Combustion Of Electropositive Metal In A Liquid

The present disclosure relates to reactions with an electropositive metal. Specific embodiments may include reactions of electropositive metals with a liquid, undergoing at least partial reaction in the liquid, e.g., a method comprising: atomizing or jetting the electropositive metal; introducing the electropositive metal into the liquid below a surface of the liquid; and producing at least partial reaction of the electropositive metal in the liquid.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage Application of International Application No. PCT/EP2015/075847 filed Nov. 5, 2015, which designates the United States of America, and claims priority to DE Application No. 10 2014 222 919.7 filed Nov. 11, 2014, the contents of which are hereby incorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure relates to reactions with an electropositive metal. Various example electropositive metals may include alkali metals, alkaline earth metals, aluminum, and zinc, mixtures and alloys thereof. Specific embodiments may include reactions of electropositive metals with a liquid, undergoing at least partial reaction in the liquid, and also to an apparatus for implementing the method.

BACKGROUND

Fossil fuels annually yield tens of thousands of terawatt-hours of electrical, thermal, and mechanical energy. The end product of the combustion, carbon dioxide (CO2), is increasingly becoming an environmental and climate problem, however.

A complete energy circuit produced with electropositive metals is shown in DE 10 2008 031 437 A1 and DE 10 2010 041033 A1. Serving as a case study here is lithium, which serves both as energy carrier and as energy store.

Application DE 10 2014 203039.0 and application DE 10 2014 209529.8, 2013E24783DE, describe the use among others of alkali metals as energy stores and their utilization in a power plant operation.

Application DE 10 2014 203039.0 here describes a construction (cyclone burner) for the combustion of, for example, lithium in CO2 or in N2-containing atmospheres with simultaneous separation of the solid and gaseous reaction products via the cyclone.

Application DE 10 2014 209529.8 describes a pore burner for electropositive metals in the combustion in gases such as, for example, CO2, N2, O2, and also gas mixtures thereof with or without steam. Here, liquid lithium is introduced into a porous tube under pressure and is burnt with a gas in the pore burner. For the pore burner described therein, ceramic tubes are among those proposed. Particularly at relatively high temperature, however, liquid alkali metals react with oxidic (oxygen withdrawal) or nitridic materials. Particularly preferred, therefore, are metals comprising materials which cannot be alloyed with alkali metal.

SUMMARY

There nevertheless is a demand for a method and for an apparatus which enables efficient removal of the products formed in the reaction with electropositive metal, without solid or liquid products entering the gas phase and being removed at cost and inconvenience, and also for a method and an apparatus with which at the same time it becomes possible to carry out efficient conversion of the energy given off in the reaction.

Some embodiments may include methods for reacting an electropositive metal, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also mixtures and/or alloys thereof, with a liquid, the electropositive metal being atomized and/or jetted into the liquid below the liquid surface, and undergoing at least partial reaction in the liquid.

In some embodiments, the electropositive metal is supplied as liquid.

In some embodiments, the liquid being selected from the group consisting of water and supercritical liquids such as carbon dioxide and sulfur oxides.

In some embodiments, the electropositive metal being atomized and/or jetted by means of a pore burner and/or a nozzle.

In some embodiments, the liquid during the reaction being at least partially vaporized, and the vaporized liquid being replaced by supply of liquid.

In some embodiments, the vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid being used at least partially for production of chemical products, and/or the energy of the vaporized liquid and/or of gaseous products formed in the reaction being at least partially converted.

In some embodiments, the liquid during or after the reaction being taken off at least partially as solution or suspension, and the energy of the solution or suspension taken off being at least partially converted.

Some embodiments may include apparati for reacting an electropositive metal with a liquid, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also alloys and/or mixtures thereof, comprising a reactor in which the reaction between the electropositive metal and the liquid takes place, at least one pore burner and/or at least one means for jetting and/or atomizing the electropositive metal into the liquid, on and/or in the reactor, at least one first supply means for the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, said supply means being designed in such a way as to supply the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, at least one second supply means for the liquid, on and/or in the reactor, said means being designed in such a way as to supply the liquid to the reactor, at least one first removal means for the solution or suspension formed in the reaction of electropositive metal and liquid, said means being designed in such a way as to remove from the reactor the solution or suspension formed in the reaction of electropositive metal and liquid, at least one second removal means for gaseous products, said means being designed in such a way as to remove from the reactor at least partially vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid, and a control means, which is designed in such way as to supply the liquid to the reactor in such a way that the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal are located in the liquid in the reactor, below the liquid surface.

In some embodiments, there is a heating apparatus for providing the electropositive metal as a liquid, said apparatus being designed in such a way as to liquefy the electropositive metal before or during the supplying of the electropositive metal.

In some embodiments, the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal being made of a material selected from the 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-nickel steel.

In some embodiments, there is at least one first means for conversion of energy, said means being connected to the at least one first removal means and being designed in such a way as to convert at least partially the energy of the solution or suspension removed.

In some embodiments, there is at least one second means for conversion of energy, said means being connected to the at least one second removal means and being designed in such a way as to convert at least partially the energy of the at least partially vaporized liquid and/or of gaseous products formed in the reaction of electropositive metal and liquid, and/or at least one means for producing chemical products, said means being designed in such a way as to convert the vaporized liquid and/or the gaseous products formed in the reaction of electropositive metal and liquid into further chemical products.

In some embodiments, there is at least one third removal means, which is connected by the first means to the means for conversion of energy and which is designed in such a way as to remove the solution or suspension removed from the first means to the means for conversion of energy, at least one first separating means, which is connected to the at least one third removal means and which is designed in such a way as to separate the liquid from the solution or suspension removed, and at least one first return means for liquid from the first separating means, which is connected to the second supply means and/or to the reactor and which is designed in such a way as to supply the liquid from the first separating means to the second supply means and/or to the reactor.

In some embodiments, there is at least one second separating means, which is designed in such a way as to at least partially separate the liquid and/or the vaporized liquid from the vaporized liquid removed and/or from the gaseous products formed in the reaction of electropositive metal and liquid, and at least one second return means for liquid and/or vaporized liquid from the second separating means, said return means being connected to the second supply means and/or to the reactor and being designed in such a way as to supply the liquid and/or the vaporized liquid from the second separating means to the second supply means and/or to the reactor.

In some embodiments, there is at least one detecting means which is located on and/or in the reactor and is connected to the control means, and which is designed in such a way as to detect the amount of liquid in the reactor.

BRIEF DESCRIPTION OF THE DRAWINGS

The appended drawings are intended to illustrate embodiments of the teachings of the present disclosure and to impart further understanding thereof. In connection with the description, they serve to elucidate concepts and principles of the teachings. Other embodiments and many of the stated advantages are apparent when considered in light of the drawings. The elements in the drawings are not necessarily shown to scale with respect to one another. Elements, features, and components that are the same, functionally identical and have the same effect are each provided with the same reference symbols in the figures in the drawings, unless stated otherwise.

FIG. 1 shows in schematic form an exemplary embodiment of a sintered metal nozzle which can be used in an apparatus according to the present teachings;

FIG. 2 shows in schematic form another exemplary embodiment of a sintered metal nozzle which can be used in an apparatus according to the present teachings;

FIG. 3 represents, in schematic form, an exemplary single-fluid nozzle for supplying liquid electropositive metal into the liquid, which can be used in an apparatus according to the present teachings;

FIG. 4 represents, in schematic form, an exemplary two-fluid nozzle for supplying liquid electropositive metal into the liquid, which can likewise be used in an apparatus according to the present teachings;

FIG. 5 shows, in schematic form, an exemplary embodiment of an apparatus according to the present teachings; and

FIG. 6 shows, furthermore, in schematic form, another exemplary embodiment of an apparatus according to the present teachings.

 DETAILED DESCRIPTION

A simple removal of the resultant reaction products, especially solid and liquid reaction products, is possible if the electropositive metal is introduced directly into a liquid with which it is able to react, meaning that the solid and liquid products and any gaseous products go directly into solution or suspension and that therefore the costly and inconvenient removal thereof is avoided. Moreover, through introduction into the liquid, the heat formed during the reaction can be taken off effectively, thereby also facilitating the reaction regime. By vaporizing the liquid here it is also possible, according to certain embodiments, to increase the vapor pressure in the system. By virtue of the reaction regime of the invention, therefore, it is also possible to enable efficient conversion of the thermal energy released on exothermic reaction, into electricity, for example, or into thermal energy for, for example, district heating. As a result of the reaction in liquid, furthermore, chemical products of value can be produced that can be simply taken from the apparatus.

The suitable selection of electropositive metals, e.g., alkali/alkaline earth metals, and also alloys thereof, allows use of the metals as physical energy stores. The electropositive metals may be prepared, for example, electrochemically utilizing electrical energy (charging procedure). The chemical energy that is consequently stored in the electropositive metals can be released again as thermal energy via a combustion process/reaction in a liquid such as water, supercritical/liquid CO2 or SO2. In subsequent operations (e.g., heat exchanger and steam turbine or gas turbine and/or expander turbine), this thermal energy can be converted back into electrical energy.

In some embodiments, a method for reacting an electropositive metal, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also mixtures and/or alloys thereof, with a liquid, includes the electropositive metal being atomized and/or jetted into the liquid below the liquid surface, and undergoing at least partial reaction in the liquid.

In some embodiments, an apparatus for reacting an electropositive metal with a liquid, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also alloys and/or mixtures thereof, comprises a reactor in which the reaction between the electropositive metal and the liquid takes place, at least one pore burner and/or at least one means for jetting and/or atomizing the electropositive metal into the liquid, on and/or in the reactor, at least one first supply means for the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, said supply means being designed in such a way as to supply the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, at least one second supply means with the liquid, on and/or in the reactor, said means being designed in such a way as to supply the liquid to the reactor, at least one first removal means for the solution or suspension formed in the reaction of electropositive metal and liquid, said means being designed in such a way as to remove from the reactor the solution or suspension formed in the reaction of electropositive metal and liquid, at least one second removal means for gaseous products, said means being designed in such a way as to remove from the reactor at least partially vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid, and a control means, which is designed in such a way as to supply the liquid to the reactor in such a way that the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal are located in the liquid in the reactor, below the liquid surface.

Some embodiments include methods for reacting an electropositive metal, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also mixtures and/or alloys thereof, with a liquid, the electropositive metal being atomized and/or jetted into the liquid below the liquid surface, and undergoing at least partial reaction in the liquid.

The electropositive metal according to particular embodiments is selected from alkali metals, e.g., Li, Na, K, Rb, and Cs, alkaline earth metals, e.g., Mg, Ca, Sr, and Ba, Al and Zn, and also mixtures and/or alloys thereof. In some embodiments the electropositive metal is selected from Li, Na, K, Mg, Ca, Al, and Zn; according to certain embodiments, the electropositive metal comprises at least lithium, sodium, or potassium or is one of these metals. Any of the stated metals, however, may be combined. The electropositive metal, moreover, is not subject to any particular limitation and may take the form, for example, of a solid or a liquid. On being supplied as a liquid, the alloy can be easily transported and the electropositive metal can be atomized or sprayed more effectively.

In some embodiments, the electropositive metal is supplied as liquid. In this way the electropositive metal can be easily transported and the reaction of the electropositive metal in the liquid can be localized more easily. According to particular embodiments, moreover, the combustion takes place at a temperature which lies above the melting point of the products formed in the reaction of the electropositive metal and the liquid. By means of this configuration, the reaction of the electropositive metal produces liquid reaction products, which may go more easily into solution or suspension/emulsion. As a result, furthermore, the means for jetting or atomizing, or pore burners for spraying or atomizing, the electropositive metal can be more easily kept free of fouling and deposits. According to particular embodiments, the reaction products of the reaction of the electropositive metal with the liquid are in the liquid, something which can easily be determined on the basis of the reactants and their properties. Thus, for example, various hydroxide salts of the alkali metals are readily soluble in water.

Suitable liquids include those which are able to react with the electropositive metal in an exothermic reaction, there being no particular limitation on these liquids. By way of example, the liquid may comprise water, nitrogen, supercritical carbon dioxide, or supercritical sulfur oxides SOx where 0<x≤4, or mixtures thereof. The method may therefore also be used for desulfurization. Depending on the liquid, different products may be obtained here with the different electropositive metals, these products possibly being obtained as solid, as liquid or else in the form of gas. Depending on the liquid selected, furthermore, the products formed in the reaction may be at least partially soluble in the liquid, allowing the products to be easily removed.

In the exemplary case of combustion in water, the solid reaction product, when using alkali metals as electropositive metal (e.g., LiOH, NaOH, KOH) may be very readily soluble in water (solubility in H2O: NaOH 1090 g/l; KOH 1120 g/l, LiOH 128 g/l) and so can easily be separated from the gaseous products in the operation.

Consequently, according to particular embodiments, in addition to energy storage and conversion, a substance of value in the liquid removed, which may be taken off as a solution or suspension, can also be obtained—in the case, for example, of simultaneous preparation of NaOH, LiOH, KOH. The corresponding enthalpies of formation for selected alkali metals as electropositive metal in the reaction with water and carbon dioxide, respectively, are shown in table 1.

TABLE 1 Exemplary enthalpies of formation in the reaction with water and carbon dioxide Reaction Enthalpy Combustion equations enthalpy kJ/mol kJ/mol 2Na + 2H2O → 2NaOH + H2 −281 −140 2K + 2H2O → 2KOH + H2 −279 −139 2Li + 2H2O → 2LiOH + H2 −404 −202 2Na + 2CO2 → Na2CO3 + CO −432 −216 2K + 2CO2 → K2CO3 + CO −473 −236 2Li + 2CO2 → Li2CO3 + CO −539 −270

Exemplary reactions with sulfur oxides are as follows:


6Li+SO2→Li2S+2Li2O


8Li+SO3→Li2S+Li2O


Li2O+SO2→Li2SO3−438.7 kJ/mol

The gaseous products hydrogen and carbon monoxide that are formed in these reactions, and also, possibly, other gaseous products in other liquids, may additionally be taken off and/or else used further as substances of value—such as, for example, CO and H2 in the case of a Fischer-Tropsch synthesis. In a reaction of electropositive metal, lithium for example, with carbon dioxide, therefore, metal carbonate, e.g., lithium carbonate, and carbon monoxide may be formed, for example, and from the carbon monoxide it is possible to recover higher products, including, for example, longer-chain carbon-containing products such as methane, ethane, etc. through to benzine, diesel, but also methanol, etc., in a Fischer-Tropsch process, for example.

Additionally, for example, in the case of a reaction of electropositive metal, lithium for example, with nitrogen, the possible products include metal nitride, such as lithium nitride, which can then be allowed to undergo further reaction later on to form ammonia.

Analogous reactions may also result for the other stated metals.

According to particular embodiments, the liquid is selected from the group consisting of water and supercritical liquids such as carbon dioxide and sulfur oxides. A supercritical liquid or supercritical fluid is understood here to be a liquid or a gas which is located above the critical pressure and the critical temperature.

In some embodiments, the electropositive metal need not have undergone full reaction in the liquid before the solution or suspension formed in the reaction of electropositive metal and liquid is removed; according to particular embodiments, however, the electropositive metal may undergo complete or substantially complete reaction before the solution or suspension formed in the reaction of electropositive metal and liquid is removed. According to particular embodiments, the electropositive metal reacts to an extent of at least 90 mol %, at least 95 mol % or at least 99 mol % with the liquid before the solution or suspension is removed.

In some embodiments, there are no particular limitations in the jetting and/or the atomizing of the electropositive metal, which may take place in a suitable way, as for example by customary nozzles or atomizers, an example being a liquid sintered metal nozzle, or alternatively by jetting/atomizing through open-pore structures such as a pore burner. In addition, both atomizing and jetting of the electropositive metal may take place into the reaction chamber through, for example, various supply devices with nozzles and/or atomizers. For the alkaline earth metals, for example, especially Ca and/or Mg, atomization in the form of powder is used in particular embodiments. For alkali metals, jetting, e.g., in the form of liquid may be more effective.

In some embodiments, the liquid includes further constituents, as for example various additives for stabilizing the liquid, particularly defoamers or other additives such as crystallization aids for the purpose of setting particular product properties (morphology).

Because the electropositive metal is supplied below the liquid surface, the solid and liquid products, and possibly gaseous products, formed in the reaction of electropositive metal and liquid are able to pass directly into solution or suspension, thereby obviating their costly and inconvenient separation, and hence facilitating the reaction regime and the construction of the apparatus. Introduction below the liquid surface, moreover, makes it possible to ensure that the electropositive metal does not come into contact with the gas space located above the liquid surface, with consequent side-reactions. By introduction into the liquid, furthermore, it is possible to remove effectively the heat produced during the reaction, something which further facilitates the reaction regime. According to certain embodiments, moreover, vaporization of the liquid can be used here to raise the vapor pressure in the system. The reaction regime according to the invention therefore makes it possible as well to enable efficient conversion of the thermal energy liberated in the exothermic reaction into, for example, electricity or thermal energy for district heating, for example. As a result of the reaction in liquid, furthermore, chemical products of value may be produced and may be taken easily from the apparatus.

For improved dissipation of the heat produced during the reaction, the reactor may include a stirrer or other means for mixing and distributing the liquid, such as a plurality of supply nozzles for liquid, for example, which may ensure effective mixing of the liquid with the electropositive metal and with the products that form, as well. In this way it is also possible to achieve targeted removal of the heat of reaction and of solid products, and so, in certain embodiments, heated relative concentration solutions of reaction products are removed in a targeted way. Corresponding stirring and/or mixing means with appropriate flow geometries may be suitably provided in dependence on the construction of the reactor, of the supply means, etc.

According to certain embodiments, the electropositive metal is atomized and/or jetted by means of a pore burner and/or a nozzle. There are no particular restrictions on the nozzle and/or the pore burner here, and they may be selected appropriately in dependence on the circumstances such as, for example, on the aggregate state of the electropositive metal and on the nature of the liquid, and on further properties such as the crosslinking behavior of the liquid, for example.

Jetting or atomizing of the electropositive metal here may take place in a suitable way, not subject to any particular restriction. There is also no particular restriction on the nature of the nozzle, which may encompass both single-fluid and two-fluid nozzles. According to certain embodiments, the electropositive metal is jetted, e.g., as a liquid. Also possible, however, is the jetting of particles of the electropositive metal. More efficient jetting, however, may be achieved by using the electropositive metal as a liquid, and optionally, through the temperature of the electropositive metal, self-ignition of the combustion reaction and/or reaction with the liquid may also be possible, removing the need for an ignition source. If it is not the case, an ignition source may also be provided for at least occasionally igniting the electropositive metal—there are no particular restrictions on this source—in order, for example, to initiate the reaction with the liquid. Use may be made, for example, of an electric arc, laser, plasma nozzle, etc., to ignite the electropositive metal.

Exemplary nozzles and nozzle geometries are shown in FIGS. 1 to 4. FIGS. 1 and 2 show, by way of example, two different geometries for sintered metal nozzles, to which the electropositive metal 1 is supplied, e.g., in liquid form, from below and/or from the side, depending on point of view, the liquid 3 being supplied through these nozzles. In this case, the reaction region 4 is located close to the nozzle exit. FIG. 1 shows a screen nozzle 2′, where the electropositive metal is jetted into the liquid through the screen at the nozzle exit, which is not subject to any particular restriction, while in FIG. 2 the exit of the electropositive metal takes place through a perforated metal plate, meaning that the nozzle corresponds to a perforated metal plate nozzle 2″.

Further nozzles with different geometries of supply of the electropositive metal, which can also be used in the above-stated nozzles and also in any other nozzles, are shown in FIGS. 3 and 4. In the case of the single-fluid nozzle shown in FIG. 3, the electropositive metal 1 is swirled in the nozzle element 2″ by a nozzle swirl element 5, whose design is not restricted to the form shown here, in order to achieve more effective atomization of the electropositive metal at the nozzle exit.

In the two-fluid nozzle shown in FIG. 4, this swirling or distribution of the electropositive metal 1 is achieved by admixing an atomizing gas 6 in an atomizing gas channel 6′, while the electropositive metal 1 proceeds through the metal channel 1′. Through appropriate setting of the nozzle geometry and of the channels, which may also be switched in terms of their positions, it is possible at the nozzle exit 7 to ensure effective atomization. In the case of combustion in liquid or supercritical CO2, for example, CO2 itself may be utilized as atomizing medium for the two-fluid nozzle; in other words, the atomizing gas may correspond to the liquid as a substance.

In accordance with the invention, however, there is no particular restriction on the atomizing gas, which may also be selected in dependence on the desired product. Atomizing gas employed comprises, for example, air, carbon monoxide, carbon dioxide, oxygen, methane, hydrogen, steam, nitrogen, dinitrogen monoxide, mixtures of two or more of these gases, etc.

Besides the various nozzles, it is also possible for different kinds of pore burners, as for example a porous pipe, and/or different kinds of mixing forms, to serve for atomization and/or jetting of the electropositive metal. Examples of such include a pipe provided with parallel capillaries, in which case the capillaries in longitudinal direction are intended for jetting. Possible embodiments, however, may also be other apparatuses traversed longitudinally or transversely (radially) by capillaries, and made from a material which is resistant with respect to the electropositive metal. In such nozzles or atomizers, for example, liquid alkali metal may enter the reactor at the end of the capillaries below the water surface. Porous nozzles are available, for example, from Exxentis AG, Switzerland.

According to certain embodiments, the electropositive metal, e.g., in liquid form, is introduced into a pore burner and jetted by means of the pore burner. According to certain embodiments, however, internal mixing as in a conventional pore burner does not take place, in order to prevent the pores becoming clogged with solid reaction products. According to certain embodiments, therefore, the pore burner is a pore burner without internal mixing. When the pore burner is used in accordance with certain embodiments, the pores serve solely to increase the surface area of the electropositive metal. In the case of continuous supply of the electropositive metal, reaction with the liquid may occur at the outlet of the pores close to the surface of the pore burner, provided it is possible to ensure that reaction products formed are conveyed from the pore burner by electropositive metal conveyed after them. This, however, is also possible if the products formed are soluble in the liquid and can be removed from the pores by dissolution. C2-C4

When the pore burner is used, moreover, the reaction can be localized at the pore burner, with the reaction products as well being obtained at or close to the pore burner, meaning that the reaction is localized and, correspondingly, that the reaction can be controlled more easily.

There are no particular restrictions on the form of the pore burner, which according to certain embodiments comprises a porous pipe as burner. According to certain embodiments, the pore burner comprises a porous pipe to which the electropositive metal can be supplied at one opening at least. The electropositive metal is preferably supplied only through an opening in the pipe, and the other end of the pipe is closed or consists likewise of the material of the porous pipe. The porous pipe in this case may be, for example, a porous metal pipe, consisting for example of iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, Zircaloy, and alloys of these metals, and also steels such as stainless steel and chromium-nickel steel. The pore burner consists preferably of a material selected from the 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-nickel steel. Suitable, for example, are austenitic chromium-nickel steels, which, for example, are highly resistant to depletion by sodium at high temperature, but also materials with 32% nickel and 20% chromium, such as AC 66, Incoloy 800 or Pyrotherm G 20132 Nb still exhibit relatively favorable corrosion behavior. There are no other restrictions on the further constituents of the pore burner, which may comprise, optionally, an ignition source, etc.

According to certain embodiments, the pore burner is supplied with the electropositive metal as a liquid in the interior of the pore burner. This leads to more effective distribution of the electropositive metal in the pore burner and to more uniform emergence of the electropositive metal from the pores of the porous pipe, allowing a more uniform reaction between electropositive metal and liquid to take place. The combustion of electropositive metal and liquid may be appropriately controlled, for example, via the pore size of the pores in the pipe, the electropositive metal used, its density—which may be associated with the temperature of the electropositive metal—the pressure at which the electropositive metal is introduced into the pore burner, the pressure of the liquid, etc. The electropositive metal may be injected into the porous pipe, for example, including with assistance of a further, pressurized gas, for example, on which there is no restriction provided it does not react with the electropositive metal—an inert gas, for example.

In the reaction, according to certain embodiments, the liquid may be at least partially vaporized, and the vaporized liquid may be replaced by supply of liquid. The amount of vaporized liquid here may be dependent on the nature of the electropositive metal and of the liquid, and also on the properties thereof such as melting or boiling temperature, type of reaction, etc., and also on the nature of supply of the electropositive metal, the reactor construction, etc., and may be determined appropriately.

According to certain embodiments, the amount of liquid which vaporizes is replaced by the equal amount of liquid, by supply; however, the subsequent introduction at least occasionally, or else once, of a greater or lesser quantity of liquid, to adjust the amount of liquid in the reactor in a different way and hence possibly also to exert influence on the reaction, in respect of the removal of heat, for example, is not ruled out. In this case, however, care should be taken to ensure that the supplying of the electropositive metal itself, if the stock of liquid in the reactor changes, takes place within the liquid, in other words below the liquid surface. According to certain embodiments, therefore, the amount of liquid supplied can be controlled. Control in this case may take place, for example, using various valves into the respective supplies of electropositive metal and/or liquid; according to certain embodiments, the amount of liquid in the reactor may also be detected, using sensors, for example, such as pH sensors, IR sensors, capacitive level sensors, ultrasonic sensors, other optical sensor types, etc.

According to certain embodiments, the vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid—where the gaseous products and/or the vaporized liquid may be at elevated pressure of, for example, more than 1 bar, at least 2 bar, at least 5 bar, or at least 20 bar—are used at least partially for production of chemical products, as for example CO and/or H2O and/or H2 in a Fischer-Tropsch synthesis, and/or the energy of the vaporized liquid and/or of gaseous products formed in the reaction is at least partially converted, preferably into thermal and/or electrical energy, more preferably using 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, optionally in conjunction with at least one generator.

According to certain embodiments, the liquid during or after the reaction is taken off at least partially as solution or suspension, and the energy of the solution or suspension taken off is at least partially converted, preferably using at least one heat exchanger and/or at least one boiler, optionally in conjunction with at least one generator.

According to certain embodiments, the liquid may be at least partially separated from the solution or suspension removed, and returned to the reaction.

At least partial conversion of the energy of the solution or suspension removed, on the one hand, and of the vaporized liquid and/or of gaseous products formed in the reaction, on the other hand, encompasses any at least partial conversion of the energy present and/or released during the reaction of electropositive metal and liquid, as for example thermal and/or kinetic energy, into another form of energy, such as electricity, process steam or district heating, for example. The energy, for example, may be converted into thermal energy of another medium such as water in, for example, a heat exchanger, or into electrical energy. The amount of energy converted here may be dependent on various factors such as efficiencies of the conversion means used, energy losses in the system, where appropriate, the control of the reaction and of the volume flows, etc.

There is no particular restriction on the at least partial conversion of energy, which may encompass, for example, conversion into thermal and/or electrical energy. According to certain embodiments, electrical energy at least is produced with the method of the invention and with the apparatus of the invention.

Therefore, the thermal energy liberated in the combustion may be converted (via an expander turbine and/or steam turbine, for example) into electrical energy. The thermal energy liberated may be converted back to power via a heat exchanger and subsequent steam turbine, for example. Higher efficiencies are attainable, for example, through the use of gas turbines in combination with steam turbines. For this purpose, according to certain embodiments, it must be ensured that the outgoing gas after metal combustion is particle-free, since these particles may otherwise cause damage to the turbine over the long term.

The gaseous products formed in the reaction (CO, for example, in the case of combustion in CO2) may be further exploited, according to certain embodiments. The vaporized liquid and/or gaseous products formed in the reaction are preferably free from solid particles and in that case can be passed via an expander turbine, for example, under pressure, this being achievable through corresponding reaction in the liquid.

In the case of the reaction of the electropositive metal with the liquid it is possible, according to certain embodiments, for release to occur not only of the reaction energy but also of solvation energy or hydration energy and/or lattice energy, in the case of formation of hydrates in water, for example. For the combustion product LiOH, for example, which is of good water-solubility, the hydration energy may be released (lithium −509 kJ/mol).

This is dependent in this case on the electropositive metals used and on the liquid used. A hydroxide solution taken off in the form of liquid, for example, from the reaction with water, as for example alkali metal hydroxide solution, may take on diverse further functions. It is even possible for the electropositive metal to be recovered from this solution in a suitable way. Fully recyclable energy circuits arise, for example, for Li via reconversion of Li2CO3 into LiCl, as specified in US 20130001097 A1, for example, and subsequent electrolysis to Li.

When Ca, for example, is used as electropositive metal, resultant Ca(OH)2 may serve for the desulfurization of conventional fossil-fired power plants.

Separation of vaporized liquid from the gaseous constituents, as may take place in accordance with certain embodiments, for them to be returned as liquid, is not subject to any particular restriction, and may take place in a suitable way. For example, water can be condensed. Optionally, vaporized liquid and/or gaseous products formed in the reaction, such as water, hydrogen, or carbon dioxide, for example, may also be discharged to the environment, from the standpoint of economics, for example.

The at least partial conversion of the energy from the solution or suspension removed, which may be at temperatures, for example, of 300° C. or more, can according to certain embodiments take place with the aid of at least one heat exchanger. This heat exchanger is then able, for example, to provide thermal energy. It is also possible for steam, for example, to be generated in the heat exchanger, this steam driving a turbine and a generator, for example, in order to generate electrical energy. Another possibility is for both thermal energy and electrical energy to be generated with the aid of the heat exchanger. The thermal energy may serve, for example, for preheating the electropositive metal and/or the liquid prior to the reaction, and so, for example, the electropositive metal may also be provided in liquid form. The thermal energy may alternatively be used for other purposes, such as district heating, for example. The electrical energy recovered may also be used in a suitable way, for power supply, for example.

According to certain embodiments, the at least partial conversion of the energy of the vaporized liquid and/or of gaseous products formed in the reaction into electrical energy is accomplished by at least one turbine and at least one generator. The nature of the turbine and of the generator is not subject to particular restriction here, as in the case of the heat exchanger above as well. According to certain embodiments, at least two turbines, positioned one after another in the flow direction of the vaporized liquid and/or of gaseous products formed in the reaction, may be used in the at least partial conversion of the energy, including, for example, an expander turbine and a steam turbine. Thus, for example, energy conversion may take place first with a gas turbine, by the combustion of one component, after which the gaseous constituents can be used in a steam turbine for energy conversion; in other words, the gaseous constituents pass through two or else more turbines one after another (in series).

In addition to the at least partial conversion of the energy of the vaporized liquid and/or of gaseous products formed in the reaction, facility may also be provided for chemical utilization of the resultant gases such as CO and/or H2. For example, the gaseous products, optionally after having been scrubbed, for the purpose of removing CO2, for example, and/or the gaseous constituents after having been dried, may be supplied to a Fischer-Tropsch synthesis apparatus, where the synthesis gas comprising CO and H2 can be used to produce higher-value chemical products such as methanol, ethanol, hydrocarbons, etc. For this purpose, optionally, H2 and/or CO and/or H2O may also be supplied from external sources to the gaseous constituents. Gas scrubbing may take place, for example, with water and/or a solution and/or suspension of a salt of the electropositive metal, as for example LiOH.

Unlike synthesis gas produced from coal or natural gas, the gases produced in the above embodiments contain no nitrogen- or sulfur-containing impurities such as NH3, HCN, H2S, COS, or oxygen, which have to be removed very expensively and inconveniently. The only impurity that may need removal is CO2. Since hydroxide is also available in the plant, it can be utilized for the scrubbing of CO2. A scrubber of this kind is very efficient.

After drying of the gases, where appropriate, a high-purity synthesis gas mixture with adjustable CO/H2 ratio can be obtained for Fischer-Tropsch processing. Depending on catalyst, for example, methanol or hydrocarbons are obtainable.

In the present case, then, according to certain embodiments, it is possible to operate a method of the invention with a gaseous product containing only CO2 or H2O, meaning that, with chemical utilization of the gaseous constituents, it is necessary to provide the other gas component of the synthesis gas, as for example from an intermediate storage facility, if an apparatus of the invention is operated alternately with a liquid comprising H2O and a liquid comprising CO2, and the gaseous products formed are removed and put into intermediate storage accordingly.

It is also possible for two apparatuses of the invention to be operated in parallel with two methods of the invention, with one method using a liquid comprising CO2 and the other using a liquid comprising H2O, and the gaseous constituents generated can then be suitably combined for a Fischer-Tropsch synthesis.

According to a further aspect, the invention relates to an apparatus for reacting an electropositive metal with a liquid, the electropositive metal being selected from alkali metals, alkaline earth metals, aluminum, and zinc, and also alloys and/or mixtures thereof, comprising a reactor in which the reaction between the electropositive metal and the liquid takes place, at least one pore burner and/or at least one means for jetting and/or atomizing the electropositive metal into the liquid, on and/or in the reactor, at least one first supply means for the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, said supply means being designed in such a way as to supply the electropositive metal to the interior of the pore burner and/or to the means for jetting and/or atomizing the electropositive metal, at least one second supply means for the liquid, on and/or in the reactor, said means being designed in such a way as to supply the liquid to the reactor, at least one first removal means for the solution or suspension formed in the reaction of electropositive metal and liquid, said means being designed in such a way as to remove from the reactor the solution or suspension formed in the reaction of electropositive metal and liquid, at least one second removal means for gaseous products, said means being designed in such a way as to remove from the reactor at least partially vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid, and a control means, which is designed in such a way as to supply the liquid to the reactor in such a way that the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal are located in the liquid in the reactor, below the liquid surface.

There are no particular restrictions on the reactor in terms of its construction and material, etc., provided the corresponding reaction is able to take place therein. It may be designed appropriately in dependence on the type, nature (e.g., temperature, pressure) and/or amount in each case of the liquid and of the electropositive metal, etc. There are also no particular restrictions on the separating means, supply means, jetting means, optional removal means and return means, etc.

The means for jetting and/or atomizing the electropositive metal here is not subjected to particular restriction and may comprise, for example, a single-fluid nozzle or a two-fluid nozzle, which may be designed as described above, or else an above-described sintered metal nozzle. The pore burner may be designed as described above.

Serving as first supply means for the electropositive metal may be, for example, tubes or hoses, or else conveyor belts, which may be heated, and which may be suitably determined on the basis, for example, of the aggregate state of the electropositive metal. According to certain embodiments, for example, the alkaline earth metals, e.g., Mg and Ca, are supplied in particle form, as powders, for example, whereas Li can be supplied as a liquid, for example. The first supply means for the electropositive metal may also, optionally, be fitted with a further supply means for an atomizing gas, or with a further supply means for a further gas for introducing the electropositive metal, optionally having a control means such as a valve, with which the supply of the electropositive metal can be regulated.

The second supply means for the liquid may also be designed in the form of a tube or hose, etc., which may optionally be heated, and the second supply means may be suitably determined on the basis of the state of the liquid, which may be a supercritical liquid. Also, a plurality of supply means may be provided for the electropositive metal or for the liquid.

According to certain embodiments, the pore burner and/or the means for jetting and/or atomizing is made of a material selected from the 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-nickel steel. Suitable for example are austenitic chromium-nickel steels, which for example are highly resistant to depletion by sodium at high temperature, though also materials with 32% nickel and 20% chromium, such as AC 66, Incoloy 800 or Pyrotherm G 20132 Nb, still exhibit relatively favorable corrosion behavior. These materials are preferred for use at relatively high temperatures, at which the reaction with the electropositive metal is able to proceed more easily.

The supply means for atomizing gas and/or further gas is likewise not subject to particular restriction and comprises, for example, tubes, hoses, etc., which may be appropriately determined on the basis of the state of the atomizing gas and/or further gas, which optionally may also be under pressure.

In an apparatus, optionally, an ignition apparatus, as for example an electrical ignition apparatus or a plasma arc, may be necessary, and this may depend on the nature and the state of the electropositive metal, as for example its temperature and/or aggregate state, on the nature of the liquid, as for example its pressure and/or temperature, and on the arrangement of components in the apparatus, such as the type and nature of the supply means, for example.

There is no particular restriction on the reactor provided it is able to accommodate the liquid. To constructively achieve both a high temperature of the vaporized liquid and/or of the gaseous products formed in the reaction of electropositive metal and liquid, of more than 200° C., for example, and even 400° C. or more, for example, and in certain embodiments 500° C. or more, and an elevated operating pressure (e.g., 5 bar or more) or a high operating pressure (20 bar or more), the internal material of the reactor may consist of high-temperature-resistant alloys, examples being those specified above and also, in an extreme case, the material Haynes 214. This material, which is intended solely to withstand the high temperature, may then be surrounded by a thermal insulation, which transmits sufficiently little heat that externally a steel wall, which additionally may also be air-cooled or water-cooled, accommodates the pressure loading.

Furthermore, the reactor may also comprise heating and/or cooling apparatuses which may be present on the reactor and/or alternatively on the various supply and/or removal means and/or, optionally, the ignition apparatus, etc. There may, furthermore, be other components present in an apparatus of the invention, such as pumps for generating a pressure or a vacuum, etc.

Nor is there any particular restriction on the removal means; for example, the second removal means for gaseous products may be designed as a tube, whereas the first removal means for the solution or suspension formed in the reaction of electropositive metal and liquid may be designed, for example, as a star wheel and/or as a tube with a syphon, or else as a tube. Here it is also possible for various valves, such as pressure valves, and/or other regulators to be provided.

Suitable material for the reactor, the separating means, jetting means and/or atomizing means, pore burners and/or, optionally, removal means and/or, optionally, the supply means, or else, for example, for apparatuses for converting energy such as turbines, coupled to generators, is for example—according to certain embodiments—a material selected from the group consisting of iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, zirconium, and alloys of these metals, and also steels such as stainless steel and chromium-nickel steel. These materials are preferred for use at relatively high temperatures, at which the reaction with, for example, liquid electropositive metal is able to proceed more simply, or the reaction mixture can easily be treated.

The apparatus of the invention has a control means which is designed in such a way as to supply the liquid to the reactor in such a way that the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal are located in the liquid in the reactor, below the liquid surface. Control here may be accomplished, for example, on the basis of measurement data or computer simulations. The control means may for example control the at least one first supply means for electropositive metal and/or the at least one second supply means for liquid in such a way that in the case of increased reaction, less electropositive metal or more liquid is supplied, but it may also, for example, control the pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal. Another possibility is a temperature control for the reactor, for the supply and/or removal means, etc. The control means here may exert control, for example, via control of nozzles, for example on or in the supply means and/or the reactors, and, respectively, the addition of electropositive metal and/or liquid, or else may control the supply means themselves, through control, for example, of pumps, etc.

According to certain embodiments, the apparatus further comprises a heating apparatus for providing the electropositive metal as a liquid, said apparatus being designed in such a way as to liquefy the electropositive metal before or during the supplying of the electropositive metal. There are no particular restrictions on this heating means.

Furthermore, according to certain embodiments, the at least one pore burner and/or the at least one means for jetting and/or atomizing the electropositive metal are made of a material selected from the 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-nickel steel.

Furthermore, according to certain embodiments, the apparatus further comprises at least one first means for conversion of energy, said means being connected to the at least one first removal means for the solution or suspension formed in the reaction of electropositive metal and liquid, and being designed in such a way as to convert at least partially the energy of the solution or suspension removed. The at least one first means for conversion of energy is not subject to particular restriction here and may comprise, for example, at least one heat exchanger and/or at least one boiler.

According to certain embodiments, the at least one first means for conversion of energy has at least one heat exchanger. In accordance with the invention, this is not subject to any particular restriction, and may for example also be coupled to at least one turbine and at least one generator for the generation of electrical energy, but may also be used, additionally or even only, for conversion into thermal energy, as for example district heating, or else for the provision of steam for other processes.

If no suitable heat exchanger can be found which allows heating in that case, for example, of air or water with corresponding pressure, it is possible to use a boiler, for example. The approach involving use of a boiler may be more promising, according to certain embodiments, and is also technically simpler, since it may be realizable at lower temperatures and only elevated pressure.

By means of one or more heat exchangers and/or one or more boilers, it is possible then, subsequently, for electrical energy to be generated, through use of a steam turbine and a generator, for example.

According to certain embodiments, the apparatus further comprises at least one second means for conversion of energy, said means being connected to the at least one second removal means and being designed in such a way as to convert at least partially the energy of the at least partially vaporized liquid and/or of gaseous products formed in the reaction of electropositive metal and liquid, and/or at least one means for producing chemical products, said means being designed in such a way as to convert the vaporized liquid and/or the gaseous products formed in the reaction of electropositive metal and liquid into further chemical products.

The at least one second means for conversion of energy is not subject to particular restriction in accordance with the invention, provided it is able to convert the energy from the vaporized liquid and/or from the gaseous products formed in the reaction of electropositive metal and liquid, and it may comprise, for example, at least one heat exchanger, boiler and/or a turbine. According to particular embodiments, the at least one second means for conversion of energy has at least one turbine and at least one generator for the generation of electrical energy. As also above in the context of the coupling to the heat exchanger, there are no particular restrictions on the turbine and the generator, and a plurality of different turbines may also be employed, connected to one or more generators. According to certain embodiments, the at least one second means for conversion of energy has at least two turbines positioned one after another in the flow direction of the vaporized liquid and/or gaseous products.

Heat may also be removed from the vaporized liquid and/or the gaseous products, however, by means of a heat exchanger, and in that case a generator is not automatically required. Combinations of turbines and heat exchangers are possible as well.

According to certain embodiments, the apparatus of the invention has at least one means for producing chemical products, said means being designed in such a way as to convert the vaporized liquid and/or the gaseous products formed in the reaction of electropositive metal and liquid into further chemical products. This is not subject to particular restriction, and may be provided suitably on the basis of the vaporized liquid and/or the gaseous products generated. For example, according to certain embodiments, the apparatus of the invention may have at least one CO2 scrubber and/or a third supply means for CO and/or H2 and/or H2O, and/or a dryer and/or a Fischer-Tropsch synthesis apparatus, thus using water and/or supercritical carbon dioxide as liquid and producing H2 or CO as gaseous product. It may therefore resemble an IGCC plant. In an apparatus of this kind, therefore, the electropositive metal serves as part of the fuel. It is also possible to provide two apparatuses of the invention, of which one uses a liquid comprising water and the other uses a liquid comprising carbon dioxide, if a Fischer-Tropsch synthesis is to be attached. The at least one CO2 scrubber and/or the at least one third supply means for CO and/or H2 and/or H2O, and/or the at least one dryer and/or the Fischer-Tropsch synthesis apparatus, are not subject to particular restriction in accordance with the invention, and may be customary apparatuses and components, respectively.

According to certain embodiments, the apparatus further comprises at least one third removal means, which is connected by the first means to the means for conversion of energy and which is designed in such a way as to remove the solution or suspension removed from the first means to the means for conversion of energy, at least one first separating means, which is connected to the at least one third removal means and which is designed in such a way as to separate the liquid from the solution or suspension removed, and at least one first return means for liquid from the first separating means, which is connected to the second supply means and/or to the reactor and which is designed in such a way as to supply the liquid from the first separating means to the second supply means and/or to the reactor. The third removal means in this case, like the other two removal means, is not subject to any particular restriction, and may be designed in accordance therewith using the corresponding material.

According to certain embodiments, the apparatus further comprises at least one second separating means, which is designed in such a way as to at least partially separate the liquid and/or the vaporized liquid from the vaporized liquid removed and/or from the gaseous products formed in the reaction of electropositive metal and liquid, and at least one second return means for liquid and/or vaporized liquid from the second separating means, said return means being connected to the second supply means and/or to the reactor and being designed in such a way as to supply the liquid and/or the vaporized liquid from the second separating means to the second supply means and/or to the reactor.

There are no particular restrictions on the first and second separating means, provided that, in the first separating means, at least partial separation into liquid for return, on the one hand, and product for removal, on the other, such as a reaction product of electropositive metal and liquid, for example, can be achieved, and, in the second separating means, vaporized liquid can be at least partially separated off. The second separating means in this case may also be located in the second means for conversion of energy, and the first separating means may also be located in the first means for conversion of energy.

Like the removal means, the first and second return means are likewise not subject to any particular restriction, and may be provided corresponding to these using the corresponding material—that is, for example, in the form of tubes or hoses.

According to certain embodiments, the apparatus further comprises at least one detecting means which is located on and/or in the reactor and is connected to the control means, and which is designed in such a way as to detect the amount of liquid in the reactor. In accordance with the invention, there is no particular restriction on the detecting means, which may comprise, for example, at least one sensor such as an IR sensor or pH sensor, capacitive level sensors, ultrasonic sensors, other optical sensor types, etc., that can be connected to the control means and that has a signal on the basis of which control may or may not be exercised in the apparatus.

In certain embodiments, as well, the solution or suspension removed may comprise solids in solution or suspension, which can be reacted further to substances of value. Thus, for example, metal nitride produced from combustion with nitrogen can be reacted by hydrolysis with water to form ammonia and alkali, with the resulting alkali then able to serve, among other things, as a scavenger for carbon dioxide and/or sulfur dioxide.

The above embodiments, designs, and developments may be combined arbitrarily with one another insofar as is rational. Further possible embodiments, developments, and implementations of the invention also include combinations not explicitly stated of invention features described above or hereinafter in relation to the working examples. In particular, the skilled person will also add individual aspects as improvements or complements to the respective basic form.

In the text below, the invention is now illustrated by exemplary embodiments, which do not in any way restrict the invention.

FIG. 5 shows a schematic representation of a first exemplary embodiment of an apparatus, in which an electropositive metal 1, such as presently an exemplary liquid alkali metal, is introduced into a reactor 10, by means of a porous sintered nozzle 2, below the surface of a liquid 3 such as, for example, a water surface or the surface of liquid, supercritical CO2 or SOx, for conversion of the chemical energy stored in the electropositive metal into electrical energy; and also the resultant product chain of substances of value, comprising, for example, H2 or CO, NaOH, KOH, LiOH.

In the apparatus of the first exemplary embodiment, the following steps are carried out:

  • a) The supplying of the electropositive metal 1 into the liquid reaction space, directly into the liquid coreactant (e.g., H2O, supercritical CO2 or SOx), optionally under pressure, by means of a porous sintered nozzle 2. The apparatus for pressurized injection of the liquid electropositive metal 1 such as an alkali metal below the liquid surface may also be configured as a conventional single-fluid nozzle with or without swirl element, as a two-fluid nozzle, as a perforated metal plate, as a plate or rod provided with capillaries/holes, or the like, as set out above.
  • b) The reaction/combustion reaction takes place in the liquid reaction space. The liquid electropositive metal 1 is introduced under pressure into the sintered nozzle 2, and enters the liquid below the liquid level through the pores of the sintered nozzle 2. At the pore surface it reacts with the liquid, such as water, CO2 or SOx. The reaction is highly exothermic, and the heat liberated may be partially converted via the solution removed, which is taken off through the first removal means 13, via a heat exchanger 13 and subsequently a steam turbine 14 with connected generator 15, into electrical energy.
  • c) Separation of the solid reaction products:
    • formed in the reaction with the liquid 3 such as water, as solid reaction products, are, for example, NaOH, KOH, LiOH or mixtures thereof if alkali metal alloys have been used
    • these solid reaction products are highly soluble in water (solubility in H2O: NaOH 1090 g/l; KOH 1120 g/l, LiOH 128 g/l) and pass into solution. This prevents clogging of the pores and associated interruption in the supply of liquid alkali metal and in the reaction. The removal of the reaction products from the pore surface is realized via their solubility in the medium utilized as a coreactant to the alkali metal, the liquid 3.
    • the LiOH, NaOH, KOH solution/suspension, when water is used as liquid 3, is passed through a first removal means 12 via a heat exchanger 13. If the plant is operated with CO2 instead of H2O, then a carbonate suspension such as an Li2CO3 suspension is removed rather than a hydroxide solution/suspension. The concentrated suspension or solution 100 leaving the heat exchanger can be obtained, directly after pressing-off, as a product of value, such as NaOH, for instance, or can be transferred for recycling, such as Li2CO3, for instance. NaOH may for example also be obtained in solution as a product of value, sodium hydroxide solution.
  • d) In the case of the exemplary combustion reaction in water as liquid 3, hydrogen (H2) is formed as a gaseous product. On account of the high temperatures, some of the water in the reactor 10 may vaporize and thus raise the pressure. The gas mixture may be passed via a second removal means 16 to a gas turbine 17 and may likewise be converted into electrical energy by means of a generator 19. From the gaseous products and/or the vaporized liquid, products or liquid may be condensed out in the condenser 18, and the liquid 3, optionally also as gas or steam with cooling, may be returned via a second return means 20 to the second supply means 11 for liquid, or directly into the reactor 10 (not shown). In the case of a reaction with carbon dioxide, CO is formed as a gaseous product, and may for example be used further or stored, like H2 as well.
  • e) Fresh liquid 3 such as water or supercritical CO2 or SOx is supplied to the combustion chamber via the second supply means 11.

An alternative embodiment is opened up by the chemical utilization of, for example, the gases H2 (reaction material H2O) and/or CO (reaction material liquid or supercritical CO2). In this case, H2 (reaction material H2O) and/or CO (reaction material liquid or supercritical CO2) are not, or are only partially, subjected to combustion in order to generate electrical energy, but are used further, as for example in a Fischer-Tropsch synthesis, and so the gas turbine 17 is at least partly replaced by the chemical utilization and can therefore be omitted or made smaller. In contrast to synthesis gas produced from coal or natural gas, the gases produced in the above embodiments contain no nitrogen-containing or sulfur-containing impurities such as NH3, HCN, H2S, COS, or oxygen, which have to be separated off at great expense and complexity. The only impurity that need be separated off in the case of CO is CO2. It can be removed from the gas, for example, via conventional CO2 scrubbers or alkali metal hydroxide, which may also come from the apparatus of the invention.

A second exemplary embodiment is shown in FIG. 6, in which the separation of a product of value from the liquid or solution removed, and returning of liquid 3, are illustrated in addition to the first exemplary embodiment shown in FIG. 5. In this case, the solution or suspension removed, after the heat exchanger 13, is introduced into a first separating means 21 such as a liquid separator, e.g., an NaOH separator, and the liquid 3 is separated off at least partially from the suspension or solution 100. The liquid 3 separated off is supplied by a first return means 22 back to the second supply means 11, or directly to the reactor 10 (not shown). In an alternative embodiment, instead of the suspension or solution 100, a solid may also be separated off.

In the present disclosure, the electropositive metal, such as a liquid alkali metal, may simply be introduced through a means for jetting or atomizing, such as a porous sintered nozzle, directly into the liquid in a reactor, which liquid serves as a coreactant for the electropositive metals in the case of the combustion/reaction. The thermal energy formed in the exothermic reaction may be converted via heat exchangers, for example, with downstream steam turbine, into electrical energy. In the case of the reaction with liquids such as water, reaction products formed include products of value such as hydrogen (H2) and the hydroxide of the electropositive metal, for example, as for example the alkali metal/alkali metal alloy used as metal fuel (see also exemplary equations in table 1). Hydrogen or the hydrogen/steam mixture, and also other mixtures of vaporized liquid and gaseous products, may be used for power generation by means of a gas turbine, such as a hydrogen gas turbine, for example.

Various embodiments may include:

    • the direct injection of an optionally liquid, electropositive metal below a liquid surface of a liquid such as water, supercritical gases, such as CO2 or SOx, for example, which serve as combustion partners/coreactants
    • a method for reaction of electropositive metals, where the solid reaction products may be dissolved in the liquid such as water and may be separated off effectively from the pores of a pore burner or of a means for jetting or atomizing by way of their (LiOH, NaOH, KOH) solubility in the liquid, water for example, without clogging
    • methods for simultaneous conversion of the chemical energy stored in electropositive metals such as alkali metals into electrical energy and/or generation of chemical substances of value such as NaOH, KOH, LiOH, H2, CO
    • emissions-free operation of a power plant with, for example, H2O.

Claims

1. A method for reacting an electropositive metal selected from the group consisting of alkali metals, alkaline earth metals, aluminum, zinc, mixtures, and alloys thereof, with a liquid, the method comprising:

atomizing or jetting the electropositive metal;
introducing the electropositive metal into the liquid below a surface of the liquid; and
producing at least partial reaction of the electropositive metal in the liquid.

2. The method as claimed in claim 1, wherein the electropositive metal is supplied as liquid.

3. The method as claimed in claim 1, the liquid selected from the group consisting of water and supercritical liquids.

4. The method as claimed in claim 1, wherein atomizing or jetting the electropositive metal includes using a pore burner or a nozzle.

5. The method as claimed in claim 1, wherein the at least partial reaction including at least partial vaporization; and

the method further comprises replacing vaporized liquid by a supply of liquid.

6. The method as claimed in claim 1, further comprising using at least part of the vaporized liquid and/or gaseous products formed in the reaction of electropositive metal and liquid to produce chemical products.

7. The method as claimed in claim 1, further comprising:

removing at least part of the liquid during or after the reaction as solution or suspension; and
at least partially converting the energy of the solution or suspension.

8. An apparatus for reacting an electropositive metal with a liquid, the electropositive metal selected from the group consisting of: alkali metals, alkaline earth metals, aluminum, and zinc, alloys and/or mixtures thereof, the apparatus comprising:

a reactor;
a pore burner or a means for jetting or atomizing the electropositive metal into the liquid on or in the reactor;
a first supply means feeding the electropositive metal to the pore burner or to the means for jetting or atomizing the electropositive metal;
a second supply means feeding the liquid to the reactor,
a first removal means for the solution or suspension formed during the reaction of the electropositive metal with the liquid;
a second removal means for at least partially vaporized liquid or gaseous products formed in the reaction of the electropositive metal and the liquid; and
a control means to supply the liquid to the reactor in such a way that the pore burner or the means for jetting or atomizing the electropositive metal are located below a surface of the liquid in the reactor.

9. The apparatus as claimed in claim 8, further comprising a heating apparatus liquefying the electropositive metal before or during feeding the electropositive metal to the reactor.

10. The apparatus as claimed in claim 8, wherein the pore burner or the means for jetting or atomizing the electropositive metal consists of material selected from the group consisting of: iron, chromium, nickel, niobium, tantalum, molybdenum, tungsten, Zircaloy, alloys of these metals, or steels.

11. The apparatus as claimed in claim 8, further comprising at least one first means for converting energy connected to the first removal means and at least partially converting the removed energy of the solution or suspension.

12. The apparatus as claimed in claim 8, further comprising second means for converting energy connected to the second removal means and at least partially converting the energy of the vaporized liquid or the gaseous products formed in the reaction of electropositive metal and liquid.

13. The apparatus as claimed in claim 8, further comprising:

a third removal means removing the solution or suspension from the first removal means to the means for conversion of energy;
a first separating means separating the liquid from the solution or suspension removed by the third removal means; and
a first return means for liquid from the first separating means, returning the liquid from the first separating means to the second supply means or to the reactor.

14. The apparatus as claimed in claim 8, further comprising:

a second separating means at least partially separating the liquid or the vaporized liquid from the vaporized liquid removed or the gaseous products formed in the reaction of electropositive metal and liquid; and
a second return means returning the liquid or the vaporized liquid from the second separating means to the second supply means or to the reactor.

15. The apparatus as claimed in claim 8, further comprising at least one detecting means located on or in the reactor detecting an amount of liquid in the reactor and communicating the amount to the control means.

16. The method as claimed in claim 1, further comprising converting at least part of energy of the vaporized liquid or of gaseous products formed in the reaction.

17. The apparatus as claimed in claim 8, further comprising a means for producing chemical products and converting the vaporized liquid or the gaseous products formed in the reaction of electropositive metal and liquid into further chemical products.

Patent History
Publication number: 20180328584
Type: Application
Filed: Nov 5, 2015
Publication Date: Nov 15, 2018
Applicant: Siemens Aktiengesellschaft (Muenchen)
Inventors: Helmut Eckert (Roettenbach), Guenter Schmid (Hemhofen), Dan Taroata (Erlangen), Renate Elena Kellermann (Erlangen)
Application Number: 15/525,719
Classifications
International Classification: F23C 99/00 (20060101);