KR20180095137A - Method for the combustion of an alloy of an electropositive metal - Google Patents

Abstract

The present invention relates to a method for the combustion of an alloy of a positive metal using a fuel gas, wherein the positive metal is selected from alkaline-, alkaline earth metals, aluminum and zinc as well as mixtures thereof, Comprises at least two positive metals, and the alloy of the positive metal is burned using a fuel gas. The invention also relates to a device for carrying out the method.

Description

METHOD FOR COMBUSTION OF AN ALLOY OF AN ELECTROPOSITIVE METAL FIELD OF THE INVENTION [0001]

The present invention relates to a process for burning an alloy of electropositive metal using a fuel gas and an apparatus for carrying out the process wherein the positive metal is selected from the group consisting of an alkali metal ), Alkaline earth metals, aluminum and zinc, and mixtures thereof, wherein the alloy of the amphoteric metal comprises at least two amphoteric metals, and in the process, the amorphous metal alloy And is burned using the fuel gas.

Fossil fuels carry electricity, heat and mechanical energy of tens of thousands of terawatt hours per year. However, the end product of combustion, carbon dioxide (CO ₂ ), is becoming an increasingly environmental and climate problem.

Over the years, a number of energy generation units have been proposed for working with heat generated from the oxidation of metallic lithium (see, for example, U.S. Patent No. 33 28 957). In this system, water and lithium react with each other to produce lithium hydroxide, hydrogen, and steam. Elsewhere in the system, hydrogen generated by the reaction between lithium and water is combined with oxygen to form additional steam. Next, the steam is used to drive a turbine or the like, and thus an energy generation source is obtained. Lithium may also be used additionally to obtain commodity materials. For example, by reacting with nitrogen to provide lithium nitride and then hydrolyzed to provide ammonia or react with carbon dioxide to provide lithium oxide and carbon monoxide. As in the case of nitrides, in each case, optionally after hydrolysis, the final end product of the solids of the reaction of lithium is an oxide or carbonate, which is then reduced again by electrolysis to lithium metal . This can be achieved by establishing circuits in which surplus power can be generated, stored and converted back to power at a desired time by wind power, photovoltaic cells or other renewable energy sources, or else chemical raw materials can be obtained.

Methods by which amphoteric metals can be used to form a complete energy circuit are described in DE 10 2008 031 437 A1 and DE 10 2010 041033 A1. Specifically, lithium serves as a case study as both an energy carrier and an energy storage means, and it is also possible to use other positive metals such as sodium, potassium or magnesium, calcium, barium or aluminum and zinc It is possible.

Particular attention should be given to the fact that solid or liquid residues may arise in the combustion of lithium depending on temperature and fuel gas. Moreover, depending on the configuration and operation of the oven for combustion of lithium metal in different atmospheres and under pressure (e.g. in liquid form), offgas and solids / liquids can be generated as combustion products have. These solid and liquid materials must be very substantially separated from the offgas.

It is important to substantially completely separate the liquid and solid combustion residues from the offgas stream so as not to generate any surface deposits or occlusions in downstream devices. More specifically, it is highly desirable to direct the off-gas stream directly to the gas turbine, since in that case it must be ensured that all particles have been completely removed from the off-gas stream. These particles cause long term damage to gas turbine blades and cause plant disruption.

Moreover, DE 10 2014 203039.0 describes the use of alkali metals as energy storage means and its use in power plant operation, and DE 10 2014 203039.0 describes the use of lithium in CO ₂ - or N ₂ - containing atmospheres The simultaneous separation of solids and gaseous reaction products by means of a cyclone burner and a cyclone.

The problem here is the high temperatures in the combustion of the positive metal and the exothermicity of the reaction, which leads to high demands on the control of the combustion device and the reaction.

It is therefore an object of the present invention to provide a process and apparatus wherein the combustion of bipolar metals can be carried out at lower temperatures. It is a further object of the present invention to provide a process by which effective combustion of bipolar metals can be effected, with avoidance of excessive cooling for the protection of the plant and therefore reduction of heat losses. It is a further object of the present invention to provide a process by which starting materials from combustion of bipolar metals can be obtained in a simple and energetically improved manner. Furthermore, it is a further object of the present invention to provide a process by which the energy required for activation of the combustion reaction can be lowered. In addition, it is an object of the present invention to provide a process wherein liquid transfer of combustion products from combustion can occur at a minimum temperature, as the longer they are held in liquid, the lower the temperature of combustion, This is also because it protects the plant.

It has now been found that the use of alloys of amphoteric metals lowers the reaction temperature of the combustion and allows for better control of the exothermic combustion reaction and more effective control of the plant, and the amphoteric metals are alkali metals, alkaline Alloys of metals, earth metals, aluminum and zinc, and mixtures thereof, and the amphoteric metal alloy comprises at least two amphoteric metals. In addition, the gas formed in the reaction, a salt thereof (for example, in the case of combustion of CO ₂ CO) (salt mixture) separated from (e.g., the carbonates in the case of combustion of CO ₂₎ is used and the liquid of the cyclone ≪ / RTI > can be carried out in a simple and effective manner by removing the molten salt. Moreover, alloys can generally be provided more easily than pure positive metals, because electrolysis of salt mixtures of various positive metals is also more efficient than electrolysis of salts of only one positive metal Can be easily and less energy-intensive.

The present invention therefore relates to a process for the preparation of aluminates containing alkali metals and / or alkaline earth metals, aluminum and / or zinc, in different reaction gas atmospheres such as carbon dioxide, nitrogen, steam, To processes and configurations for combustion.

In one aspect, the present invention relates to a process for burning an alloy of a positive metal with a fuel gas, wherein the positive metal is selected from alkali metals, alkaline earth metals, aluminum and zinc, and mixtures thereof Wherein the alloy of the amphoteric metal comprises at least two amphoteric metals, and in the process, the alloy of the amphoteric metal is burned using the fuel gas.

In a further aspect, the invention relates to an apparatus for the combustion of an alloy of a bipolar metal, wherein the bipolar metal is selected from alkali metals, alkaline earth metals, aluminum and zinc, and mixtures thereof, Wherein the alloy comprises at least two amphoteric metals,

A pore burner or unit for atomizing an alloy of a positive metal,

A feed unit-feed unit for an alloy of a positive metal, preferably in liquid form, into a pore burner or unit for atomizing the alloy preferably comprises an alloy of a positive metal in liquid form A feed unit for the fuel gas, designed to feed the fuel gas, and a feed unit designed for feeding the fuel gas to the purging burner or unit for atomizing the alloy,

Optionally, a heating device for providing an alloy of a bipolar metal in liquid form is provided, wherein the heating device is designed to liquefy an alloy of a bipolar metal.

Further aspects of the invention can be deduced from the dependent claims and the more detailed description, and also from the drawings.

The accompanying drawings are intended to illustrate embodiments of the invention and to provide a further understanding of the invention. In the context of the description, the appended drawings serve to explain the principles and concepts of the present invention. Many other embodiments and the advantages mentioned will become apparent with reference to the drawings.

The elements of the figures are not necessarily to scale with respect to each other. The same elements, features, and components having the same function and the same effect are given the same reference numerals in the drawings of the drawings, respectively, unless otherwise stated.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows in an overview form an exemplary arrangement for the apparatus of the present invention.
Figure 2 shows in a schematic form a detailed view of a further exemplary arrangement for an apparatus of the present invention.
Figure 3 shows in further detail a further detail of an additional exemplary arrangement for the apparatus of the present invention.
Figure 4 schematically illustrates an exemplary cross-section through an exemplary apparatus of the present invention in the region of the feed unit of carrier gas to a reactor.
Figure 5 shows in a schematic form a further possible arrangement for the apparatus of the present invention.
6 illustrates, in schematic form, another possible arrangement for the apparatus of the present invention.
Figure 7 shows a scheme for an exemplary reaction of carbon dioxide with an amphoteric metal according to the present invention to provide a carbonate, which may be carried out by a process according to the present invention.
Figure 8 shows a method for further exemplary reaction of nitrogen and an amphoteric metal alloy according to the present invention to provide nitride and further conversion products, which may be carried out by a process according to the present invention.

In a first aspect, the present invention relates to a process for burning an alloy of a positive metal using a fuel gas, wherein the positive metal is selected from the group consisting of alkali metals, alkaline earth metals, aluminum and zinc, And an alloy of a positive metal comprises at least two positive metals, and in the process, an alloy of a positive metal is burned using a fuel gas.

In certain embodiments, the positive metal of the alloy (L) is selected from the group consisting of alkali metals, preferably Li, Na, K, Rb and Cs, alkaline earth metals, preferably Mg, Ca, Sr and Ba, And Zn, mixtures thereof and / or alloys thereof. In preferred embodiments, the amphoteric metal of the alloy is selected from Li, Na, K, Mg, Ca, Al and Zn and the alloy further preferably comprises at least two selected from Li, Na, K, Ca and Mg Wherein the alloy comprises at least lithium or magnesium, more preferably in certain embodiments. However, it is possible to combine any of the metals mentioned. The alloy is additionally, not particularly limited, and may be, for example, in solid or liquid form. Preferably, however, the alloy in the combustion is a liquid, since a simple transfer of the alloy may occur in this manner.

In certain embodiments, useful fuel gases are fuel gases that are capable of reacting with the alloy (L) mentioned in the exothermic reaction, but these are not specifically limited. By way of example, the fuel gas may comprise air, the oxygen, carbon dioxide, hydrogen, water vapor, nitrogen oxides, NO _x, for example, dinitrogen monoxide, nitrogen, sulfur dioxide, or mixtures thereof. Thus, the process can also be used for desulfurization or NOx removal. According to the fuel gas, it is possible here to obtain various products which may be in solid, liquid, or otherwise gaseous form using various alloys (L).

For example, the reaction of an alloy (L), such as an alloy of lithium and magnesium, with nitrogen may result, in particular, of a metal nitride, such as a mixture of lithium nitride and magnesium nitride, which, in turn, The reaction of the alloy (L) such as lithium and sodium with carbon dioxide can be carried out in the presence of a metal carbonate such as a lithium carbonate and a sodium carbonate, a carbon monoxide, a metal oxide such as a mixture of lithium oxide and sodium oxide, Otherwise, metal carbides such as lithium carbide and sodium carbide, or mixtures thereof, can result, for example, longer-chain hydrocarbon products in the Fischer-Tropsch process, such as methane , Ethane, benzene, diesel as well as methanol and the like Further high that - while the use of carbon monoxide to obtain the product of value as possible, for example, to obtain the acetylene, it is possible to use a metal carbide, a carbide such as lithium and sodium carbide. In addition, for example, it is also possible to use, for example, dinitrogen monoxide as a fuel gas to form a metal nitride. Similarly, alloys of lithium and potassium result in, for example, a salt mixture of the corresponding lithium and potassium salts at the time of combustion, and an alloy of sodium and potassium at the time of combustion, for example, resulting in a salt mixture of the corresponding sodium and potassium salts . Corresponding reactions can also be carried out using alloys comprising three or more metals such as lithium, sodium and potassium. For example, magnesium and calcium, or alloys of magnesium and zinc or of magnesium and aluminum, etc., are equally conceivable. For conversion to nitrides, preference is given to, for example, Li / Mg or any mixture of alkaline earth metals, in particular Mg / Ca, but for example Be does not work either. Suitable alloys for combustion with CO ₂ are, for example, Na / K, Na / Li / K, Li / K, Li / Na, Li / Mg, For example, alloys with barium can also be obtained and used in a simple manner, since barytes are very common in nature.

Similar reactions to other metals mentioned in alloys may also occur.

One exemplary reaction for Na / K alloys is as follows:

The use of alloys due to the lower melting temperature of the salt mixture compared to the melting temperatures of the individual alkali metal and alkaline earth metal carbonates can enable the flexible adjustment of the flame temperature while ensuring the removal of the salt mixture in liquid form.

For example, in the case of combustion of lithium in a carbon dioxide or nitrogen atmosphere, the adiabatic flame temperature of the stoichiometric combustion reaction is in the range of over 2000K.

Additional enthalpy of the reaction of individual positive metals with various fuel gases has been reported, and the exothermicity of the reactions is evident from this.

Table 1: Enthalpy generation in reactions of individual positive metals

The exothermic reaction releases heat at a heat level comparable to the thermal level in the combustion of carbon-based energy carriers under air. For these reasons, a simpler control of the combustion reaction is advantageous.

It is not excluded that, in addition to the two positive metals selected from alkali metals, alkaline earth metals, aluminum and zinc and mixtures thereof, additional components, such as additional metals, are present in the alloy L. In certain embodiments, these additional components comprise less than 50 wt.%, Preferably less than 25 wt.%, More preferably less than 10 wt.%, And even more preferably less than 5 wt.%, ≪ / RTI >

However, in certain embodiments, the alloy comprises only metals selected from alkali metals, alkaline earth metals, aluminum and zinc, and mixtures thereof, although unavoidable impurities may also be present in the alloy, for example, less than 1% It can be present in an amount.

According to the present invention, the quantitative proportions of the positive metals and any additional components in the alloy (L) are not particularly limited. However, in certain embodiments, the alloy components may be alloyed, i.e., eutectic mixture of metals, with a possible temperature deviation of the melting point of the salt mixture or alloy below + 200 < To a minimum of the melting point and / or a minimum of the melting points of the corresponding salts. Preferably, in the case of alloys, there is a minimum value of the melting point (eutectic mixture) and / or the minimum value of the melting point of the corresponding salts (eutectic mixture / eutectic). The corresponding melting points of the salts or alloys formed upon combustion can be ascertained in a suitable manner from known phase diagrams or calculated in a simple manner. For example, in the case of an alloy of sodium and potassium, the salts obtained during combustion with carbon dioxide are sodium carbonate and potassium carbonate, with a minimum melting point of 709 ° C at a molar ratio of sodium salt to mixture of 0.59 . In the case of lithium and sodium, a value of 498 [deg.] C was confirmed in the molar ratio of sodium salt to mixture of 0.49 for carbonates. In the case of lithium and potassium, for carbonates, there are actually two melting point minima at 503 캜 at the molar ratio of lithium salt to mixture of 0.416 and 0.61, the melting temperature is only minimized between these values, Are also included. In certain embodiments, the ratio of positive metals and additional components in the alloy is selected to provide a melting point of formed salts that is lower than the lowest melting point of each of the individual salts; In other words, the melting point for the lithium carbonate / sodium carbonate system, for example, is lower than the melting point of the lithium carbonate because the potassium carbonate has a higher melting point.

In certain embodiments, the alloy of the amphoteric metal is burned in liquid form. In this manner, the alloy can be easily transported and the reaction of the alloy with the fuel gas can be localized more easily. In certain embodiments, the combustion occurs additionally at a temperature exceeding the melting point of the salts formed in the reaction of the fuel gas with the alloy of the amphoteric metal. This configuration results in liquid reaction products upon combustion of the alloy and the liquid reaction products are relatively easy to remove from the gas reaction products formed in contrast to the reaction products in the form of dusts or powders Can be separated. Moreover, it is possible here to more easily control the combustion reaction, since the reaction products with the highest melting point, i. E. The salts, are in liquid form and further gases and any liquid reaction products or non- For example, liquid alloy (L) or liquid metal can be easily removed from the reaction site. This is particularly advantageous when, for example, in the case of atomization or combustion using a pore burner, combustion occurs at the outlet site of the alloy from the feed unit.

The atomization of the alloy may be carried out here in an appropriate manner and is not particularly limited. The type of nozzle is likewise not limited in particular, and may include one-phase and two-phase nozzles. In certain embodiments, an alloy (L) of a positive metal is atomized, preferably atomized in liquid form, and burned using a fuel gas. An alternative possibility is the atomization of alloy particles. However, more efficient atomization can be achieved by using an alloy (L) in liquid form, in which case self-ignition of the combustion reaction as a result of temperature is also possible, so that no ignition source may be required.

In certain embodiments, the alloy of the amphoteric metal is guided to the pore burner in liquid form and burned with the aid of a pore burner, the fuel gas is optionally directed to the outer surfaces of the pore burner and the alloy of the bare metal . However, in certain embodiments, no internal mixing occurs, such as in conventional pore burners, to avoid clogging of pores by solid reaction products. In certain embodiments, the pore burner is thus a pore burner that does not have an internal mix. In certain embodiments, in the case of the use of a pore burner, the pores merely serve to increase the surface area of the alloy (L). However, in the case of continuous feeding of an alloy (L) of a positive metal, the reaction with the fuel gas can be carried out in the following manner, if the reaction products formed can be ensured to be delivered out of the pore burner by the further transfer of the alloy (L) Can occur at the exit of pores near the surface of the pore burner. However, in certain embodiments, the combustion reaction is carried out only at the outside of the pores of the pore burner, for example at the surface of the pore burner, or even after the release of the alloy L from the pore burner, Occurs.

In certain embodiments, there is an additional requirement for a reactor / combustion space in which combustion of an alloy (L) using fuel gas may occur, for example in the case of atomization or combustion with the aid of a pore burner. Here too, if combustion can occur in the reactor / combustion space, the reactor / combustion space is not particularly limited.

In the case of the use of pore burners, there is a further advantage that the combustion can be localized to the pore burner, in which case the combustion products are also obtained in the pore burner or near the pore burner. On the other hand, for example, in the case of atomization, the reaction products are obtained throughout the reactor, the solid and liquid reaction products must again be separated from the gas reaction products in a complicated manner, and in the case of combustion using a pore burner, There is localization of the solid and liquid reaction products, which facilitates the separation of the solid and liquid reaction products from the gaseous combustion products. In this way, the entire combustion device can also be made more compact, and the combustion can be configured to be gentler with respect to the device through localization of the combustion process.

The pore burner is not particularly limited in the aspect of the shape of the pore burner, and in certain embodiments includes a porous tube as a burner. In certain embodiments, the pore burner comprises a porous tube, and the porous tube may be supplied with at least one orifice of an alloy L. Preferably, the alloy (L) is fed only through one orifice of the tube and the other end of the tube is closed or similarly made of the material of the porous tube. Here, for example, the porous tube can be made of a metal such as, for example, iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zircaloy and alloys of these metals, and also alloys of steel such as stainless steel and chromium- A porous metal tube. The pore burners are preferably formed from a group consisting of iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zircaloy and alloys of these metals and also steels such as stainless steel and chromium- It is made of selected material. Suitable examples are, for example, austenitic chromium-nickel steels which are highly resistant to sodium corrosion at elevated temperatures, but are not limited to AC 66, Incoloy 800 or Pyrosom G 20132 Nb (Pyrotherm G 20132 Nb), 32% nickel and 20% chromium also exhibit relatively favorable corrosion properties. The additional components of the pore burner are not subject to any further restrictions and may include a feed unit for the metal M and optionally an ignition source and the like.

In certain embodiments, the pore burner is supplied with an alloy (L) in liquid form within the pore burner. This results in a better distribution of the alloy L in the pore burner and a more homogeneous discharge of the alloy from the pores of the porous tube, resulting in a more homogeneous reaction between the alloy L and the fuel gas. The combustion of the alloy L and of the fuel gas can be effected, for example, by the pore size of the pores of the tube, the alloy L to be used, the density thereof, which can be correlated with the temperature of the alloy L, The pressure entering the burner, the pressure of the fuel gas or the application / feed rate; In certain embodiments, for example, alloys (L) comprising lithium and sodium are correspondingly used in liquid form, i.e., for example, in excess of the melting point of the alloy. Here, the additional gas is not limited, for example, if the liquid alloy L can be injected into the porous tube using the help of additional gas under pressure and no further gas reacts with the alloy L, It is an inert gas. Next, the liquid alloy L is delivered to the surface through the pores of the tube and is burned with the gas to provide the respective reaction product (s).

In certain embodiments, the fuel gas is directed to the outer surfaces of the stoichiometric burner and burned with the alloy (L). This can reduce or prevent clogging of the pores of the porous tube, thereby preventing cleaning of the pore burner or otherwise reducing wear.

The combustion of the alloy (L) at the surface of the porous tube reduces the tendency for the passage of small particles into the gas space / reaction space, so that at most, relatively large droplets of reaction products are generated, Can be easily separated and can be deposited on the reactor wall, for example, by a cyclone. The main part of the combustion products can be separated, for example, in liquid form. In this case, the reactor wall can be cooled, for example using heat exchangers, in which case the heat exchangers can also be connected to the turbines and generators.

In certain embodiments, combustion is conducted at a temperature that exceeds the melting point of the salts formed in the reaction of the fuel (L) with the fuel gas. The salts formed in the combustion of the alloy (L) and the fuel gas may have a melting point exceeding the melting point of the alloy (L), so that supply of the liquid alloy (L) at an elevated temperature may be required. Combustion at temperatures above the melting point of the formed salts can additionally avoid contamination or coverage of pore burners or nozzles by the formed salts such that the pore burners or nozzles can also be used for cleaning the pores, Can be better protected. This allows for better operation and reduced cleaning of the device and also longer usage times without cleaning. It is also possible that the liquid reaction product simply falls off the burner. Preferred materials for the burners and nozzles in particular in the case of such processes at temperatures exceeding the melting point of the salts formed are those which are capable of withstanding these temperatures such as iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten , Zircaloy and alloys of these metals and also steels, such as stainless steel and chrome-nickel steel.

Thus, the combustion temperature is preferably higher than the melting point of the respective reaction product (s), so that the pores of the nozzle or pore burner are not blocked and the reaction products can be transported away. In addition, depending on the reaction product, a certain degree of mixing between the liquid alloy (L) and the reaction product may also occur, so that combustion may occur locally at the pore opening or at the nozzle outlet, Can be distributed over the surface. This can be controlled, for example, through the feed rate of the alloy (L).

Through the supply of the alloy (L) as the alloy of the at least two positive metals, it is possible to achieve a melting point lowering of the alloy and of the formed metal salts compared to the respective metals, so that the process is carried out at lower temperatures, The device can be implemented in a more gentle manner and the use of highly refractory materials in the device can be reduced or avoided.

The gaseous products formed in the reaction (e.g., CO in the case of the combustion of CO ₂ ) can be further utilized separately from the solid and liquid combustion products. In the combustion process, the salts formed in the pyrogenic reaction can be drawn in liquid form, and the off-gas (consisting of any gaseous reaction products and any excessively introduced reaction gas) is passed through the expander turbine without solid particles Lt; RTI ID = 0.0 > pressure. ≪ / RTI > It is possible to ensure a lower combustion temperature through appropriate use of alkali metal and / or alkaline earth metal alloys or alloys of Al and / or zinc, with adjustment via air ratio (stoichiometry of reaction). Due to the low melting temperature of the salt mixture, the removal of products in liquid form can be more easily ensured. Thus, it is possible to avoid the use of expensive burner materials. Furthermore, at the different temperatures as a function of the stoichiometry (air ratio) of the combustion reaction, potentially higher dynamics in the combustion process are possible, while ensuring the removal of the salt mixture formed in liquid form.

In addition, in certain embodiments, to stabilize the off-gas temperature within a certain temperature range, a certain excess amount of fuel gas may be introduced into the fuel gas, for example, 1.01: 1 or more, preferably 1.05: 1 or more, More preferably a molar ratio of fuel gas to metal (M) of 5: 1 or more, even more preferably 10: 1 or more, such as even 100: 1 or more have. The fuel gas may also serve here for the removal of heat at the inflator portion, such as a turbine.

In the process, in the case of the combustion of the alloy (L) by means of the fuel gas, the separation of the offgas from the solid and / or liquid reaction products can additionally be carried out, in which case, In the reaction step, the fuel gas is burned with the alloy (L), off-gas and further solid and / or liquid reaction products are formed, and in the separation step, the off gas is separated from the solid and / or liquid reaction products . In this case, in the separation step, an additional carrier gas may be added, and the carrier gas may be removed as a mixture with the offgas. Here, the carrier gas may also correspond, for example, to off-gas resulting in off-gas corresponding to the supplied carrier gas, or otherwise to a fuel gas. Thus, in the process of the present invention, in certain embodiments, it is possible to separate reaction products after combustion.

According to the present invention, the carrier gas is not particularly limited and may correspond to the fuel gas, but may also be different from the fuel gas. The carrier gases used may be, for example, air, carbon monoxide, carbon dioxide, oxygen, methane, hydrogen, water vapor, nitrogen, dinitrogen monoxide, mixtures of two or more of these gases, It is now possible for various gases such as methane to serve for heat transfer and to remove the reaction heat of the reaction of the metal (M) and the fuel gas from the reactor. The various carrier gases may be suitably matched, for example, to the reaction of the fuel gas and the alloy L, possibly to achieve synergistic effects here. The gas optionally used in the supply of the alloy L may likewise correspond to the carrier gas.

For example, in the combustion of an alloy (L) consisting of lithium and sodium and carbon dioxide, when carbon monoxide can be formed, the carrier gas used can be, for example, carbon monoxide and can optionally be circulated, And may be at least partially recycled back as a carrier gas. In this case, the carrier gas is matched to the off-gas so that a portion of the carrier gas can be selectively recovered, for example, as a valuable product for subsequent Fischer-Tropsch synthesis, while the carrier gas is burned Based on the carbon dioxide used, preferably up to 90 vol% or more, more preferably up to 95 vol% or more, even more preferably up to 99 vol% or more, based on the carbon dioxide used, And particularly preferably to the extent of 100% by volume, there is at least partial conversion of the carbon dioxide to carbon monoxide as a whole and is recovered as a valuable product. The more carbon monoxide is generated, the cleaner the carbon monoxide is removed.

For example, in the case of the combustion of an alloy (L) and nitrogen consisting of lithium and magnesium, the carrier gas used may be, for example, nitrogen, so that unreacted nitrogen in the off-gas from the combustion, together with the nitrogen carrier gas, offgas ", so that, if desired, the separation of the gas can be carried out in a simpler manner and in certain embodiments can be carried out using alloys (L) and nitrogen May not even be required in the case of an appropriate, preferably quantitative, combustion of the fuel. For example, it is possible to easily remove ammonia from the nitride formed by scrubbing or cooling.

In certain embodiments, at least a portion of the off-gas may correspond to a carrier gas. For example, based on the total volume of offgas, the offgas may be at least 10 vol%, preferably 50 vol% or more, more preferably 60 vol% or more, even more preferably 70 vol% , And even more preferably up to 80% by volume or more of the carrier gas. In certain embodiments, the fuel gas may correspond to a carrier gas to an extent of 90 vol% or more based on the total volume of the off gas, and in some cases may correspond to a carrier gas to an extent of even 100 vol% have.

In certain embodiments, in the process of the present invention, the mixture of off-gas and carrier gas may be fed at least partially back into the separation step as a carrier gas and / or as a fuel gas to the combustion step. The recycle of the mixture of offgas and carrier gas can be, for example, 10 vol% or more, preferably 50 vol% or more, more preferably 60 vol% or more, based on the total volume of the carrier gas and offgas, , Even more preferably greater than or equal to 70 vol%, and even more preferably greater than or equal to 80 vol%. In certain embodiments, the recycle of the mixture of offgas and carrier gas may be conducted to an extent of 90 vol% or more based on the total volume of carrier gas and offgas. In the preferred embodiments according to the invention, the off-gas formed is a carrier gas, for example, the reaction between the fuel gas and the alloy can be carried out in such a manner that carbon dioxide is used as the fuel gas and carbon monoxide as the carrier gas, The mixture of carrier gas and offgas is essentially based on a mixture of offgas and carrier gas, preferably to an extent of 90 vol% or more, more preferably to an extent of 95 vol% or more, More preferably up to about 99 vol% or more, and more preferably up to about 100 vol%. In this case, the carrier gas may subsequently be circulated and recovered in such an amount as to be modified by the combustion of the fuel (L) and the fuel gas. It is now possible to obtain a valuable product, such as carbon monoxide, which can be subsequently recovered, when the separation of the carrier gas and the off gas is selectively carried out as compared to the pure circulation of the carrier gas.

In certain embodiments, the separation step of the process of the present invention is carried out in a cyclone or cyclone reactor. The cyclone reactor is not particularly limited in terms of the setup of the cyclone reactor herein, and may have the form, for example, as possessed by standard cyclone reactors.

For example, a cyclone reactor may be connected to feed units for a fuel gas, an alloy L and a carrier gas (which may optionally also be combined and then fed together into a reaction zone), such as rotationally symmetric A reaction zone in the form of a rotationally symmetric upper section,

For example, a separation zone having a conical configuration, and

A removal device in the form of, for example, a star feeder for solid and / or liquid reaction products from combustion of the metal (M) using fuel gas, and an off-gas after combustion of the metal (M) And an expansion chamber into which a removal unit for a mixture of two gases occurring after mixing of the carrier gas can be connected.

These device components are typically present, for example, in cyclone separators. The cyclone reactor used in accordance with the present invention may alternatively have different configurations and may optionally also include additional zones. For example, individual zones (e.g., reaction zones, separation zones, expansion chambers) may also be combined in one component of the exemplary cyclone reactor and / or extend across two or more components of the cyclone reactor . Here, for example, it is also possible that the carrier gas is also undergoing the reaction of the fuel gas with the alloy L, or even added to the already completed zone.

The cyclone keeps the reaction products in the center of the reactor, e.g., the furnace space, generally. One advantage of using a pore burner is that combustion at the surface of the porous tube does not result in any small particles, such as in the case of atomization, so that the off-gas does not have solid or liquid particles, It is also possible to connect to the downstream gas turbine or the expansion turbine in a manner that is also possible. However, it is also possible to achieve an efficient separation of the off-gas from the solid and liquid reaction products in the case of atomization of the alloy L by appropriate supply of the carrier gas. Under these circumstances, using this combustion concept, it is possible to introduce the off-gas stream directly into the gas turbine after combustion of the alloy L and separation of the reaction products.

In certain embodiments, the off-gas temperature can be controlled through an excess amount of gas in the different combustion processes such that the off-gas temperature is higher than the melting temperature of the reaction products or mixtures thereof.

In certain embodiments, the cyclone reactor additionally comprises a grid, wherein the solid and / or liquid reaction products can be removed from the combustion of the alloy (L) by means of a fuel gas. These grids can additionally prevent subsequent vortexing of solid and / or liquid reaction products in the cyclone reactor.

The reaction products of combustion preferably use at least one inflator turbine and / or at least one gas turbine, such as a steam turbine, and / or at least one heat exchanger and / or at least one boiler, For which purpose it is possible, in certain embodiments, to use formed solid and / or liquid reaction products, or otherwise to use gas reaction products, for example using a reactor heat exchanger. Thus, the thermal energy emitted in the combustion can be converted to electrical energy (e.g., via the inflator turbine and / or the steam turbine). The heat energy to be released can be converted back to electric power, for example, by a heat exchanger and a downstream steam turbine. For example, higher efficiencies are achievable through the use of gas turbines that cooperate with steam turbines. For this purpose, in certain embodiments it is to be ensured that the off-gas does not have particles after metal burning, because these particles can otherwise cause long-term damage to the turbine.

When using a cyclone reactor with a carrier gas supply, in certain embodiments, for example, a mixture of offgas and carrier gas, for example in and / or after removal from the reactor and / or from the reactor, For heat transfer, or for heat transfer in a heat exchanger or turbine, such as a gas turbine or an inflator turbine.

In addition, in certain embodiments, the mixture of carrier gas and offgas may be under elevated pressure after combustion, e.g., greater than 1 bar, at least 2 bar, at least 5 bar, or at least 20 bar.

Furthermore, in a further aspect of the present invention, an apparatus for the combustion of an alloy (L) of a bipolar metal is disclosed, wherein the bipolar metal is selected from alkali metals, alkaline earth metals, aluminum and zinc, , And the alloy (L) of the amphoteric metal comprises at least two amphoteric metals,

A pore burner or unit for atomizing an alloy (L) of a positive metal,

A feed unit-feed unit for an alloy (L) of positive metal, preferably in liquid form, into the interior of a pore burner or unit for atomizing the alloy (L) is preferably a feed unit- Designed to supply the alloy (L) to a pore burner or unit for atomizing the alloy (L)

A feed unit for fuel gas, designed to supply fuel gas, and

Optionally, a heating device for providing an alloy (L) of a bipolar metal in liquid form is provided and the heating device is designed to liquefy an alloy (L) of bipolar metal.

The unit for atomization of the alloy L is not particularly limited herein and may include, for example, a one-phase nozzle or a two-phase nozzle. The pore burner may be configured as described above. The feed unit used for the alloy L may be, for example, tubes or hoses that can be heated, or otherwise conveyor belts, the heating of which may be, for example, As shown in FIG. Optionally, the feed unit for alloy L may also be connected to an additional feed unit for gas, optionally with a control unit such as a valve, by which the supply of alloy L Lt; / RTI > Likewise, it is possible that the feed unit for the fuel gas is constituted as a tube or a hose which can be selectively heated, in which case the feed unit can be suitably determined based on the state of the gas, Lt; / RTI > It is also possible that some feed units are provided for the alloy L or fuel gas.

In certain embodiments, the feed unit for the fuel gas is arranged to guide the fuel gas at least partially and preferably fully to the surface of the pore burner or to the outlet of the nozzle. This achieves an improved reaction between the alloy (L) and the fuel gas.

Moreover, in preferred embodiments, the pore burner is configured such that the reaction products formed in the combustion and optionally the unreacted alloy (L) are removed by gravity, such as by pore burners vertically mounted in the reactor and pointing towards the surface of the earth To be removed from the surface of the pore burner. In the case of vertical arrangement of the porous combustion tubes in the furnace space, the formed liquid reaction product may flow out of the tube and then downwardly into the furnace bottom. In this way, an alloy (L), possibly composed of lithium and sodium, which has not reacted in the pore burner in advance, is also burned and the heat of reaction is released into the flowing fuel gas and carrier gas.

In certain embodiments, the pore burner or nozzle may be made of a metal such as iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zircaloy and alloys of these metals, and also steels, such as stainless steel and chromium- ≪ / RTI > Suitable examples are austenitic chromium-nickel steels which are highly resistant to, for example, sodium corrosion at elevated temperatures, but can be used in combination with AC 66, Incoloy 800 or Pyrotherm G 20132 Nb Materials with 32% nickel and 20% chromium also exhibit relatively favorable corrosion properties. These materials are preferred for use at relatively high temperatures, where the reaction with the liquid alloy (L) and optionally with the liquid metal salts formed can take place in a simpler manner.

In certain embodiments, the apparatus of the present invention may further comprise a separation unit for the products of combustion of the alloy L, the separation unit being designed to separate the combustion products of the fuel L and the combustion products of the fuel L, The separation unit is preferably a cyclone reactor.

The separating unit can here serve for the separation of the offgas from the combustion of the alloy L using the fuel gas,

- A reactor in which a pneumatic burner or unit for atomization is provided, a feed unit for an alloy (L) is mounted or provided, and a fuel gas is supplied, that is, a feed unit for fuel gas is connected or provided;

- A feed unit for the carrier gas, designed to supply a carrier gas to the reactor;

- A removal unit for a mixture of offgas and carrier gas, designed to remove the mixture of offgas and carrier gas from the combustion of the alloy (L) using fuel gas; And

- And a removal unit for solid and / or liquid reaction products from the combustion of alloy (L) with fuel gas, designed to remove solid and / or liquid reaction products from the combustion of the alloy (L) .

The feed unit for the carrier gas is likewise not particularly limited, and it is possible to appropriately determine the feed unit for the carrier gas based on the state of the carrier gas, including for example, tubes, hoses and the like, It can also be under pressure.

If the combustion of the fuel gas and the alloy L can occur in the reactor, the reactor is likewise not particularly limited. In certain embodiments, the reactor may be a cyclone reactor as shown in FIG. 1 as an example and as detailed in the further embodiment of FIG.

In certain embodiments, the cyclone reactor comprises feed units for a fuel gas, an alloy (L) and a carrier gas, and a reaction zone in which a pore burner, for example in the form of a rotationally symmetrical top section,

For example, a separation zone having a conical configuration, and

A removal device in the form of, for example, a molding feeder for solid and / or liquid reaction products from the combustion of alloy L using fuel gas, and a mixture of offgas and carrier gas after combustion of alloy L in the fuel gas And an expansion chamber to which a removal unit for a mixture of two gases occurring later can be connected.

These device components are typically present, for example, in cyclone separators. The cyclone reactor used in accordance with the present invention may alternatively have different configurations and may optionally also include additional zones. For example, individual zones (e.g., reaction zones, separation zones, expansion chambers) may also be combined in one component of the exemplary cyclone reactor and / or extend across two or more components of the cyclone reactor .

An exemplary cyclone reactor is shown in Fig. The cyclone reactor 6 shown in Fig. 1 has a reaction zone 20a, a separation zone 20b and a separation zone 20b together with the reaction zone 20a in the upper component 6a, And with the expansion chamber 20c. A feed unit 1 for a fuel gas, for example in the form of a selectively heated tube or hose, and a feed unit 2 for an alloy L, for example in the form of a selectively heated tube or hose, And the alloy (L) is supplied to the pore burner (3). According to figure 1, the alloy L is fed with the aid of a feed unit 2 'for the gas, for example a tube or hose, and the feed of gas is controlled using a valve 2' ' . The alloy L and the fuel gas are fed to the reaction zone 20a. Through the feed unit 4, a carrier gas is supplied to the zone 4 'for gas distribution, and then a carrier gas from the zone 4' is supplied to the nozzles 5 allowing the cyclone to form, To the separation zone 20b. The details of this feed unit 4 and nozzle 5 with zone 4 'for gas distribution are shown in cross-section in Fig. 4 (an example without stove burner 3) by way of example, It is also possible that there are more nozzles 5 at an appropriate distance in the ring around the inner wall of zone 4 'to create. The solid and / or liquid reaction products are removed from the lower component 6b comprising the expansion chamber 20c via a removal unit 7 for solids and / or liquid reaction products of the combustion of the alloy (L) , But the mixture of the off-gas and the carrier gas is removed through the removal unit 8 for the mixture of the off-gas and the carrier gas.

Alternatively, in the apparatus of the present invention, an ignition device, such as an electric ignition device or a plasma arc, may be required, which may depend on the nature and state of the alloy (L), such as the temperature of the alloy (L) Conditions, characteristics of the fuel gas, such as the pressure and / or temperature of the fuel gas, and the arrangement of the components of the apparatus, e.g., the nature and characteristics of the feed units.

(E. G., 5 bar or greater) or higher (e. G., Greater than or equal to 5 bar), e. G., Greater than or equal to 200 deg. C, e. G. Even greater than or equal to 400 deg. (20 bar or greater) operating pressure, the internal reactor material may be made of alloys of high heat resistance, such as the alloys described above, and in extreme cases even of Haynes 214 material . It is then possible to arrange the thermal insulation around this material, which is assumed to withstand only high temperatures, to allow a sufficiently small amount of heat to pass, so that the steel wall on the exterior - the steel wall - Can be cooled or water-cooled - Absorbs compressive stress. The off-gas can then be fed to an additional process step at an elevated or higher operating pressure.

Furthermore, the reactor, for example the cyclone reactor, may also be present in the reaction zone, separation zone and / or expansion chamber and also in various feed and / or removal devices, optionally a burner, and / Heating and / or cooling devices. Moreover, additional components such as pumps for the generation of pressure, vacuum, etc. may be present in the apparatus of the present invention.

In embodiments in which the reactor takes the form of a cyclone reactor, the cyclone reactor may comprise a grid, wherein the grid is configured such that solids and / or liquid reaction products are removed through the grid during combustion of the alloy (L) . Moreover, such a grid may alternatively and additionally be present in other reactors that may be provided in the apparatus of the present invention. The use of a grid in a reactor or cyclone reactor can achieve better separation of solid and / or liquid reaction products in the combustion of the alloy (L) from the mixture of offgas and carrier gas with the fuel gas. This grid is shown by way of example in Fig. 2, where the grid 6 'is present, for example, in the cyclone reactor 6 shown in Fig. 1, and on the removal unit 7 and below the removal unit 8 And is present in the lower component 6b. It is possible to ensure reliable separation of solid and liquid reaction products or mixtures thereof, preferably by a grid which is at a sufficiently large distance from the reactor wall. In this way, already deposited solid or liquid combustion products are also not vortexed by the cyclone.

The geometry of the feed units for the carrier gas is not particularly limited as long as the carrier gas can be mixed with the off-gas from the combustion of the fuel (L) and the fuel gas. The cyclone is preferably formed here, for example, using the apparatus shown in Fig. The cyclone may alternatively be generated by different arrangements of feed units, one with respect to the other. For example, it is not impossible that a feed unit for the carrier gas is also present at the top of the reactor close to the feed units for the alloy L and fuel. Correspondingly, the appropriate geometric structures for implantation can easily be determined in an appropriate manner, for example based on flow simulations.

And the elimination units are not particularly limited, for example, it is possible for the elimination unit for the mixture of offgas and carrier gas to be constructed as a tube, while the solid and / or liquid reaction products of combustion of the metal (M) For example, as a forming feeder and / or as a tube with a siphon. It is also possible here that various valves, such as pressure valves and / or additional regulators, are provided. For example, the exemplary elimination unit 7 shown in Fig. 3 of the cyclone reactor 6 shown in Fig. 1, in this regard, comprises a siphon 9, a valve 10 for degassing, (11), but is not limited to such a removal unit. This siphon of the solid and / or liquid reaction products of the combustion of the alloy (L) with the fuel gas, optionally with a supply pressure regulator suitable for the particular operating pressure, makes it possible, for example, Lt; / RTI >

In certain embodiments, the removal unit for a mixture of offgas and carrier gas may also include a separation device for offgas and / or carrier gas and / or for separate components of offgas.

In certain embodiments, the removal unit for a mixture of offgas and carrier gas is configured to remove the carrier gas from the carrier gas, such that the mixture of offgas and carrier gas is fed at least partially into the reactor as a carrier gas and / And / or a feed unit for the fuel gas. Here, the ratio of the recirculated gas may be 10 vol% or more, preferably 50 vol% or more, more preferably 60 vol% or more, or even more preferably 10 vol% or more, based on the total volume of the carrier gas and the off- More preferably 70% by volume or more, and even more preferably 80% by volume or more. In certain embodiments, recirculation of the mixture of offgas and carrier gas can be accomplished to an extent of 90 vol% or more based on the total volume of carrier gas and offgas.

In certain embodiments, the apparatus of the present invention additionally includes at least one boiler and / or at least one heat exchanger and / or at least one heat exchanger, Of the gas turbine and / or at least one inflator turbine. Thus, in the apparatus of FIG. 1, including for example a cyclone reactor 6, one or more heat exchangers and / or boilers and / or gas turbines and / or inflator turbines, not shown, , To the removal unit 8 and / or to the unit connected to the removal unit 8.

It is also possible that heat exchange occurs in the cyclone reactor 6 itself, for example in the reaction zones 20a and / or in the outer zones of the separation zone 20b, or alternatively in the zone of the expansion chamber 20c, In this case, corresponding heat exchangers may also be connected to the turbines for power generation in the generators.

Thus, the off-gases can be sent as a mixture with the carrier gas, for further use, for example, heating of the boiler for raising the steam, release of heat in the heat exchanger, operation of the turbine,

It is possible, for example, to use a boiler, if it is not possible to find a suitable heat exchanger by means of a suitable heat exchanger, for example, the air with the appropriate pressure is heated and directed to the gas turbine as an alternative to offgas. In certain embodiments, the manner of using the boiler is more promising and technically simpler, since the boiler can only be implemented at lower temperatures and at elevated pressures.

With the aid of one or more heat exchangers and / or one or more boilers, it is then possible to generate electrical energy through the use of, for example, steam turbines and generators. Alternatively, it is possible for the mixture of off-gas and carrier gas to be directly directed to the turbine, for example a gas turbine or an inflator turbine, thereby producing power directly. This, however, requires very good removal of solids and / or liquid reaction products from combustion of the alloy (L) and the fuel gas, as can be provided in particular using a grid of reactors, according to the invention. The choice of whether a boiler or a heat exchanger is to be used may also be dependent on the plant, although it may depend, for example, on whether solid reaction products are formed or liquid reaction products are produced. In the case of liquid reaction products, such as liquid Li ₂ CO ₃ and Na ₂ CO ₃ , special heat exchangers may be required, for example in the case of solid reaction products formed, while the reactor wall may serve as a heat exchanger. In the case of a corresponding separation of the mixture of offgas and carrier gas from the solid and / or liquid reaction products, direct guidance of the mixture of offgas and carrier gas to the turbine may also be possible, / Or boilers may not be required in the off-gas stream.

In certain embodiments, the apparatus of the present invention may include a withdrawal apparatus in a removal unit for a mixture of off-gas and carrier gas, and the recovery apparatus may include a feed unit for the carrier gas and / Through the connection of a removal unit for a mixture of offgas and carrier gas to the feed unit for the carrier gas and / or to the feed unit for the fuel gas , It is designed to remove a portion of the mixture of off-gas and carrier gas. This portion may be greater than 1 volume%, preferably greater than or equal to 5 volume%, and more preferably greater than or equal to 10 volume%, based on, for example, the total volume of the mixture of off-gas and carrier gas. In addition, in certain embodiments, less than or equal to 50 vol%, preferably less than or equal to 40 vol%, more preferably less than or equal to 30 vol%, more preferably less than or equal to 30 vol%, based on the total volume of the mixture of off- Preferably 20 vol% or less, can be removed from the recycled mixture of offgas and carrier gas. Next, the recovered gas may be available, for example, as a valuable product for further reactions, such as when carbon monoxide is discharged and converted to higher-value hydrocarbons in the Fischer-Tropsch process.

It is also possible that the removed solids are further converted into valuable materials. For example, metal nitrides prepared from combustion with nitrogen can be converted to ammonia and alkali by hydrolysis with water, in which case the alkali formed also acts as a scavenger for carbon dioxide and / or sulfur dioxide can do.

The above embodiments, configurations and developments, if feasible, can be combined with one another as desired. Further possible configurations, improvements and implementations of the present invention also include combinations of features of the present invention that have been described above or which are described below with reference to operational examples but which are not explicitly mentioned. More specifically, those skilled in the art will also add the individual aspects to each basic form of the invention as improvements or additions.

The present invention will now be illustrated with reference to example embodiments, which are not intended to limit the invention in any way.

In an exemplary embodiment, for example, an alloy (L) consisting of lithium and sodium is used in liquid form, i.e., in excess of the melting point of the alloy. A liquid alloy L consisting, for example, of lithium and sodium can be introduced into the pore burner and then directly, optionally after ignition to initiate the reaction, a specific fuel gas such as air, oxygen, carbon dioxide, sulfur dioxide, Hydrogen, water vapor, nitrogen oxides NO _x , such as dinitrogen monoxide or nitrogen. Combustion of the alloy L can be achieved in the apparatus shown in Fig. 1, for example, in an amount greater than the stoichiometric amount of the fuel gas, so as not to produce excessively high off-gas temperatures. Alternatively, the fuel gas may be added in an amount less than the stoichiometric or stoichiometric amount as compared to the metal (M). After combustion, a carrier gas (e.g. nitrogen, air, carbon monoxide, carbon dioxide and ammonia), which may also correspond to the fuel gas, is diluted to reduce the temperature and to generate a cyclone for deposition of solid or liquid reaction products ). The hot off-gas stream may then be used for heating the boiler or for heat transfer in a heat exchanger, and the like.

In the second exemplary embodiment, in the apparatus shown in Figure 1, the fuel gas used may be carbon dioxide and the carrier gas used may be carbon monoxide. The used alloy (L) is, for example, one of lithium and sodium, for example, in a liquid form. Liquid alloy flows into the pore burner 3, and then reacts directly with the fuel gas. This may be the case where an electric ignition or an additional ignition burner is required. In its variant, for example, a reaction can also be achieved using an alloy of sodium and potassium according to this example, in which case the alloy of sodium and potassium may be in liquid form at room temperature.

The combustion of the alloy (L) is preferably carried out in the pore burner (3) together with the amount of carbon dioxide required in the stoichiometric aspects, but slightly above the stoichiometric amount or slightly above the stoichiometric amount (for example, 0.95: 1 to 1: 0.95 for the ratio of CO ₂ : alloy (L)). In the case of using a very large amount of carbon dioxide, for example, it is possible that the carbide is formed as a salt, and then acetylene can be obtained therefrom.

In the second stage, in the middle of the reactor / furnace 6, in the zone 4 ', the combustion products are mixed with the carbon monoxide carrier gas blown into the reactor 6 by the nozzles 5. This results in a cyclone, in which the effect of the cyclone is that the solid and / or liquid reaction products are vortexed in the reactor wall and are mainly deposited there. Preferably, an excess amount of carrier gas is used to ensure that the heat generated through combustion is transmitted far enough. As a result, it is possible to adjust the temperature of the reactor 6 appropriately.

For combustion in pure carbon dioxide, the lithium carbonate-sodium carbonate mixture formed in the case of the eutectic mixture has a melting point of 498 ° C. Liquid reaction products during combustion can be expected when the combustion temperature of the reaction products is maintained above at least 498 [deg.] C, by the mixing of the carrier gas and / or the fuel gas through the feed units 1, The feed units may here be used for cooling in a strong exothermic reaction so that the plant is not heated too much, and the lower temperature limit may be the melting point of the salt mixture formed. When the cyclone is additionally operated with gases other than carbon dioxide, such as air or additional gases, it is also possible that, for example, oxides of lithium and sodium are formed as a mixture in the reaction products. After separation of the liquid and solid reaction products, which can be improved by the grid 6 ', a mixture of off-gas and carrier gas is introduced into the boiler, for example, to drive the steam turbine with the downstream generator Or for evaporation of water to operate other technical devices (e.g., heat exchangers). The mixture of off-gas and carrier gas cooled by this process can then be reused as a carrier gas, for example, for heating of the cyclone in a furnace. Thus, residual heat from the off-gas after the evaporation process is utilized in the boiler and only the required amount of carbon dioxide in the stoichiometric aspects for combustion with Li / Na, for example coal-fired power plant Lt; RTI ID = 0.0 > off-gas < / RTI >

In certain embodiments, the combustion may be performed with a certain excess amount of fuel gas, for example, greater than 1.01: 1, preferably greater than 1.05: 1, more preferably greater than 1.05: 1, to stabilize the offgas temperature within a certain temperature range Can be carried out at a molar ratio of fuel gas to alloy (L) of 5: 1 or more, even more preferably of 10: 1 or more, such as even 100: 1 or more, It is possible not only to add additional fuel gas or carrier gas for absorption, but also to introduce the inlet of the alloy L and the addition of the fuel gas in the arrangement of the nozzles as shown in Figures 1 and 4. [ In certain embodiments, the off-gas temperature in the different combustion processes can be controlled through an excess of gas so that the off-gas temperature may be higher than the melting temperature of the reaction products or mixtures thereof.

It is possible to enrich carbon monoxide in the off-gas by recirculation of the off-gas cooled by the downstream process step. In certain embodiments, it is possible to recover a portion from the off-gas and thus obtain a gas mixture of carbon monoxide and carbon dioxide with a significantly higher proportion of carbon monoxide. Subsequent separation of the gas may purify the carbon monoxide to remove the carbon dioxide, and the carbon dioxide may be further used in the circulation or in the burner.

By recirculating the CO product gas, it is possible to further lower the combustion temperature in the oven. Lowering the combustion temperature will also be possible with an excess of CO ₂ . However, this excess should be about 16 times higher than the stoichiometric amount, and therefore the CO product gas will be highly diluted in excess CO ₂ . Therefore, in certain embodiments, it is reasonable to recycle a portion of the CO product gas to the burner and use it as a thermal ballast to lower the temperature. It is preferable here to set a specific reaction temperature by recycling a certain amount of the mixture of the off-gas and the carrier gas as the carrier gas. In this case, there is no formation of a CO / CO ₂ mixture which has to be separated in a complicated manner. The product gas consists mainly of CO and only small impurities of CO ₂ . In the steady state, most of the CO is circulated, and the amount of CO removed from the circuit is as much as the amount modified by the reaction of CO ₂ with Li - Na - and also generally with a bipolar metal alloy. For example, such circuitry may occur when CO is used as the carrier gas in a ratio of 90 vol% or more based on a mixture of off-gas and carrier gas. Thus, while a suitable amount of carbon dioxide can be supplied constantly to the combustion process, the corresponding amount of carbon monoxide can be continuously recovered from the circuit as a valuable product.

A corresponding reaction scheme is also illustrated by way of example in FIG. At CO ₂ removal 101, carbon dioxide is separated from off-gas 100 from a combustion power plant, such as, for example, a coal-fired power plant, which is then used as a carrier gas at step 102 It is burned together with the alloy. This forms the carbonate salt mixture 103, and a mixture of the carrier gas and the off gas, including CO ₂ and CO, can optionally be passed through the boiler 105 after the separation 104, The steam turbine 106 and hence the generator 107 are operated. There is recycle of off-gas 108 as carrier gas, and it is possible to discharge CO in step 109. [

In a third exemplary embodiment, the fuel gas and the carrier gas used in the apparatus shown in Figure 1 may be nitrogen. The alloy (L) to be used is, for example, one of lithium and magnesium in liquid form. The alloy L is fed to the pore burner 3 and then reacts directly with the fuel gas. This may be the case where an electric ignition or an additional ignition burner is required.

The combustion of the alloy L is carried out in the pore burner 3 together with the amount of nitrogen required in the stoichiometric aspects, but the ratio of the stoichiometric amount or less than the stoichiometric amount (e.g., N ₂ : the alloy L ) To the ratio of 0.95: 1 to 1: 0.95).

In the second stage, in the middle part of the reactor 6, the combustion products are mixed with a carrier gas, such as nitrogen, which is injected into the reactor 6 through the nozzles 5. This results in cyclones, the effect of cyclones being that the solid and liquid reaction products are vortexed in the reactor wall, and are mainly deposited there. The feed units may here be used for cooling in a strong exothermic reaction so that the plant is not heated too much, and the lower temperature limit may be the melting point of the salt mixture formed. If the cyclone is operated with gases other than nitrogen, such as air or carbon dioxide or additional gases, it is also possible that an oxide or carbonate is formed in the reaction products. After the separation of the liquid and / or solid reaction products, which can be improved by the grid 6 ', the off-gas is introduced into the boiler, for example, to drive the turbine with the downstream generator, Is utilized for evaporation of water to operate devices (e. G., Heat exchangers). Then, the cooled off-gas after this process can be reused, for example, to generate a cyclone in the reactor 6. Thus, residual heat from the off-gas after the evaporation process is utilized in the boiler and only the amount of nitrogen required in stoichiometric aspects for combustion must be obtained, e.g., by fractionation of air.

In certain embodiments, the combustion may be performed with a certain excess amount of fuel gas, for example, greater than 1.01: 1, preferably greater than 1.05: 1, more preferably greater than 1.05: 1, to stabilize the offgas temperature within a certain temperature range Can be carried out at a molar ratio of fuel gas to alloy (L) of 5: 1 or more, even more preferably of 10: 1 or more, such as even 100: 1 or more, It is possible not only to add additional fuel gas or carrier gas for absorption, but also to introduce the inlet of the alloy L and the addition of the fuel gas in the arrangement of the nozzles as shown in Figures 1 and 4. [

A corresponding reaction scheme is also illustrated by way of example in FIG. Nitrogen is separated from air 200 in air fractionation 201 and then combusted with alloy L in step 202 using nitrogen from air fractionation 201 as a carrier gas as well. This mixture of the off gas and the carrier gas containing lithium nitride and magnesium nitride forms a nitride salt mixture of 203, and N ₂ (204) can be guided through the boiler 205, with the help of steam turbine 0.0 > 206 < / RTI > and therefore the generator 207 are operated. There is a recycle of off-gas 208 as a carrier gas. Ammonia 210 may be obtained from the nitride salt mixture 203 by hydrolysis 209 to form a hydroxide 211 capable of reacting with carbon dioxide to provide carbonate 212.

In the fourth exemplary embodiment, it may also be possible to use two reactors connected in series, for example two cyclone reactors, in the case of using air as the fuel gas, for example, in this case, Oxygen from the alloy and air can be used to produce an oxide mixture, the off-gas mainly comprising nitrogen, which then reacts with the alloy L as a fuel gas in the second cyclone reactor to form a metal Nitride can be provided. In this case, for example, nitrogen can act as a carrier gas, which can also be obtained from the first off-gas or, for example, if it is circulating, from the first off-gas itself.

A fifth exemplary embodiment is shown in Fig. 5, wherein the reactor is similar to the reactor shown in Fig. Alloy L, such as Na / K, is fed to the cyclone reactors 6 (6a, 6b) in the liquid form, optionally at room temperature, through a pneumatic burner 3 and a fuel gas, Lt; / RTI > A particularly advantageous feature is the injection of fuel into the cyclone reactors 6a, 6b at points with high gas velocities, so that the liquid metal droplets can be easily removed from the pore burner 3. It is possible to adjust the off-gas temperature through the stoichiometry of the reaction. This is advantageously chosen such that the salt mixture formed is kept in liquid form. In this case, the melting temperature of the salt mixture can be lowered to about 700 占 폚, compared to 900 占 폚 for potassium carbonate and 858 占 폚 for sodium carbonate.

After combustion, the reaction products are separated by a cyclone, for example, the salt products of the liquid form of the alloy (L) are recovered at the reactor outlet and collected in a vessel (15) for solid and liquid reaction products. By means of the heat exchanger 12, thermal energy can be obtained from these reaction products at the lower end of the reactor, for example at the reactor wall where salt melt flows out, and then this energy is transferred to the steam turbine 13 and the generator (14). Thus, the hot, and particle-free gas removed under pressure can be converted to power with high efficiency. The off-gas is directed to the inflator turbine 16 through the elimination unit 8 from which power can eventually be obtained using the generator 14 '. In the case of an excess amount of CO ₂ in the reaction gas, the off-gas can be recycled as the reactive gas to the cyclone reactor 6 after discharge from the inflator turbine 16, and therefore the CO concentration in the off-gas can be increased. Thus, the recycle of the off-gas occurs through the recycle unit 18, and the off-gas can eventually be used as the carrier gas in the cyclone reactors 6 (6a, 6b). In addition, the off-gas can be withdrawn through the withdrawal port and fed to the off-gas separation 17, for example using CO ₂ as the fuel gas and CO as the product of the carrier gas and combustion have.

A sixth exemplary embodiment is shown in Fig. 6 where atomization of the alloy L takes place at the end of the feed unit 2 instead of the pore burner 3 and then in the reaction space 30, The reaction occurs together with the fuel gas from the fuel cell 1. Thereafter, the formed reaction products are transferred to the cyclone reactors 6 (6a, 6b). Although the reaction space 30 is connected laterally in FIG. 6, if the reaction products undergo cyclone separation, the reaction space 30 may also be connected in other ways, for example, to a cyclone reactor at the top.

The present invention describes the proper use of alloys of bipolar metals as physical energy storage means that can be generated electrochemically through the utilization of renewable electrical energy (overproduction, charging processes). Emission of the energy storage means can be achieved in the form of a combustion process in carbon dioxide, nitrogen, oxygen, air, air, and the like.

The present invention, in certain embodiments, can ensure separation of gas reaction products from salts formed in the reaction by the use of a cyclone and the liquid removal of the salt mixture. In addition, through the use of alloys (L) of bipolar metals and the use of lower melting temperatures of salt mixtures formed in the case of combustion compared to individual metal compounds, the combustion reaction at lower temperatures is also achieved It is possible to avoid the use of expensive materials for the combustion space, while at the same time ensuring the liquid removal of the salt mixture. The re-conversion of the heat energy released from the combustion into electric power is carried out, for example, through the use of an expander turbine for gases which can be removed under pressure and at high temperatures or by heat exchangers of the reactor wall and subsequently by the steam turbine .

Through the construction of the apparatus of the present invention, solid or liquid reaction products or mixtures thereof, in particular, through the use of porous combustion tubes, are separated from the formed offgas in a simple manner and are thus obtained, for example, from gas turbines or inflator turbines, , Or it is possible to send offgas for use in a boiler. In addition, in this manner, the entire combustion device can also be made more compact, and the combustion can be configured to be more gradual to the device through localization of the combustion process.

In addition, a reactor such as a furnace, such as a furnace, can be run at elevated operating pressure, and thus the combustion and deposition process can be matched to the respective conditions of the downstream stage. In certain embodiments, the possibility of a separation of the fuel gas and the carrier gas for the establishment of the cyclone enables recirculation of the off-gases after the release of heat. Recirculation is easily possible with this configuration. Gas mixtures are also possible as fuel gas and carrier gas. By recycling the off-gas after the process step (s), it is possible to save energy and materials.

Claims (13)

A process for burning an alloy of electropositive metal using a fuel gas,
Wherein the positive metal is selected from alkali metals, alkaline earth metals, aluminum and zinc, and mixtures thereof,
Wherein the alloy of the positive metal comprises at least two positive metals,
Wherein the alloy of the positive metal is burned using the fuel gas,
A process for burning an alloy of a positive metal with a fuel gas. The method according to claim 1,
Wherein the alloy of the positive metal is burned in liquid form,
A process for burning an alloy of a positive metal with a fuel gas. 3. The method according to claim 1 or 2,
Wherein the combustion occurs at a temperature exceeding the melting point of the salts formed in the reaction of the fuel gas with the alloy of the amphoteric metal,
A process for burning an alloy of a positive metal with a fuel gas. 4. The method according to any one of claims 1 to 3,
Wherein the alloy of the positive metal is guided into a pore burner in liquid form and burned with the aid of the pore burner, the fuel gas is selectively directed to the outer surfaces of the pore burner, Which is burned together with the metal alloy,
A process for burning an alloy of a positive metal with a fuel gas. 4. The method according to any one of claims 1 to 3,
Preferably, the alloy of the positive metal in liquid form is atomized and burned using the fuel gas,
A process for burning an alloy of a positive metal with a fuel gas. 6. The method according to any one of claims 1 to 5,
The reaction products after said combustion are preferably separated by the aid of cyclone,
A process for burning an alloy of a positive metal with a fuel gas. 7. The method according to any one of claims 1 to 6,
The reaction products of the combustion preferably comprise at least one expander turbine and / or at least one steam turbine and / or at least one heat exchanger and / or at least one boiler Used to generate energy,
A process for burning an alloy of a positive metal with a fuel gas. An apparatus for the combustion of alloys of amphoteric metals,
Wherein the amphoteric metal is selected from alkali metals, alkaline earth metals, aluminum and zinc, and mixtures thereof, and wherein the alloy of the amphoteric metal comprises at least two amphoteric metals,
The apparatus comprises:
A pore burner or unit for atomizing the alloy of the positive metal,
A feed unit for an alloy of the positive metal, preferably in liquid form, into the interior of the pore burner or unit for atomizing the alloy, the feed unit comprising a feed unit, preferably in the form of a liquid, Designed to supply an alloy of a malleable metal to said pore burner or unit for atomizing said alloy,
A feed unit for fuel gas, designed to supply fuel gas, and
Optionally, a heating device for providing an alloy of the positive metal in liquid form,
The heating device being designed to liquefy the alloy of the positive metal,
Apparatus for the combustion of alloys of amphoteric metals. 9. The method of claim 8,
And a feed unit for the fuel gas is arranged to direct the fuel gas at least partially to the surface of the pore burner,
Apparatus for the combustion of alloys of amphoteric metals. 10. The method of claim 9,
Wherein the pore burner is arranged such that the reaction products formed from the combustion and optionally the positive metal are separated from the surface of the pore burner by gravity,
Apparatus for the combustion of alloys of amphoteric metals. 11. The method according to any one of claims 8 to 10,
The pore burner or unit for atomizing the alloy of the positive metal is selected from the group consisting of iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zircaloy and alloys of these metals and also steels, stainless steel, and chromium-nickel steel.
Apparatus for the combustion of alloys of amphoteric metals. The method according to any one of claims 8 to 11,
Further comprising a separation unit, preferably a cyclone, for the products of combustion of the positive metal,
The cyclone preferably has a perforated plate,
Apparatus for the combustion of alloys of amphoteric metals. 13. The method according to any one of claims 8 to 12,
Further comprising at least one inflator turbine and / or at least one steam turbine and / or at least one heat exchanger and / or at least one boiler,
Apparatus for the combustion of alloys of amphoteric metals.

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