JP2010521278A - Novel series power plant process and method for providing a hydrogen carrier reversibly usable in the power plant process - Google Patents

Abstract

In the case of crude oil reserves, the time limit can be estimated. It is preferred to use a starting material containing silicon dioxide as a raw material.

Description

  This application is based on European Patent Application No. 06 126 325.7 filed December 18, 2006 and US Patent Application No. 11 / 746,608 filed May 9, 2007. Insist. This application is further based on European Patent Application No. 07 100 387.5 filed January 11, 2007 and US Patent Application No. 11 / 746,620 filed May 9, 2007 with the European Patent Office. Claim priority.

Carbon dioxide is a compound composed of carbon and oxygen, and is a colorless and odorless gas. At low concentrations, it is a natural component of air, occurs in living organisms during cellular respiration, and also occurs in the combustion of carbon materials with sufficient oxygen. From the origin of industrial, CO ₂ component in the atmosphere has been increased significantly. The main reason for this is known as anthropogenic CO ₂ release, in CO ₂ emission caused by humans.

  Carbon dioxide in the atmosphere absorbs part of the heat radiation. From this characteristic, carbon dioxide is regarded as a greenhouse gas and is one of the causes of the greenhouse effect.

For these reasons, and for other reasons, research and development are currently being conducted from different directions to explore ways to reduce anthropogenic CO ₂ emissions. In particular, in connection with energy production carried out by the combustion of fossil fuel carriers such as coal or gas, or in other combustion processes (eg during garbage incineration), there is a need to reduce CO _2. Yes. Hundreds of millions of tons of CO ₂ are released into the atmosphere every year by the process.

At first as described, combustibles required for generating the heat to generate CO _2. To date, CO ₂ has been used with sand contained in oil-containing sand (SiO ₂ ), oil-containing shale (SiO ₂ + [CO ₃ ] ² ), bauxite or tar-containing sand or tar-containing shale, and other mixtures. No one has yet reached the idea of reducing emissions and even acquiring new raw materials and especially energy from the products obtained by the new method.

  In the novel method, instead of using a naturally occurring mixture of sand and oil, hydrocarbon-containing industrial waste or natural waste after mixing sand may be used if possible. It is also conceivable to use natural asphalt (also called mineral pitch) instead of the oil component. Pure sand or a mixture of building stone and asphalt containing sand components is particularly preferred.

  However, water glass, a mixture of sand and acid or base may be used. In order to provide the hydrocarbon component required for the present invention, mineral oil is mixed into the water glass (microemulsion method).

  The present invention can also be applied particularly preferably to clean beaches and sandbars contaminated, for example after a tanker accident. For this reason, a vehicle having one or more reaction areas according to the present invention is most suitable, preferably a ship having one or more reaction areas according to the present invention. For this reason, contaminated sand containing heavy oil is treated in the field and converted into a valuable product without impacting the environment, and at the same time energy is obtained.

It is known that the reserves of oil-containing sand (SiO ₂ ) and oil-containing shale (SiO ₂ + [CO ₃ ] ² ) exceed the world oil reserves many times. The technical methods applied to separate oil and mineral are currently inefficient and very costly. Although natural asphalt exists at multiple points on the earth, it is currently mined on an industrial scale, primarily in Trinidad.

Sand is generated everywhere on the Earth's surface, to varying degrees. Most of the generated sand contains quartz (silicon dioxide; SiO ₂ ). However, since the silicon component is present in gneiss, mica, granite, slate and bauxite, these rocks may be used.

  The object of the present invention is to provide such possible raw materials and to disclose their technical production methods. The chemical knowledge used in the process is characterized in that silicon present in sand, shale, and other mixtures is involved in the reaction and a reversible hydrogen carrier is provided.

A serial sequence of each reaction (herein referred to as energy-material serial coupling or EMC ² ) is a feature of the present invention. Each of these reactions is mutually related such that the amount of energy released increases with each reaction step and other (preferably higher value or higher energy) reaction products are provided to each reaction step. Combined. For this purpose, the individual reaction zones / zones in which the partial reactions take place are connected to one another thermally and / or for the transfer of reactants.

  On the other hand, the present invention aims to generate and provide energy in the form of a reversible hydrogen carrier that can be transported harmlessly, and to provide an alternative possible approach for providing hydrogen to consumers. And

  According to the invention, silicon is obtained in the first partial reaction of the power plant process from one or more of the following starting materials: oil-containing sand, oil-containing shale, bauxite, gneiss, mica, granite, slate. The use of the number 1 does not indicate that the partial reaction is performed first. The mixture of one or more starting materials mentioned is used in the first partial reaction and is liquefied by adding an acid or base, for example to improve transportability through a pipe. In this case, the acid or base may be reused by heating with the first energy provider.

  In a preferred embodiment of the invention, especially after ignition, silicon (specifically a powder at a suitable temperature) is reacted with pure (cold) nitrogen (specifically nitrogen from the atmosphere). Take advantage of the fact that silicon nitride is produced. This is because the reaction is strongly exothermic. The generated heat may be used, for example, in a reactor in a power plant process. The reaction of silicon to produce silicon nitride is referred to herein as a second partial reaction.

により、長鎖シランが生成される。これは、燃料電池技術及びエンジンの両方において用いられる。当該シランは、可逆的な水素キャリヤーの考えられる形態である。 In the first partial reaction according to the invention, silicon generated in the power plant process from oil-containing sand, oil-containing shale, bauxite, gneiss, mica, granite and / or slate is surface active and It may be treated catalytically with hydrogen (specifically using magnesium and / or aluminum as a catalyst) so that monosilane is produced. Reacting silicon to produce monosilane is referred to herein as a third partial reaction. The monosilane is removed from the reaction chamber and subjected to a catalytic pressure reaction (fourth partial reaction) at another position. Equality

As a result, a long-chain silane is produced. This is used in both fuel cell technology and engines. The silane is a possible form of a reversible hydrogen carrier.

However, in the process according to the present invention, silicon (for example, silicon powder) is nitrided at about 1400 ° C. in a nitrogen (N ₂ ) atmosphere to produce silicon nitride Si ₃ N ₄ . This type of reaction is a variation of the second partial reaction.

により与えられる。これにより、当該反応においてＮＨ_３及び二酸化珪素が生成される。ＮＨ_３は、極めて優れた水素キャリヤーである。シリコンナイトライドの加水分解は、比較的遅く進行する。そのため、本発明によれば、当該シリコンナイトライドを、フレークとして、粉末として、若しくは多孔質の形態で使用し、その結果、極めて大きな表面積とする。これにより、シリコンナイトライドの加水分解をより効率的にそして急速に行うことができる。当該アプローチは、シリコンナイトライドの加水分解において表面加水分解が重要な役割を果たすという知見に基づいている。そのため、当該加水分解は、シリコンナイトライドの表面が故意に拡張されているためより効率的となる。加水分解を用いてＮＨ_３を生成するためにシリコンナイトライドを反応させることは、ここでは、第５部分反応と称する。Ｓｉ_３Ｎ_４ナノ構造体若しくはナノ結晶を使用することは、ここでは特に効果的である。これらＳｉ_３Ｎ_４ナノ構造体若しくはナノ結晶は、例えばゾルゲルプロセスから得られる。また、ゾルゲルプロセスのためのエネルギーは、本発明に係る部分反応の１つから取り出される。 The silicon nitride may then be converted to NH ₃ using, for example, hydrolysis. The specific reaction carried out in the hydrolysis is the following equation:

Given by. Thereby, NH ₃ and silicon dioxide are generated in the reaction. NH ₃ is a very good hydrogen carrier. Hydrolysis of silicon nitride proceeds relatively slowly. Therefore, according to the present invention, the silicon nitride is used as flakes, as a powder, or in a porous form, resulting in a very large surface area. Thereby, the hydrolysis of silicon nitride can be performed more efficiently and rapidly. The approach is based on the finding that surface hydrolysis plays an important role in the hydrolysis of silicon nitride. Therefore, the hydrolysis is more efficient because the surface of silicon nitride is intentionally expanded. Reacting silicon nitride to produce NH ₃ using hydrolysis is referred to herein as the fifth partial reaction. The use of Si ₃ N ₄ nanostructures or nanocrystals is particularly effective here. These Si ₃ N ₄ nanostructures or nanocrystals are obtained, for example, from a sol-gel process. Also, the energy for the sol-gel process is taken from one of the partial reactions according to the present invention.

Silicon, NH ₃ , and silane are very good energy providers. These are transported to the consumer without problems where the hydrogen is removed. However, hydrogen peroxide is most appropriate as an energy provider. Hydrogen peroxide is generated in another partial reaction according to the present invention. This is tied to or combined with the power plant process. This is also true for the production of silicon, NH ₃ , or silane and is combined with or tied to the power plant process.

  Further details and advantages of the present invention are described below based on embodiments.

  Various aspects of the invention are schematically illustrated in the drawings.

FIG. 1 shows a diagram of a first partial reaction according to the invention. FIG. 2 shows a diagram of the second partial reaction according to the invention. FIG. 3 shows a diagram of a third partial reaction according to the invention. FIG. 4 shows a diagram of the fourth partial reaction according to the invention. FIG. 5 shows a diagram of the fifth partial reaction according to the invention. FIG. 6 shows a diagram of a sixth partial reaction according to the present invention. FIG. 7 shows a diagram of the seventh partial reaction according to the present invention. FIG. 8 shows a diagram of the eighth partial reaction according to the present invention. FIG. 9 shows a diagram of the ninth partial reaction according to the present invention. FIG. 10 shows a diagram of the tenth partial reaction according to the present invention. FIG. 11 shows a diagram of an eleventh partial reaction according to the present invention. FIG. 12 shows a diagram of the twelfth partial reaction according to the present invention. FIG. 13 shows a diagram of the thirteenth partial reaction according to the present invention. FIG. 14 shows a diagram of the fourteenth partial reaction according to the present invention. FIG. 15 shows a diagram of the fifteenth partial reaction according to the present invention. FIG. 16 shows a diagram of the first embodiment according to the present invention. FIG. 17 shows a diagram of the second embodiment according to the present invention. FIG. 18 shows a diagram of the third embodiment according to the present invention. FIG. 19 shows a diagram of the fourth embodiment according to the present invention. FIG. 20 shows a diagram of the fifth embodiment according to the present invention. FIG. 21 shows a diagram of a sixth embodiment according to the present invention.

Hereinafter, the present invention will be described based on examples. While CO ₂ is released as energy is gained, the first embodiment relates to reducing or completely eliminating CO ₂ emissions using the present invention in power plant operations.

In one subject method, a new compound (referred to as a product) is generated from a starting material (referred to as a free form or reactant), but according to the present invention, a series of chemical reactions are performed in the subject method. Is done. The (partial) reaction according to the invention is set so that a considerable amount of CO ₂ is consumed and / or combined.

  In the first embodiment, for example, sand mixed with mineral oil, heavy oil, tar and / or asphalt is used as the first energy provider, or oil-bearing shale is used as the starting material. However, one or more of the following first energy providers may be used: lignite, anthracite, peat, wood, gas.

The starting material is fed into a reaction chamber, for example in the form of an afterburner or a combustion chamber. In addition, CO ₂ is supplied to the chamber. In the first embodiment, the CO ₂ is generated in large quantities when energy is obtained from fossil fuels. To date, CO ₂ exhaust gas has usually escaped into the atmosphere. Although not always necessary, it is preferable to additionally supply air to the chamber at the beginning of the first partial reaction. In place of or in addition to the atmosphere, steam at 407 ° C. or higher or supercritical H ₂ O may be applied to the method. However, in order to successfully apply supercritical H ₂ O to ongoing processes, it is preferred to use high pressure in the corresponding reaction / combustion chamber. A pressure of 150 bar or higher has proved to be particularly preferred, and a pressure of approximately 300 bar is particularly preferred.

すなわち、開始材料に存在する水晶成分が結晶性シリコンに変換される（第１部分反応）。 In addition, nitrogen is fed into other points in the process (specifically during the first partial reaction) or into the combustion chamber, respectively. Further, a plurality of catalysts or one type of catalyst may be used for one or more partial reactions. Perform reduction in the chamber under appropriate environmental conditions. The condition is shown in a very simple form as follows:

That is, the crystal component present in the starting material is converted into crystalline silicon (first partial reaction).

The mineral oil contained in the sand used serves as the first energy provider, and in the method according to the present invention, a compound similar to hydrogen (H ₂ ) and graphite (ie, coke form) at a temperature of 1000 ° C. or higher. Most of them are thermally decomposed (ie during the first partial reaction). However, other first energy providers may be used with the starting material as well. Therefore, hydrogen is removed from the hydrocarbon chain of the first energy provider in the ongoing first partial reaction. As described below based on the examples, hydrogen may be bound to one of the reversible energy carriers already mentioned according to the invention. However, hydrogen introduced directly into the process or hydrogen originating from water such as gaseous alkanes or steam may be used for one or more partial reactions.

Silicon nitride as an energy carrier:
In order to be able to provide powdered or flaky silicon nitride, silicon generated in the process (specifically during or at the end of the first partial reaction) is injected or transferred into the chamber. May be. Alternatively, it may be dropped from above through the trajectory. Nitrogen (specifically nitrogen from the atmosphere), preferably pure nitrogen (containing 90-100 volume% nitrogen), is injected into the chamber or trajectory. Silicon burns and reacts with nitrogen to produce silicon nitride, which is present in the chamber at a temperature above 1000 ° C, preferably above 1350 ° C. The reaction (second partial reaction) is strongly exothermic. The amount of heat generated in the reaction (second partial reaction) (referred to as second energy) is used to heat another starting material (in this case, for example if the first provider added earlier is consumed) The amount of heat released in the partial reaction may be used to supply sufficient energy to the first partial reaction), which may be used to separate the heat from the second process (second partial reaction) You may supply in series to an endothermic process (specifically 6th partial reaction). In addition to this, or instead of this, the amount of generated heat may be used. A medium (eg water) is heated and thereby drives a gas turbine or a steam turbine (conventionally gaining energy).

For example, porous silicon nitride may be generated by drying silicon nitride under extreme conditions. For drying, an approach using a kind of autoclave is preferred. In the autoclave, temperature and pressure increase. On the other hand, the required amount of heat (referred to as second energy) may be obtained from the above-described exothermic process (specifically, the second partial reaction). The pressure and temperature should be chosen so that the phase boundary between the gas and the liquid is indistinguishable before cooling and / or drying is performed. Porous silicon nitride is produced in the process (sixth partial reaction). However, the sixth partial reaction may be modified such that silicon nitride nanostructures or nanocrystals are produced in the sol-gel process. These silicon nitride nanostructures or nanocrystals may be used as a reversible energy storage means or as a starting material for providing NH ₃ .

In the second embodiment, the present invention is applied in connection with the pyrolysis method of Piromex AG (Switzerland). However, the present invention may be used as a supplement to or as an alternative to the oxyfuel process. Thus, for example, using the present invention, energy-material serial coupling (EMC ² ) may be performed according to the following approach. As an alternative to the oxyfuel process, aluminum, preferably liquid or powdered aluminum (which may be produced using, for example, the twelfth partial reaction) is added and (instead of oil or coal) The oil-impregnated sand is first burned with oxygen (O ₂ ) and then preferably with nitrogen and possibly aluminum (Wacker accident) (seventh partial reaction) to generate additional heat. However, since the heat generated in the exothermic seventh partial reaction is large, oil or coal may be excluded from the first energy provider here.

  In the seventh partial reaction, aluminum removes oxygen from silicon dioxide and is oxidized to produce aluminum oxide. The partial reaction functions particularly when no or only a small amount of oxygen is introduced from the outside. This is because oxygen instantly forms a thin film on the aluminum surface, thereby quasi-passivating the aluminum. Therefore, embodiments in which the nitrogen atmosphere is at least temporarily pre-defined in the reaction region are particularly preferred.

  When nitrogen combined with silicon compounds is required, it is preferable to obtain a pure nitrogen atmosphere from the atmosphere by burning propane gas with the oxygen component of air (known as propane nitration). However, other methods exist for separating oxygen and nitrogen. A reverse osmosis method, a classical Linde method, or a method using a perovskite membrane is considered as another possible method. Providing nitrogen is referred to as the eighth partial reaction.

According to the invention, aluminum may be used. Currently, it is only possible to cost-effectively obtain aluminum from bauxite. Bauxite contains approximately 60% aluminum oxide (Al ₂ O ₃ ), approximately 30% iron oxide (Fe ₂ O ₃ ), silicon oxide (SiO ₂ ) and water. This means that bauxite is typically always “contaminated” by iron oxide (Fe ₂ O ₃ ) and silicon oxide (SiO ₂ ).

Al ₂ O ₃ has a very high lattice energy and may not be chemically reduced. However, aluminum can be industrially produced by molten salt electrolysis of aluminum oxide A ₂ O ₃ (cryolite-alumina method). Al ₂ O ₃ is obtained, for example, by the Bayer method. In the cryolite-alumina method, aluminum oxide is dissolved in cryolite (salt: Na ₃ [AlF ₆ ]) and electrolyzed. Aluminum oxide dissolves in cryolite melt in order not to react at the high melting temperature of 2000 ° C. of the aluminum oxide. Therefore, the operation temperature in the method is only 940 ° C to 980 ° C.

In molten salt electrolysis, liquid aluminum is generated at the cathode and oxygen is generated from Al ₂ O _{3 at the} anode. Carbon black (graphite) is used as the anode. These anodes must be continuously replaced because they are burned out by the resulting oxygen.

  In another aspect, an electrically conductive plasma may be used as the anode. Thus, the conventional anode will be replaced by a strong anode. The plasma is preferably generated in a region on the trough with an appropriate configuration and electrode activity.

  The extremely high energy consumption due to the high binding energy of aluminum is considered a significant disadvantage of the cryolite-alumina process. Also, the generation and release of occasional fluorine is a problem for the environment.

  In the method according to the present invention (9th partial reaction), process cooling may be realized by applying bauxite and / or aluminum oxide to the method. Excess thermal energy in the system may be consumed by the bauxite and / or aluminum oxide. This is carried out in the same manner as the method in which scrap iron is supplied to the molten iron in the blast furnace for cooling when the molten iron becomes excessively hot. For this reason, for example, bauxite may be introduced into the reaction chamber as a block crushed to an appropriate size in advance using a shredder (crusher). In addition, if a desired temperature in the reaction chamber is exceeded, bauxite and / or aluminum oxide may be introduced (specifically using an optical sensor) through a suitable control loop that measures the temperature in the reaction chamber.

  If the method may become uncontrollable (see Wacker Accident), cryolite may be used as a supplement, thereby reducing the temperature in the system by emergency cooling based on new cryolite. However, a rare gas emergency saturation system that saturates the reaction chamber with a rare gas (preferably argon) in an emergency (or before this happens) is more appropriate. The noble gas emergency saturation system can be used for each partial reaction. Further details about the chemical sequence and energy process described above are provided from the next page.

Quartz sand reacts exothermically with liquid aluminum or powdered aluminum to produce silicon and aluminum oxide (as by-products) according to the Holman-Wyberg textbook (seventh partial reaction):

Silicon burns with nitrogen at 1350 ° C. to produce silicon nitride. The reaction is exothermic as described above (second partial reaction):

Silicon then reacts exothermically slightly with carbon to form silicon carbide (tenth partial reaction):

However, silicon carbide may be obtained endothermically from sand and carbon at approximately 2000 ° C. (11th partial reaction):

  The endothermic process for obtaining the silicon carbide is powered up by heat (second energy) generated during the reaction of silicon dioxide with aluminum (seventh partial reaction) and / or nitrogen (second partial reaction), for example. May be. Silicon carbide may be obtained in the same reaction chamber or downstream or adjacent reaction chamber (10th partial reaction or 11th partial reaction).

In order to regenerate aluminum from the by-product bauxite or aluminum oxide Al ₂ O ₃ (12th partial reaction), aluminum and oxygen were electrolyzed without adding cryolite to liquid Al ₂ O ₃ (melting point 2045 ° C.). Is generated. The twelfth partial reaction is strongly endothermic and may be used to cool an exothermic reaction (see, for example, the ninth partial reaction). For this reason, the corresponding reactions may be thermally combined with each other. That is, the endothermic process for recycling aluminum may be powered up using heat generated during the reaction of silicon dioxide with aluminum and / or nitrogen, for example. However, in order to overcome the high lattice energy of Al ₂ O ₃ , current is required in addition to the heat.

Silane products:
Magnesium reacts with silicon to produce magnesium silicide:

Magnesium silicide reacts with hydrochloric acid to produce monosilane SiH ₄ and magnesium chloride:

The synthetic route works with aluminum. As a result, aluminum silicide Al ₄ Si ₃ is produced as an intermediate material. Higher order silanes can be obtained by polymerization of SiCl ₂ with SiCl ₄ only and subsequent reaction with LiAlH ₄ as shown in the prior art.

  However, according to the present invention, monosilane is preferably produced according to a method called third partial reaction. It is understood that a route through aluminum silicide or magnesium silicide is an alternative.

  Yet another basic aspect of the present invention is described below.

  In order to use the first energy provider more effectively, the first energy provider is not yet mixed with the starting material (sand, bauxite, slate, gneiss, mica, and / or granite) It may be preheated separately. Thus, for example, the crude oil may be boiled until it boils before it is mixed with the starting material.

  Instead of or in addition to the first energy provider, the furnace may be provided with external or internal heating means to supply the heat required to initiate the reaction (specifically, the first partial reaction) ). An induction furnace is particularly suitable. However, the process according to the present invention (specifically, the first partial reaction) may be combined with a conventional power plant process that operates using fossil fuel (specifically, hard coal). In that case, the starting material is heated using at least a portion of the exhaust heat generated in a conventional power plant process.

In another embodiment of the present invention, the reaction of the starting material can be initiated by contacting silicon (eg, powder form) with nitrogen and / or aluminum (powder form or liquid). The silicon used here is initially obtained in the first partial reaction. At the end of the first partial reaction, part of the obtained silicon may be stored. This eliminates the need for later initiating the series process according to the present invention with a first energy provider that generates CO ₂ .

In order to prevent the CO ₂ generated when the first energy provider is burned with oxygen in the early stage of the process from being released into the atmosphere, the flue gas generated in the process is sent to the reaction chamber via a return pipe or return duct. You may return. It is particularly preferred to introduce the flue gas to flow through or around sand, bauxite, slate, gneiss, mica or granite. When the first energy provider containing hydrocarbons is “consumed” in the first partial reaction, the flue gas is first transferred to a cooling tower or downstream decontamination system (such as a desulfurization system) or filter.

However, as described above, water glass may be used. Water glass is a water-soluble alkali silicate. These are generally the following composition: i.e. having the _{M 2 O · nSiO 2 (n} = 1~4), glassy, i.e., amorphous, non-crystalline compound. To date, sodium and potassium silicates have been frequently used industrially. According to the invention, sodium silicate, potassium silicate, and aluminum silicate or a mixture of two or more of these silicates may be used.

Since aluminum exhibits a chemical behavior similar to that of silicon, a combination of a process using a silicon compound (herein referred to as a silicon product) and a process using an aluminum compound is particularly suitable. For example, it is particularly preferable to use an aluminum silicate containing SiO ₂ and Al ₂ O ₃ . Providing the corresponding silicate and / or producing water glass is referred to as a third partial reaction.

  Silicates or water glasses etc. may be used as starting materials for the process according to the invention, or they are mixed with eg sand or other starting materials (14th partial reaction), eg more suitable for the second partial reaction. A starting material (referred to as starting material I) may be obtained.

  To produce a mixture of one or more first energy providers (specifically mineral oil) (15th partial reaction), silicates or water glass may be used and are necessary to start the process according to the invention. Silicate or water glass may be used to provide a hydrocarbon component and to provide a reactant (referred to as starting material II) that accelerates or accelerates the reaction.

As mentioned at the outset, sulfur residues accumulate on fossil fuels burned in power plants. According to European Patent Application No. 06 126 325.7, H ₂ O ₂ may be provided as an energy carrier in a fossil fuel based power plant process.

According to the invention, pure (= water free) H ₂ O ₂ is not suitable and can explode spontaneously when it comes into contact with a metal, for example. (Aqueous solution) is circulated. The limit value of 70% is referred to herein as the critical concentration limit.

The solution is selected according to the present invention such that the concentration of H ₂ O ₂ is below the critical concentration limit. The solution is then transferred to the consumer (filling station, end consumer). Energy may be generated at the consumer by removing hydrogen and / or oxygen from the solution and using the hydrogen and / or oxygen as an energy supplier and / or fuel.

Oxygen may be used in the reaction to peroxosulfuric acid. As described above, the peroxosulfuric acid can be obtained from the atmosphere, CO ₂ exhaust gas from the power plant process, and silicon dioxide reduction process (first partial reaction), respectively.

H ₂ O ₂ is particularly suitable as energy or fuel. Transferring the reversibly available hydrogen carrier produced in accordance with the present invention to the consumer may be performed in a variety of ways (specifically by transport vehicles). The transfer is definitely a problem. This is because the handling of the hydrogen carrier is not relatively critical.

  In use, hydrogen and / or oxygen of a reversibly usable hydrogen carrier may be removed. Thereafter, the hydrogen may be used, for example, in a fuel cell.

  In the following, various preferred approaches for the technical implementation of the invention will be described with reference to the schematic drawings. It should be noted that the outline of the reaction zone in the form of a combustion chamber or furnace is to be understood as merely an example. It is clear that the method according to the invention can also be used in differently designed combustion chambers or furnaces.

  FIG. 16 shows a first embodiment. As shown in FIG. 16, two horizontally operated combustion furnaces 10 and 20 (specifically, blast furnaces) are arranged adjacent to each other. The first combustion furnace 10 has an outlet region 11, and the second combustion furnace 20 has an outlet region 21. In each case, exhaust gas (combustion exhaust gas) is generated. The first combustion furnace 10 is filled with fossil fuel 12 (specifically, hard coal), and the fossil fuel reacts with oxygen (specifically, oxygen in air) and burns. A large amount of heat is released during the well-known process. The heat is partially transferred to the medium (specifically water) through the heat exchanger 13 and the resulting steam is used to drive the turbine and thereby obtain an electric current.

  According to the present invention, various reactions proceed in series. In the embodiment shown, there is a thermal coupling for the second combustion furnace 20. That is, the two furnaces 10 and 20 are thermally combined with each other directly or indirectly. This is indicated by the arrow W1 in FIG.

  Thermal coupling may be performed in the present embodiment or other embodiments in which two furnaces stand upright with the wall surfaces facing each other. The coupling is via an appropriate passive thermal bridge (specifically using a heat conductor) or via an active thermal bridge (specifically using a heat exchanger or a corresponding transfer medium). May be executed.

  In the second combustion furnace 20, one of the starting materials 22 containing silicon oxide is heated by the amount of heat W <b> 1 provided by the first furnace 10. That is, the reaction that proceeds in the first furnace 10 is generally used as the first energy provider for the first partial reaction according to the present invention. In the first partial reaction, silicon dioxide is converted to silicon. For example, air (or pure nitrogen) containing a typical nitrogen component may be introduced into the furnace 20 by a lance 24 or similar means. Obviously, the introduction position may be selected separately. Silicon reacts with nitrogen to produce silicon nitride (see second partial reaction). The reaction is strongly exothermic and the amount of heat generated is partially or wholly conducted to the medium (specifically water) via the heat exchanger 23, and the resulting water vapor is used to drive the turbine. It may be driven to acquire current.

  A variation of the first embodiment that uses the second heat to support or enable another partial reaction is particularly preferred. Therefore, for example, as shown in FIG. 16, a reaction region 38 that absorbs silicon nitride resulting from the second partial reaction and converts it into porous silicon nitride, silicon flakes, or silicon powder may be provided. Good. They have a very large volume for supplying heat and / or for reactants and / or pressure and have a very large surface area. The sixth partial reaction can be supported by the second heat of the second partial reaction via appropriate thermal coupling. This is indicated by the arrow W2 in FIG.

  Silicon nitride may be removed by freight vehicle 31 as shown in FIG.

CO ₂ may be introduced into the furnace 20 (this step is optional). CO ₂ may be guided from the exhaust gas region 11 of the first furnace 10 to the second furnace 20, or may be reduced by introducing CO ₂ from the atmosphere, that is, detoxified.

A second embodiment is shown in FIG. As shown in FIG. 17, a horizontally operated combustion furnace 20 may be provided. One of the starting materials 22 comprising silicon dioxide is heated in the combustion furnace 20 by the combustion of a first energy provider (specifically fossil fuel such as oil and / or tar). In particular, silicon is generated in the first partial reaction according to the present invention. As in the first embodiment, silicon nitride and heat are generated by introducing nitrogen. However, in an alternative method of the process, silicon may react with carbon to produce SiC (see 10th partial reaction). The carbon may be originate from fossil fuel or CO _2. This is optional, but may be introduced into the furnace 20 (specifically through the supply port 25). The partial reaction proceeds exothermically, however, less heat is transferred than the second partial reaction.

As described above, CO ₂ may be introduced into the furnace 20 in the _second embodiment.
In order to support or enable another partial reaction, a variation of the second embodiment in which the second heat W2 is used is particularly preferred. Thus, for example, as shown in FIG. 17, the resulting silicon carbide from the tenth partial reaction is absorbed and dried, sintered, while supplying heat and / or another reactant and / or pressure. A reaction zone 30 may be provided for purifying. The another partial reaction may be supported and allowed by the second heat of the tenth partial reaction by appropriate thermal coupling, as indicated by arrow W2 in FIG.

  The silicon carbide or purified silicon carbide may be removed by the freight vehicle 31 as shown in FIG.

  FIG. 18 shows a third embodiment. As shown in FIG. 18, a horizontally operated combustion furnace 20 may be provided. One of the starting materials 22 comprising silicon dioxide is heated in the combustion furnace 20 by the combustion of a first energy provider (specifically fossil fuel such as oil and / or tar). In particular, silicon is obtained in the first partial reaction according to the invention. Similar to the first embodiment, silicon nitride and heat are generated by introducing nitrogen. However, the partial reaction proceeds extremely exothermically. Aluminum oxide 42 (which may or may not contain cryolite) is used as a coolant in the separated reaction zone 40 to cool the furnace 20 and thereby control the second partial reaction. . The reaction zone 40 at least partially surrounds the furnace 20. Aluminum oxide 42 may be introduced from above and is converted to liquid aluminum 43 due to the large amount of heat released by the furnace 20. This may be drained downward, for example. When the electrode for (molten salt) electrolysis is provided in the reaction region 40, the conversion (reduction process) proceeds.

The reaction zone 40 comprises, for example, a steel trough. This is covered with a carbon material for (molten salt) electrolysis. These details are not shown in FIG. A liquid electrolyte (aluminum oxide that may or may not contain cryolite) is placed in the trough. An anode (specifically, carbon black) connected to the positive electrode of the power source is immersed in the electrolyte. The trough is used as a cathode and connected to the positive electrode. Heavier than the reduced aluminum electrolyte in the twelfth partial reaction (see equation below) and therefore collects on the bottom of the trough. From there, it is removed, for example, using a suction tube.

The starting material for this electrolysis (also known as molten salt electrolysis) is a mixture of clay minerals such as bauxite, aluminum oxide and aluminum hydroxide (Al (OH) ₃ ). Silicon dioxide is usually present in bauxite. To date, bauxite has been initially separated from the iron oxide contained (specifically using the Bayer method). In addition, the silicon oxide that “contaminates” the bauxite is then generally separated. According to the invention, it is not always necessary to carry out a complex separation of the components of the mixture. This is because there is sufficient energy in the process and the preparation of pure aluminum is not a major concern.

  In aluminum products used industrially to date, bauxite (which may or may not contain the components of the above mixture) may be diluted with water to produce ammonium hydroxide. Good. The bauxite may be mixed with water vapor or supercritical water (above 407 ° C. at high pressure) to produce aluminum hydroxide.

Ammonium oxide is produced by heating aluminum hydroxide to approximately 1200-1300 ° C. (specifically using the second energy):

  The aluminum hydroxide may or may not contain cryolite as described above, but is then subjected to (molten salt) electrolysis.

  The cooling effect may be promoted or reduced by adding bauxite and / or aluminum oxide in a controlled manner. In this embodiment, high purity aluminum is generated along with the product of the second partial reaction.

  In another preferred embodiment schematically shown in FIG. 19, aluminum 43 is added in liquid or powder form to silicon dioxide 22 in the reaction zone (specifically, the reaction zone of furnace 20). The addition of aluminum is indicated by arrow 46 in FIG. In this embodiment, aluminum is also obtained in the twelfth partial reaction using (molten salt) electrolysis. The (molten salt) electrolysis is carried out in the reaction zone 40 in the form of a trough covered with a carbon material 44. Aluminum 43 is produced from aluminum oxide 42 (which may or may not contain cryolite) in the trough when high current is applied to the carbon material 44 used as the anode and cathode. . The aluminum 43 may be disposed at the bottom by a suction pipe and may be removed from the bottom, or may be discharged downward through the fall pipe 45. Liquid aluminum may be transported from the discharge point to the reaction area of the furnace 20 to remove oxygen from the silicon dioxide. A nitrogen atmosphere is preferably present in the furnace 20 during the phase of the process.

  Similar to the known thermite reaction (aluminum is used as a reducing agent, for example as a reducing agent to reduce iron oxide to iron), the aluminum is used here as a reducing agent to remove oxygen from silicon dioxide. The This reaction (seventh partial reaction) proceeds very exothermically and a very large amount of heat is released. This amount of heat may be applied in parallel to the aluminum manufacturing process (12th partial reaction) and / or the amount of heat may be used (using heat exchanger 23) to generate current. May be.

  Two possible embodiments are schematically illustrated in FIGS. 20 and 21. FIG. Use a furnace mounted horizontally or slightly diagonally in both cases.

The energy-material series coupling (EMC ² ) according to the present invention is distinguished in that the process proceeds beyond thermal equilibrium in the dissipative structure, as in the anatomy of cells and organs.

  According to the present invention, instead of operating the combustion process with oxygen up to that point, a nitrogen combustion process may be substituted.

According to the invention, a so-called silicon product is produced. Here, the term silicon product refers to the following (intermediate) products: silicon nitride (specifically powder, flake form or porous form), silicon (specifically flake or powder) , Silicon carbide, monosilane or long chain silane, magnesia silicide, SiCl ₂ , SiCl ₄ , silicon, and other components such as aluminum, calcium, or magnesia (silicate) are used to illustrate the conversion of the composition. These silicon products have heretofore been produced in a chemically very clean form, for example in the semiconductor field. For example, pure silicon has a purity of 98-99.5%, or 99.9999999% or less.

To date, the potential of these materials as energy carriers (each supplier) has not been recognized. When these silicon products are produced in a manner similar to a power plant or power plant process, they can be produced in large quantities at relatively affordable conditions. It is believed that these silicon products are a special advantage of silicon products that they can be converted to SiO ₂ depending on the reaction partner. The SiO ₂ material is absolutely environmentally friendly and easy to process. Preferably, the silicon product produced in accordance with the invention in a power plant or by a method similar to a power plant process has a purity in the range of 50-97%. Silicon products having a purity of 75-97% have proven particularly beneficial. Such silicon products can be produced in large quantities in low-cost large-scale plants and at the same time are suitable as energy carriers (respectively suppliers).

Claims (19)

A method for supplying energy in a power plant process,
Introducing into the reaction zone a starting material comprising at least one selected from the group consisting of sand, bauxite containing silicon dioxide, quartz, gneiss, mica, granite, slate;
Supplying a first energy provider to initiate a reaction in which the starting material is heated and silicon is generated from the starting material;
Using silicon in the first partial reaction that proceeds exothermically and can release heat;
Using the heat as a second energy, replacing the first energy provider in heating the starting material, and / or for at least one other partial reaction or series of partial reactions at the end of the silicon product yield, Providing the required energy.   The method of claim 1, wherein the first energy provider is added to the starting material, or the starting material is already included in the first energy provider.   The method according to claim 1, characterized in that a first energy provider comprising hydrocarbons, preferably at least one selected from the group consisting of oil, tar, asphalt, coal, is used.   The method according to claim 1, 2 or 3, wherein in the first partial reaction, silicon is reacted with nitrogen to produce silicon nitride, and a large amount of energy is released.   The method according to claim 1, 2, or 3, wherein in the first partial reaction, silicon is reacted with carbon to form silicon carbide, and a large amount of energy is released.   4. A method according to claim 1, 2 or 3, characterized in that the starting material is supplied with liquid or powdered aluminum in order to remove oxygen from the starting material silicon dioxide. And CO _2, liquid or powder and aluminum, is fed, the aluminum of claim 1, 2 or 3, characterized in that taking out oxygen from the CO ₂ becomes aluminum oxide by reducing CO ₂ Method.   The method according to claim 1, wherein the partial reactions proceed continuously or simultaneously.   9. A method according to any of claims 1 to 8, characterized in that the silicon product has a purity in the range of 50-97%, preferably in the range of 75% -97%. A device for providing energy, a first reaction zone for receiving at least one starting material;
Means for heating the starting material using a first energy provider;
A second reaction zone for receiving at least one first material and converting the first material to a second material;
The apparatus, wherein the second reaction zone is thermally combined with the first reaction zone so that heat generated in the first reaction zone is supplied to the second reaction zone. The first reaction region receives one or more starting materials comprising sand, gneiss, mica, granite, slate, building stone containing silicon dioxide;
11. The apparatus of claim 10, wherein the apparatus is designed to receive at least one first energy provider selected from the group consisting of oil, tar, asphalt and coal.   12. The apparatus according to claim 11, further comprising means for supplying oxygen and / or nitrogen in the first reaction zone.   Device according to claim 10, 11 or 12, characterized in that it provides an active or passive thermal coupling.   The apparatus according to claim 10, 11 or 12, further comprising means for changing from an oxygen-containing atmosphere to a nitrogen-containing atmosphere.   13. A device according to claim 10, 11 or 12, characterized in that it comprises cooling means to obtain a cooling effect during or after performing the exothermic partial reaction by adding bauxite and / or aluminum oxide. The cooling means comprises a receptacle area, preferably a trough;
16. The receptacle area according to claim 15, wherein the receptacle area is designed and arranged so that heat is removed from the first reaction region or the second reaction region by introducing the bauxite and / or aluminum oxide into the receptacle area. apparatus.   16. The apparatus according to claim 15, wherein the cooling means is designed and arranged so that bauxite and / or aluminum oxide is introduced directly into the first reaction zone or the second reaction zone.   The apparatus according to claim 10, further comprising a rare gas emergency saturation system capable of introducing a rare gas into the first reaction region or the second reaction region. The first material is at least one selected from the group consisting of oil-containing sand, oil-containing shale, bauxite, gneiss, mica, granite, shale;
The apparatus according to claim 10, wherein the second material is silicon or a silicon product.

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