,

Single fluid pressure nozzles take place. For this purpose more identical or different nozzles may be provided for introducing the metal M tall and the primary gas as evenly as possible into the outer ¬ area between the inner wall and outer wall. According to certain embodiments, the metal M is supplied liquid. Accordingly, it can be pre-heated, the metal M prior to feeding ge ¬ is suitable, for example by suitable heating means. For example, Li may be preheated to a temperature of about 500 to about 1000 K, eg from about 550 to about 750 K, for example about 570 K to about 705 K, for example about 610 to about 690 K. Likewise, the primary gas can be preheated to set a suitable temperature in the melting chamber, for example with suitable heating devices. For example, a primary gas consisting of CO 2 as a fuel gas and CO as a heat transfer gas to a temperature of about 400 to about 1000 K, eg from about 450 to about 850 K, for example about 470 K to about 705 K, eg about 540 to about 620 K preheated. For other fuel gases and heat transfer gases or generally other primary gases as well as for others

Metals M can give rise to other temperatures, these also being dependent on the metal M used, the mixing ratio of fuel gas and heat transfer gas and other components of the primary gas, the stoichiometry of the combustion, etc., and may depend on a desired temperature in the Melting chamber and / or a desired temperature of a liquid product and / or a desired temperature of a product gas mixture are suitably adjusted. In certain embodiments, metal sprays having particle sizes less than 200-250 ym, e.g. less than 250 ym, less than 230 ym, less than 210 ym or less than 200 ym, used.

The atomization of a molten metal of the metal M, if DIE ses is introduced in liquid, such as a lithium melt can be rea ¬ lisiert advantageously by different sputtering. Examples which may be called single-fluid, two ¬ substance and / or pore nozzles, for example:

• Single fluid pressure nozzles

 • Two-fluid nozzles

• pore nozzles These are not particularly limited in terms of their design. In this case, for example, a spraying of the liquid metal can take place in a two-substance nozzle, in which a negative pressure can be generated by the primary gas flow, so that metal tropics are formed. Alternatively, liquid metal drops can also be produced in a single-substance nozzle.

However, it is not excluded that the metal M is alternatively or additionally supplied in solid form, for example as a powder, by means of suitable nozzles, these nozzles are also not limited.

For the supply as a powder as well as for the supply as a liquid, the particle size of the metal M is not particularly limited. For the present method can therefore ver ¬ different particle size distributions of the starting material, in particular of the metal M used, which can, at ¬ play, by means of sieve analysis or by laser diffraction be ¬ agrees wherein these are not restrictive here for the process.

The supply of metal M and primary gas may be via a plurality of nozzles and a plurality of primary gas inlets to achieve a good distribution of metal M and primary gas in the exterior of the melting chamber between the outer and inner walls.

The supply of metal M through a nozzle takes place in accordance with certain embodiments in such a way that no reaction with the fuel gas takes place at the nozzle itself in order to avoid clogging of the nozzle. This can be accomplished for example by setting an appropriate temperature of the nozzle and / or by mixing metal M and fuel gas and primary gas until au ¬ ßerhalb the nozzle. According to certain embodiments, a turbulence of the supplied metal M and / or of the primary gas takes place through the nozzles and / or primary gas inlets, which can be achieved, for example, by means of corresponding nozzles

Nozzle geometries can be achieved. According to certain embodiments, at least one resulting product of the combustion of the metal M with the

Fuel gas is liquid deposited on fuses within the combustion chamber, wherein the melt catcher are connected to the inner wall. Melt catchers represent struts which, in addition to the inner wall, can be connected to one another or to a central body. These extend, according to certain embodiments, from the inner wall into an inner area of the melting chamber and not into the outer area. In the case of a hollow cylinder as an inner wall, for example, like the spokes of a wheel, they may be arranged inwards towards the central axis of the hollow cylinder, wherein the melt catchers may or may not have an angle to the horizontal.

The melt catchers can ensure that a resulting liquid product can be separated to a large extent from the product stream. In particular, a suitable adjustment of the angle φ of the supply of metal M and / or primary gas is advantageous. For this purpose, the melt catchers may be provided at a suitable point in the melting chamber, for example in an inner region of the melting chamber within the inner wall, or in a region below this inner region. The melt catchers may in this case be connected to themselves or to a central shape which, according to certain embodiments, is arranged concentrically with the inner wall and / or outer wall. The design of the melting catcher here is not particularly be ¬ limits and can be made suitable, for example on the basis of in "Ake T, R Beittel, Lisauskas R, Riley D., Slag Tap Firing System for a Low Emission Boiler. Netl.doe.gov 2008 "referred to in the design of the

Refluxer and therefore in this regard is added to this description by reference. The number of melting scavengers is not particularly limited and can be suitably adjusted, for example, taking into consideration the gas flow in the melting chamber. It may for example be from 4 to 40, for example 8 to 32, for example 12 to 18 or 16 to 26, for example 24. Also, the blocks Di ¬ not limited length depth of the melt scavengers, as well as non their shape, which may for example be approximately rectangular, or a widening of the width of a central axis of the melting chamber toward the inner wall. Also, the fuses may be disposed away from the horizontal plane at an angle of inclination, for example from the inner wall inwardly downwardly, which is not particularly limited so as to better decelerate the gas flow in the melting chamber. In addition, the distance between two melt catchers can be suitably adjusted to reduce the flow cross section. Concerning all these design possibilities the Schmelzfänger becomes again on Ake T, Beitel R, Lisauskas R, Riley D., Slag Tap Firing System for a Low Emission Boiler. Netl.doe.gov 2008 reference.

The fuses may be centrally secured to a central body, such as a tapered cone, which may be solid, for example. Also at this a deposition of a liquid product of the combustion of metal M and fuel gas can take place.

According to certain embodiments, the melt catchers are connected centrally in an inner region of the melting chamber and / or in a bottom region of the melting chamber below the inner region with an upwardly tapered cone.

By suitable adjustment of the melt catcher and its design, an improved separation of liquid gas products of the combustion of metal M and fuel gas can take place. For example, the melt catchers may have a height to width ratio greater than 2: 1, for example 3: 1 or more or 4: 1 or more, at least at one point of connection in the center of the melting chambers, for example in the case of the connection of several melt catchers or the melt catcher to a central body, such as a cone tapering upwards.

According to certain embodiments, the produced during combustion of the fuel gas with the metal M product gas ¬ mixture, as defined above, from below by Schmelzfän- ger passed, disconnecting the optionally contained, entrained liquid products of the combustion of fuel gas and metal M suitable to be able to. For this purpose, the gas stream, which initially comes from above in the outer region, deflected in a bottom region of the melting chamber, for example on an inclined floor. By redirecting the gas flow and passing through the melt catcher, the gas flow can be accelerated. In this case, the liquid product droplets can then also be conducted to the melt catchers as a result of the inflow of metal M and / or primary gas and the resulting rotational flow.

To ensure that the liquid products to the

Melt trap and possibly a central fastening body such as a tapering cone to be deposited as a liquid and direction drain for a melt ablau ¬ fen, the melt catcher and possibly the central mounting body may be heated, for example with residual heat. In order to achieve a better separation as well as a good conversion of metal M and fuel gas, according to certain embodiments, the fuel gas in a, for example ge ¬ wrestle, stoichiometric excess - as a molar ratio - to the metal M (ratio actually introduced fuel gas to amount of fuel gas for a stoichiometric conversion;

hereinafter also referred to as λ), which is preferably at least 1.1, more preferably at least 1.15 or more, even more preferably at least 1.20 or more, more preferably 1.3 or more.

In the combustion of fuel gas and metal M, according to certain embodiments, at least one liquid product is formed within the melting chamber, whereby further liquid and / or gaseous products may also be formed.

In the melting chamber, the products are preferably not solid, but liquid separated to a discharge of Fest ¬ stoffPartikeln with a remaining gas stream comprising heat transfer gas optionally together with a product gas and / or unused fuel gas and / or another gas such as a secondary gas to avoid. For this purpose, the temperature within the melting chamber is regulated in such a way that a temperature prevails at which arising products of the combustion of metal M and fuel gas are liquid and / or gaseous. This can, for example, by suitably adjusting the Tem ¬ temperature of the metal M and / or the primary gas or Brennga- ses, setting a suitable angle φ, setting a suitable inflow of metal M and / or primary gas (volume flow or mass flow), suitable stochastic, feed a heat transfer gas and / or secondary gas, etc. are ensured.

In a combustion of, for example, Li as metal M and CO 2 , a temperature at the outlet or the liquid product produced L1 2 CO 3 and / or Li 2 0 should be between about 1100 K and 1450 K, since at too high a temperature is L1 2 CO 3 decompose zen can and may take place at a too low temperature the formation of solid carbon and / or carbonate, which may as "ash" on the walls, heat exchangers, etc. abset ¬ zen. According to certain embodiments, it is along the outer and / or the inner wall of the melting chamber, as already indicated above, introduces a secondary gas from above into the outer area. least along the inner wall a secondary gas introduced from above into the outer area. According to certain embodiments, the supply of the secondary gas takes place such that at least in an upper region of the outer region there is a laminar flow of the secondary gas. The supply of the secondary gas takes place according to certain embodiments above the supply of the primary gas or at least at the same level. As a result, the walls of metal M and / or liquid products from the combustion of metal M and fuel gas can be protected. According to certain embodiments, the

Feed rate of the secondary gas higher than the supply ¬ speed of the primary gas. Thereby re insbesonde ¬ the walls may be well protected in the area of supply of the primary gas and of the metal M.

The secondary gas can as the primary gas containing a gas component or a plurality of gas components, which allows heat transfer from the reaction, or may also be such a heat transfer gas such as CO at a combustion of CO 2, but may also be a gas mixture, such as at ¬ play recirculated exhaust gas, for example comprising or consisting of CO and CO 2 , for example, if as pri ¬ märgas also a C0 2 / CO mixture is used. Also, the secondary gas, as well as the primary gas and / or the metal M, can be preheated to set a suitable temperature in the melting chamber, for example with ge ¬ suitable heaters. With a suitable adjustment of the temperature profiles of primary gas and secondary gas or the tem- perature when flowing the flow of two in the melting chamber can be specifically controlled so that both ¬ play, at least can slip off during in a particular area to one another, or also achieves a turbulent flow can be.

According to certain embodiments, the flow rate of the secondary gas is at least at the feed higher than the flow rate of the primary gas at least the feed. Thus, a secondary gas is supplied to flow to both the inner wall in the outdoor area as well as on the outer wall in the outer region, the two secondary gas streams of the type of gas and / or the Strömungsgeschwin- can go ¬ clearly distinguish speed and / or be the same.

An electrical ignition or an additional pilot burner may be required to start the reaction. After the ignition process, the metal flame is usually self-sustaining, although further ignition is not excluded according to the invention.

In a further aspect, the present invention relates to a melting chamber, comprising:

an outer area between an outer wall and an inner wall of the melting chambers;

an inner area within the inner wall of the melting chamber;

a bottom portion located below both the outside and inside of the melting chamber, including a substantially inwardly inclined bottom connected to the outside wall;

a drain for a melt, which is located centrally in Bodenbe ¬ rich and is connected to the inclined floor; a plurality of nozzles above and in an upper area of the outside of the melting chambers, respectively, which are formed, a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, in the outside of the melting chamber bring in;

a plurality of primary gas inlets at an upper portion of the outer region of the melt comber which are to ausgebil ¬ det comprising introducing a primary gas, a fuel gas into the outer ¬ range of the melting chamber;

at least one gas outlet at an upper end of the comber for indoor ¬ realm of melting;

wherein the plurality of primary gas inlets and / or the plurality of nozzles are formed such, the primary gas and / or to introduce the metal M substantially tangential to the outer and / or inner wall at an angle φ to the vertical in the outer region of the melting chamber between the outer wall and the inner wall of the melting chamber, wherein the vertical substantially parallel to the outer wall and the inner wall extends.

With the melting chamber according to the invention, the inventive method can be carried out. Thus, the various components of the melting chamber may also be such as have already been described in connection with the method according to the invention.

In particular, the outer region between the outer wall and the inner wall of the melting chamber and the inner region within the inner wall of the melting chambers, as well as the outer and the inner wall, as described above ge ¬ forms his. In order to better deposit a liquid product of the reaction of fuel gas and metal M, the inner and / or outer wall can also be cooled. Any cooling of the wall can also be achieved by introducing a secondary gas along the wall.

The bottom portion, which lies below both the outer region and the inner region of the melting chamber, comprising ei ¬ NEN essentially inwardly inclined bottom, which is connected to the outer wall, a lower portion below the inner wall, the edge of the inner wall spaced from the inclined bottom. He is also not particularly limited.

In addition, the inwardly inclined floor is not particularly limited. According to certain embodiments of the inwardly sloping bottom is inclined such that a FLÜS ¬ Siges reaction product of the reaction of metal M and fuel gas can drain towards the drain. The floor can also be tilted in different sections at different angles be, or may be constantly inclined at a certain angle to the ground.

The sequence for a melt is used to a liquid product of the combustion of metal M and fuel gas from the

Dissipate the melting chamber. It is located in the ground area and possibly under it and is not particularly limited. The in the bottom region and optionally to melt scavengers and / or a central body such as an upwardly tapering cone accumulating liquid product of the combustion of metal M and fuel gas can take place over the course and a wide ¬ ren treatment step or a further processing, a bearing, etc. ., which is not limited here. The position of the drain is central in the floor area, ie, for example, along a central axis with concentric inner and outer walls or around this axis. This may depend, for example, on the nature of for indoor ¬ kingdom, for example, the presence of melting vessels and / or a central body such as to supply pointed upward taper, so that for example the drain may be located around the cone or even a centra may represent ¬ les "hole". according to certain embodiments, in the process as possible, no obstructions, such as grids, etc., exist. at the outlet can also be in accordance with certain embodiments, a negative pressure is applied, for example, using corresponding pumping arrangements to establish a good and To ensure fast drainage of the liquid product of metal M and fuel and to avoid prolonged residence in the melting chamber.

The plurality of nozzles above and in an upper portion of the outside of the molten chambers, respectively, which are formed, a metal M, which is selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, in the outdoor area the melt chamber are not particularly limited, nor are the plurality of primary gas inlets in an upper area of the outer area of the melting chambers, which det are to introduce a primary gas comprising a fuel gas in the outer ¬ area of the melting chamber. As above described in connection with the inventive method, the primary nozzles and gas inlets together or be arranged separately, in accordance with certain embodiments, however, are arranged together in order to achieve rapid mixing of Me ¬ M tall and fuel gas.

The atomization of a molten metal of the metal M, if DIE ses is introduced in liquid, such as a lithium melt can be rea ¬ lisiert advantageously by different sputtering. Examples which may be called single-fluid, two ¬ substance and / or pore nozzles, for example:

Einstoffdralldruckdüsen

 Two-fluid nozzles

 pores nozzles

These are not particularly limited in terms of their design. In this case, for example, a spraying of the liquid metal can take place in a two-substance nozzle, in which a negative pressure can be generated by the primary gas flow, so that metal tropics are formed. Alternatively, liquid metal drops can also be produced in a single-substance nozzle.

However, it is not excluded that the metal M is alternatively or additionally supplied in solid form, for example as a powder, by means of suitable nozzles, which are not limited and may also comprise single-fluid and / or two-fluid nozzles.

For the supply as a powder as well as for the supply as a liquid, the particle size of the metal M is not particularly limited. For the present method can therefore ver ¬ different particle size distributions of the starting material, in particular of the metal M used which at ¬ play by means of sieve analysis or laser diffraction be which are not restrictive to the process here.

In addition, the plurality of primary gas inlets is not particularly limited in terms of Ausgestal ¬ tion. As already shown, the nozzles and primary gas inlets can also be arranged such that metal M and primary gas are substantially at the same place in the same place

Melting chamber are supplied, for example, in the same direction and at the same angle φ. For this example, nozzles such as single-fluid nozzles can be installed at a certain angle, such as the angle φ to the vertical and with tangential outflow to the walls in the melting chamber, for example in the form of Injektorblöcken. Correspondingly, the injection can also be suitably adjusted by means of two-substance nozzles and / or pore nozzles.

The number of nozzles and primary gas inlets is not particularly limited and is preferably selected such that a good distribution of metal M and primary gas in the

Schmelzkämmer, in particular in the outer area, can take place, and this, for example, the geometry of the Schmelzkam ¬ mer, their volume, other installations, etc., may depend. For example, more than 3 nozzles and / or primary gas inlets may be provided, for example 4 or more, 8 or more, 15 or more, 30 or more, 50 or more, or 80 or more. The number of nozzles and primary gas inlets may be the same or different. For example, it is also possible to provide a plurality of primary gas inlets per nozzle for the metal M. Also, the nozzles for the metal M and the primary Gaseinläs ¬ se be summarized, for example, in two-fluid nozzles.

The supply of metal M and primary gas can take place via a plurality of nozzles and a plurality of primary gas inlets, in order to ensure a good distribution of metal M and primary gas in the

Outside of the melting chamber between the outer and inner wall to achieve. The at least one gas outlet at an upper end of the in ¬ nenbereichs the melting chamber is also not particularly limited, and the removal of a product gas mixture is used after the separation of the liquid products of the combustion of metal M and fuel gas. It may have a diameter corresponding to that of the interior of the melting chamber or may be smaller.

According to certain embodiments, the erfindungsge ¬ Permitted melting chamber further comprises at least one secondary gas inlet passage in an upper portion of the outer region of the melting chamber, which is adapted to introduce a secondary gas along the outer and / or inner wall of the melting chamber. According to certain embodiments, the erfindungsge ¬ Permitted melting chamber comprises a plurality of secondary gas inlets at an upper portion of the outer region of the melt comber which are adapted to a secondary gas along the äuße ¬ ren and / or inner wall of the melting chamber to introduce. The secondary gas inlets are in this case preferably arranged in the outer region of the melting chamber such that the secondary gas is introduced along the outer and / or inner wall along. For this example, annular gaps, a plurality of nozzles, etc. may be arranged. In this way, a good protective effect of the respective wall relative to the primary gas and / or the metal M can be achieved.

According to certain embodiments, the erfindungsge ¬ Permitted melting chamber further comprises a plurality of melting vessels that are connected in the interior of the melting chamber with the inner wall. These may be as described above in connection with the method according to the invention. According to certain embodiments, the melt catchers are connected centrally in the interior of the melting chamber and / or in the bottom region of the melting chamber below the interior with an upwardly tapered cone.

An electrical ignition or an additional pilot burner may be required to start the reaction. After this Ignition is the metal flame usually selbststerhal ¬ tend, with a further ignition according to the invention, however, is not excluded. A combustion of an atomized metal M or metal drop can be realized for example by means of a Schmelzkammerfeu ¬ augmentation, as is exemplarily shown in Figures 3 to eighth 3 shows the principle of a melting chamber according to the invention of a melting chamber furnace. In a possible embodiment, the lid of the melt combustion chamber exemplarily has 96 primary gas inlets 1 as gas feeds (shown in a square fashion in FIG. 3, gas flow with black arrows), via which the primary gas is introduced into the process at an angle to the normal in the direction of rotation. Below the primary gas inlets 1 nozzle packets for atomizing the liquid metal are provided in parallel (not shown). The number of nozzles depends on the mass flow of metal required for the combustion power and the mass flow achievable per nozzle, which is not particularly limited. Depending on the design of Me ¬ tallzerstäubungseinheit / nozzle, the number of the nozzle packages can be changed. At the inner and outer edges, annular gaps are provided as secondary gas inlets 2 for the supply of secondary gas, which can provide a protective film on the inner and outer walls (see Fig. 3, secondary gas inlets 2). By injecting metal drop spray and primary gas (irrespective of the design of the nozzle geometry) at a defined angle, a rotational flow sets in the melting chamber. The flow of particles and gas flows to the bottom of the chamber, where it is deflected and then flows upwards towards the boiler (which is positioned above the melting chamber and not shown in the figure for simplicity) through a gas outlet 5 (to the boiler).

The separation of the particles from the flow can take place in several steps, with respect to the structure here Reference is also made to FIGS. 4 to 8. On the one hand, the particles are conveyed by inertial forces to the outer wall 6 (see FIGS. 4 to 6), where they adhere and flow in the direction of inclined bottom 8. On the other hand, 9 melt catchers 3 are attached to the end of the inner wall or inner partition 7 and the cone 6 located centrally on the bottom 6.

The flow or gas flow 10 is greatly accelerated when passing the melt catcher 3, since the flow ¬ cross-section tapers, here for example approximately halved, and deflected; this reduces the flow component in the direction of rotation ¬ tion. The particles can no longer follow the flow 10 and collide against the side of the melt catcher 3 (see

Particle paths 11 in Fig. 7) and flow inward direction cone 9 and ultimately by a drain or a Draina ¬ Ge 4, for example, for L 1 2 CO 3 in a combustion of Li in CO and / or C0 second The principle of the deposition of the melt catcher 3 is shown in Fig. 7 and a representation of the melt catcher 3 with inner cone is shown in Fig. 8. Figure 7 shows the case Gasströ ¬ mung 10 as well as particle paths 11 between two melting vessels 3, wherein the particles bounce off a melting scavenger. 3

As shown in Figure 8, the deposition on the

3, for example, due to the inclination 3a of the melt catchers or the distance 3b between two melt catchers 3-which, for example, causes a reduction or increase in the flow cross-section. Via the outlet 4a of the melt, the separated particles can drain to the drainage 4.

The principle generally corresponds to a variation of the inertia deposition, like "Came M. Mechanical engineering process ¬ 2, Springer-Verlag, 1997" and is hereby included by Re ¬ ference. The size of the angle is adjusted in accordance with certain embodiments - as stated above - according to the particles used. If the angles are too small, neither the wall nor the melting trap will work because the particles follow the flow without encountering interfaces. Another way to improve the

Separating efficiency by geometry is adaptations of the melting catcher 3 (for example, raising the height-to-width ratio) gege ¬ ben.

In yet another aspect, the present OF INVENTION ¬ dung relates to a slag tap furnace comprising the erfindungsge ¬ Permitted melting chamber and a boiler, which is mounted above the melt chamber and which is connected thereto. The connection itself here is not particularly be ¬ limits and can be done in such a way as usual in

Melting chamber firing takes place. The boiler is also not particularly limited, and has also been described above as an example in to ¬ connexion with the inventive method. Essentially, the boiler in the melting chamber firing serves to heat use from the product gas mixture.

In DE102014202591, DE102014203039, DE102014210402,

DE102014209529, DE102014219276, DE102014219274,

DE 102014219275, DE102014222919, DE102008031437 disclose Offenba ¬ ments that the invention, as is clear in the above explanations, considered in an advantageous manner on the subject of metal combustion. For example, both an energy conversion / storage concept about electro-positive metals are described, as well as possible implementation ¬ concepts. In addition, concepts for individual compo ¬ components such as nozzles or ignition devices are also described. As is apparent from the comparison with the present disclosure, the subject of the invention, as can be seen from the above explanations of the invention, goes beyond the disclosures of these documents and, as can be seen from the above description, stands out advantageous manner and based on an inventive idea from. This is true, although the invention, especially their training, individual technical realizations contained in these revelations can to contain as it as is clear from the above explanation, in the inventive manner, especially in new beneficial ¬ exemplary combination uses it.

The above embodiments, refinements and developments can, if appropriate, be combined with one another as desired. Further possible refinements, developments and implementations of the invention also include combinations of features of the invention which have not been explicitly mentioned above or described below with regard to the exemplary embodiments. In particular, the person skilled in the art will also add individual aspects as improvements or additions to the respective basic form of the present invention.

The invention will be further explained in detail with reference to various examples thereof. However, the invention is not limited to these examples.

Examples

preliminary tests

Preliminary considerations for an exemplary combustion of Li as metal M with CO 2 as fuel gas and CO as heat transport gas

In the following, the principle of the method according to the invention is explained with reference to exemplary embodiments for the combustion of lithium in CO 2 and CO 2 -containing atmospheres.

Regardless of the chosen atomization technology / design, a primary gas inlet is provided around an atomization unit. Essential for economic implementation here are a possible completeness, ¬-ended conversion of the fuel, temperature distribution, and efficient recovery of the reaction end product. Lithium is usually Herge ¬ poses with fused salt electrolysis. For this process, efficiencies of about 42% are obtained (according to standard potential 4.04 V, normally 6.7 - 7.5 V ie 60% -53%), calculated from process data without

Temperature correction of the normal potential. This would groove ¬ Zung from renewable sources slightly more than half as large as in the use of hydrogen (surplus electricity depending on whether (LHV from the lower calorific value or heating value, lower heating value) or HHV (gross calorific value or to Calorific value, higher heating value).

By way of example, the combustion for lithium is shown in the following reaction equations.

Li + C0 2 -> ■ ^ Li 2 C0 3 + H CO - 270 kJ

Li + H 2 O -> LiOH + HH 2 - 202 kJ

An alternative combustion of lithium with nitrogen would be as follows:

3 Li + HN 2 - Li 3 N - 207 kJ

The subsequent hydrolysis provides for the latter case almost twice the amount of energy.

Li 3 N + 3 H 2 O -> ■ 3 LiOH + NH 3 - 444 kJ

Since the combustion of lithium depending on the temperature and fuel gas solid and / or liquid residues arise, it must take special consideration.

As a primary gas in particular a mixture of Koh ¬ dioxide and carbon monoxide is used. The lithium is used in the liquid example, ie above the melting point of 180 ° C. The liquid lithium can be atomized into fine particles in a nozzle and then reacts directly with the respective fuel gas. For the combustion could be the

Particle size distribution of the lithium in the atomization of interest, which was consequently modeled for different nozzles and was examined with respect to the behavior during Ver ¬ burn.

First, various particle size distributions of Li were modeled with a single-fluid spin nozzle and a two-fluid nozzle depending on the nozzle diameter and experimentally investigated.

In a first exemplary preliminary test, a

Assumed particle size distribution with: (. 50% by weight of the par ¬ Tikel are smaller than the specified value). Dio (. 10% by weight of the particles are smaller than the specified value), d 5 o and dgo (90 wt% of the particles are smaller as the specified value) of 28.2, 84.4 and 175.7 mm. This resulted in a good reactivity in the combustion. The particle size distribution was determined microscopically, whereby the areas of the respective particles were automatically determined from the images and the equivalent area of the sphere of the same projection area (area-equivalent diameter) was calculated from the determined area. This is then indicated as a particle diameter.

In addition, further particle size distributions were modeled as shown in FIG. By way of example, FIG. 1 shows the dependence of the particle size distribution for Li on the diameter of the nozzle during the atomization of lithium with the aid of a single-fluid spin-pressure nozzle. The nozzle diameter d D in mm and the particle diameter d P on the y-axis are shown on the x-axis. This then corresponds, for example, approximately to the droplet distribution in the case of liquid lithium.

FIG. 2 shows the dependence of the particle size distribution on the atomization gas velocity during atomization a lithium melt with the aid of a two-fluid nozzle Darge ¬ provides. In addition, the theoretically calculated value d 5 o 'is given for the d 5 o value. Shown is the

Particle diameter d P as a function of the gas velocity v G , in particular the calculated gas velocity (calculated from the volume flow of the atomizing gas, here C0 2 , and the gap width of the nozzle).

Having different particle size distributions which WUR experimentally determined with the given in Table 1 values ¬ was conducted a simulation with respect to the separation of particles, the relative degree of reaction and the excess of CO2, the values are given in Table 2 below. Table 1: Determined particle size distributions (for

material nozzles)

Figure imgf000035_0001

Table 2: Results of the simulation

Figure imgf000035_0002
It was found that metal sprays with particle sizes smaller than 200-250 μm are preferred and can be realized by the process according to the invention, even with different nozzles. Corresponding experimental evidence was successfully performed (data not shown).

embodiment A simulation of combustion of Li with CO 2 as a fuel gas with a mixture of CO 2 and CO (heat transfer gas) as a primary gas was performed in a melting chamber shown in Figs. 3 to 8 as described above. In the figure 3 - as stated above - in this case the nozzles are not shown in detail, but are arranged together with the primary gas inlets.

Parameters of the configuration of interest for the lithium combustion in the simulation are in this case a high conversion to L1 2 CO 3, as good as possible and, preferably, complete separation of Ab ¬ L1 2 CO 3 and a hot exhaust gas outflow or

Which is as free as possible of Parti ¬ angles and preferably free of particles of product gas mixture outlet, to then use this in a boiler to produce steam and electricity. In this case, it was considered that may apply fes ¬ ter carbon and solid carbonate below 1100 K, wohinge ¬ gen over 1450 K to decompose L1 to Li 2 CO 3 2 0 and CO 2 be ¬ begins. A goal here is that the L1 2 CO 3 is liquid, so that it flows downwards due to gravity down to the drain, where it can form a liquid layer on the wall, which runs off. The temperature on the wall should be above the melting temperature of L1 2 CO 3 for this purpose. The simulation was performed using CFD (computational fluid dynamics) calculations with 96 primary gas inlets, below which were the liquid-lithium nozzles (packs of 25). Secondary gas (recirculated exhaust gas, ie, CO / CO 2 ) was supplied through two annular gaps in the outer area on the inner and outer walls of the upper ceiling of the melting chambers to form a protective film for the upper region of the walls. In addition, the melting chamber 24 comprised melt catchers, wherein the inclination angle of the melt catcher was 15 ° with respect to the horizontal with an inclination to the inside. The simulation was carried out such that a Auslasstempe ¬ temperature of the product gas mixture so that the wall ¬ temperatures were sure about 1100K 1373K, was. CFD solver ANSYS Fluent (1360000

Hexahedron cells k-omega SST turbulence model, Strahlungsmo ¬ dell with discrete ordinates adiabatic walls (1,360,000 hexahedron cells, k-omega SST turbulence model, discrete ordinates radiation model, adiabatic walls), wherein additionally the combustion of the lithium in the model has been worked ¬ . This model of the combustion of lithium may be Fischer P, Schiemann M, Scherer V, Maas P, Schmid G, Tataata D, "A numerical model of the combustion of single lithium particles with C02", Fuel 2015; 160: 87 - 99, to which reference is hereby made and the content of which is hereby fully incorporated by reference.

The model is divided into five sub-steps of the

Subdivided lithium combustion process, including inert heating of the metal, melting of the metal, igniting the Me ¬ talls in the reaction gas atmosphere, gas phase and Oberflä ¬ chenverbrennung of metal with reaction gas - here CO2, inert ¬ cooling and phase change of the product. It was assumed that the experimentally observed low formation of Li 2 O can reduce the degree of conversion. Boundary conditions of the simulation was calculated Plus with the process simulation program Aspen to determine the necessary flows for an outlet ¬ temperature of 1373K. To achieve a thermal energy input of 100 MW, a lithium flux of 10 t / h with a fuel gas / heat transfer gas flow of 75/148 t / h (CO2 / CO) was required. With the reaction product L 12CO 3 So Strö ¬ me 41.07 kg CO / s and 2.8 kg Li / s yielded 20.83 kg CO 2 / S. Lithium is added at a temperature of 673 K, and the

CO / C02 mixture having an average temperature of 591 K. For a faster simulation was a 1/8 From ¬ section of the melting chamber using symmetry planes used (see FIG. 4).

The speed at the secondary inlet inside was 9.98 m / s, the speed at the secondary inlet outside 13.51 m / s, and the speed at the primary inlets 11.06 m / s. The Incorporation of the gas flow and the metal took place at the same angle.

There were five different gas and particle feed angle φ (0 ° - ie vertically down, 1.5 °, 15 °, 22.5 ° and 30 °) and three different primary gas atmospheres with unterschiedli ¬ C02-metal ratios (λ = 1, 1.15, 1.3) to study the conversion of Li and the separation of liquid products (Li 2 C0 3 , Li 2 0).

The simulation was carried out such that all developing Parti ¬ kel or drops collide with a wall and / or floor, which can be hot here. The diameter of the simulated melting chamber (outer wall, without taking into account its thickness) was 12 m, the diameter of the inner wall 6 m (simulated without thickness), and the height 7 m.

The simulation was carried out after evaluating the preliminary tests with a specific particle size distribution from a specific nozzle. It has a particle distribution was adopted by: (. 10% by weight of the particles are smaller than the specified value). Dio, d 5 o (. 50% by weight of the particles are smaller than the attached ¬ passed value) and dgo (90% by weight of Particles smaller than the specified value) of 28.2, 84.4 and 175.7 mm. The mean particle size was 136 μm (particle size distribution: Ro ¬ sin-Rammler with 20 different diameters).

Various results of the simulation are shown in FIGS. 9 to 19.

Among other things, the temperature distribution in the reactor chamber must be taken into consideration. In the application example of the combustion of lithium with a thermal power of 100 MW, a temperature window between 993 K (melting temperature L1 2 CO 3 ) and 1583 K (decomposition temperature L 1 2 CO 3 ) is advantageous for enabling a liquid withdrawal of the reaction products. FIGS. 9 and 10 show by way of example the corresponding temperature profile for a lambda value of 1.3 and an injection angle or angle φ of 30 °.

FIG. 9 shows results of a simulation with a reaction gas excess of 1.3 and an introduction angle of

30 ° in a melting chamber according to the invention - as shown in Figure 6, wherein the temperature in K in the xz-sectional plane is shown on ¬ . High temperatures occur in the lower third of the outdoor area (right), where the heat of reaction emerges through the reaction, whereas in the upper area of the outdoor area no heating takes place. When passing the gas stream into the interior, a substantially homogeneous temperature distribution in the range of 1200 to 1400 K can be achieved. Also good to see is the protection of the outer and inner wall in the upper part of the exterior by the secondary gas. The protective effect of the secondary gas stream in the Au is ¬ ßenbereich clearly recognizable in particular by the end of the upper quarter of the melting chamber. Figure 10 shows the results obtained in Figure 9 of Tempe ¬ raturverteilung on the walls of an inventive

Melting chamber in the 1/8 segment - as shown in Figure 4.

A large amount of CO 2 reacts in the upper third of the

Melting chamber, which is also consistent with the degree of reaction in Figure 14 and a representation of the mass fraction of CO 2 (data not shown). The increase in the gas phase tempera ture closes this reaction zone and lies below because of the heat transfer and the high speed in this area. After the reaction, the wall temperature is always over 1100 K, which guarantees a liquid film on the wall.

FIG. 11 shows the axial velocity v ax in the z direction (z axis upward) in the xz plane, as shown in FIG. 6, in m / s in the simulation with a reaction gas excess of 1.3 and 1 Introduction angle of 30 ° are ent ¬ taken. In the outdoor area (right) is a slow Flow downwards with values below 0. After deflection and passage of the melt catcher, there is a fast flow upwards in the middle area of the inner area (left). The figure 12 is analogous to Figure 11, the results of the RA ¬ Dialen velocity V r in the x-direction (x-axis to the right) in the xz plane - as shown in Figure 6 - in m / s in the Si ¬ mulation to take a reaction gas excess of 1.3 and an introduction angle of 30 °. In particular, this is very strongly negative from the lower edge of the inner wall into the inner area. In the upper area, on the other hand, it is rather positive, both outdoors and indoors. At the cone also prevails above a positive radial Geschwin ¬ speed, on the ground and the end it is something negative.

Figure 13 shows analogously to Figure 11, the results of the tangentia ¬ len speed v tan in y-direction (y-axis in the Zei ¬ chenebene in) in the xz plane - as shown in Figure 6 - in m / s in the simulation with a reaction gas excess of 1.3 and an introduction angle of 30 °. Inside this is between the inner wall and the cone is positive, negative otherwise, whereby more particularly to a high negative value in the bottom area and there in particular on the cone, so un ¬ terhalb the melting scavengers obtained. Outside, the flow is directed to the viewer, and there is a

Acceleration of the flow in the lower area. After the deflection of the flow there is only a small flow in the y-direction. Figures 14 to 16 are exemplary particle trajectories of exemplary introduced metal particles with the relative degree of conversion X rel in the simulation with a Reakti ¬ onsgasüberschuss of 1.3 and an inlet angle of 30 ° (Figure 14), 15 ° (Figure 15) and 0 ° (FIG. 16) in a melt chamber cutout shown according to FIG. In

Figure 14 at an angle φ of 30 ° can be observed after about half of the reactor, a nearly vollständi ¬ ger burnout or reaction of the particles. However, in FIG not converted all particles more, and also can ver ¬ multi-pass particles through the melt catcher. In a vertical feed, as in FIG. 16, a majority of the particles pass through the melt catchers, and a reduced reaction is also observed as in FIG.

FIG. 17 shows the results of the turbulent intensity I t of a simulation with a reaction gas excess of 1.3 and an introduction angle of 30 ° in the xz plane of a melting chamber according to the invention - as shown in FIG. Strong turbulence can be seen especially in the interior and especially above the melt catcher. Analogous result ¬ se result (not shown) for the turbulent kinetic energy.

Figures 18 and 19 show the dependence of the conversion ¬ rate (Figure 18) and the outlet temperature of the gas and the product particles / gobs at the outlet (Figure 19) from the Einleitwinkel of the metal droplets and the primary gas, and the ratio of lambda (λ) between the actual Gas mass flow and at least necessary reaction gas mass flow for a complete reaction of the metal drops. Lambda is here the ratio of the mass flows of actual reaction gas / minimum reaction gas (for a complete theoretical implementation):

Lambda (λ) = mass flow ratio reaction ¬ gas / reaction gas Minimum

 (Lambda = reaction gas / minimum reaction gas). In particular, with a low lambda value, a greater difference in the degree of reaction is dependent on the angle φ, as can be seen in Figure 18, where a change in the angle of 22.5 ° to 23 °, a difference of 0.6 m% (mass percent ) at λ = 1.3, from 0.8 m% at λ = 1.15, and from 2.7 m% at λ = 1.

As shown in FIG. 19, for different values of λ, different temperatures for the gas phase at Outlet or the border to the boiler LIGas, L1.15Gas and

LI .3Gas as well as different temperatures of the particles in collision with the wall LIPart L1.15Pard and L1.3Part. At low λ of 1, the temperatures of the gas at the outlet are low (between 1270 and 1242 K), with λ = 1.15 between 1328 and 1273 K and with λ = 1.3 between 1351 and 1292 K, where essentially two Influences were observed, namely the particle behavior and the reaction rate. In genü ¬ quietly CO 2 in the gas stream, the Li-particles react very rapidly towards a maximum combustion and then cool to the local temperature of the gas stream before reaching the discharge. In addition, the free flow time is reduced by larger angles, which can lead to lower gas outlet temperatures, especially with a smaller amount of fuel gas, CO 2 . On the other hand, the outlet temperature of the particles increases for larger angles φ and lower λ values, since fewer particles react before colliding with the wall.

The advantageous values for lambda, entry angle of the metal spray and their dependencies for the exemplary embodiment are shown in FIGS. 18 and 19. For a Schmelzkammerfeu ¬ tion with a power of 100MW th an introduction angle of 22.5 ° or 23 ° and an increased lambda value, for example ¬ 1.3, particularly advantageous. Too large an angle can lead to a reduced reaction, especially in the outdoor area, which of course also still a reaction can take place on the wall, but where there is a lower temperature. Too high a value of lambda leads to a diffusion-limited reaction.

It thus turned out first that a small stoichiometric excess of CO 2 is advantageous.

In the application example with lithium as a metal fuel and a Schmelzkammerfeuerung with a performance of

100MW th proved to be an inlet angle of 22.5 ° 23 ° and a height to width ratio of the melt catcher 3 (at the point of attachment to the inner cone) of 4: 1 as advantageous. The Ver- hhällnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnn

It is true that the law of the invention is based on the concept of excellence

EEiinnzzeellppaarrttiikkeellrreeaakkttiioonneenn wwiitthh LLii bbeeii 660,000 to 770,000 °° CC aanndd CCOO 22 bbeeii

550000 °° CC iinn eeiinneemm EEiinnzzeellppaarrttiikkeellrreeaakkttoorr kkoonnnntteenn ddiiee SSiimmuullaattiioonnss--

Figure imgf000043_0001

As is clear from the exemplary embodiments of the invention described above, the solution according to the invention is characterized, inter alia, by the fact that, for the combustion of metals in gases, for example CO2 or N 2 -containing gases, individual of the elements enumerated below together with advantages and / or or combinations thereof include:

• It is a substantially homogeneous or homogeneous Tem ¬ peraturverteilung in the combustion chamber permits (inter alia controlled via the injection angle, possibly selected behaves ¬ nis actual reaction gas mass flow to necessary for complete reaction of the fuel

 Gas flow).

• A stable operation is possible at a temperature level at which the reaction products solid at room temperature remain liquid and a liquid withdrawal from the combustion chamber is possible.

• The introduction of the metal particles and the reaction gas into the reaction chamber at a certain angle allows both mixing of the reactants, complete conversion of the fuel, so the metal M, a homogeneous temperature distribution and a Flüssigab ¬ train the products.

A Schmelzfängerstruktur may be provided for the separation of liquid, drop-shaped Abbrandprodukten from the exhaust gas, which further use of the allows the combustion of thermal energy.

But the invention is not limited to this and other example ¬ mentioned by way of embodiments restricted but may also include other possible embodiments, such as in particular different technical solutions relating to the use of alternative combustion plants for metals, such as a cyclone burner as in the

DE102014203039 is known. A comparison of the present disclosure with the disclosure of

DE102014203039, which is included in the present description at least in this context herein by reference, shows what details are used and can he ¬ inventive contribution that goes beyond recognizing.

Claims

claims
1. A method for burning a fuel gas in one
Melting chamber, in which method a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, is burned with the fuel gas, wherein the metal M and a primary gas comprising the fuel gas from above into an outside area the melt chamber between an outer wall and an inner wall of the melting chamber, wherein the metal M and / or the primary gas are introduced substantially tangentially to the outer and / or inner wall at an angle φ to the vertical in the outer region of the melting chamber, wherein the vertical extends substantially parallel to the outer wall and the inner wall
2. The method of claim 1, wherein the angle φ is in a range of about 5 ° to about 60 °.
3. The method of claim 1 or 2, characterized in that the combustion is such that a homogenous temperature distribution We ¬ sentlichen is ensured when burned.
4. The method according to any one of the preceding claims, wherein the metal M and the primary gas are introduced together or introduced into the melting chamber.
5. The method according to any one of the preceding claims, wherein at least one resulting product of the combustion of Me talls M is deposited with the fuel gas liquid at Schmelzfängern innerha the combustion chamber, wherein the Schmelzfänger are connected to the inner wall.
6. The method according to claim 5, wherein the melt catchers are connected centrally in an inner region of the melting chamber and / or in a bottom region of the melting chamber below the inner region with an upwardly tapering cone.
7. The method of claim 5 or 6, wherein a resulting in the combustion of the fuel gas with the metal M Pro ¬ duktgasgemisch is passed from below through the Schmelfänger.
8. The method according to any one of the preceding claims, wherein along the outer and / or the inner wall of the melting chamber, a secondary gas is introduced from above into the outer area.
9. The method according to any one of the preceding claims, wherein the fuel gas is introduced in a stoichiometric excess to the metal M.
10. The method according to any one of the preceding claims, wherein the fuel gas is selected from the group consisting of air, nitrogen, water and / or carbon dioxide.
11. melting chambers, comprising:
an outer area between an outer wall and an inner wall of the Schme1kkämmer;
an inner area within the inner wall of the melting chamber;
a bottom portion located below both the outer portion and the inner portion of the melting chamber, including a substantially inwardly inclined bottom connected to the outer wall;
a drain for a melt, which is located centrally in Bodenbe ¬ rich and is connected to the inclined floor; a plurality of nozzles above and in an upper area of the outside of the melting chambers, respectively, which are formed, a metal M selected from alkali metals, alkaline earth metals, Al and Zn, and alloys and / or mixtures thereof, in the outside of the melting chamber to bring in;
a plurality of primary gas inlets in an upper area of the outer area of the melting chambers, which are provided with det are to introduce a primary gas comprising a fuel gas in the outer ¬ area of the melting chamber;
at least one gas outlet at an upper end of the comber for indoor ¬ realm of melting;
wherein the plurality of primary gas inlets and / or the plurality of nozzles are formed, the metal M and / or the primary gas substantially tangential to the outer and / or inner wall at an angle φ to the vertical in the outer region of the melting chamber between the outer wall and the inner wall of the melting chamber, wherein the vertical extends substantially parallel to the outer wall and the inner wall.
12. A melting chamber according to claim 11, further comprising at least one secondary gas inlet in an upper region of the outer region of the Schmelzkämmer, which is adapted to introduce a secondary gas along the outer and / or inner wall of the melting chamber.
13. A melting chamber according to claim 11 or 12, further comprising a plurality of fuses, which are connected in the interior of the melting chamber with the inner wall.
14. Melting chamber according to claim 13, wherein the melt catcher are connected centrally in the inner region of the melting chamber and / or in a bottom region of the melting chamber below the inner region with an upwardly tapering cone.
15. Melting chamber firing comprising:
a melting chamber according to any one of claims 10 to 13; and a boiler, which is mounted above the melting chamber and which is connected thereto.
PCT/EP2016/082865 2016-10-04 2016-12-29 Method and arrangement for generating power WO2018065078A1 (en)

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