Process for generation of thermal and radiant energy, hydrogen and carbon monoxide by oxidizing metal and organic compound

Abstract

Disclosed is a process for oxidizing a metal and for generating hydrogen and carbon monoxide by using a reactor having a reaction chamber with an inlet zone for reactive materials, a central zone and an outlet zone for a product gas. In this process a first reactive material and a second reactive material are used, each comprising selected components comprising selected metals and organic compounds. In the process a first flame is generated by reacting the first reactive material present in the inlet zone. This first flame generates and supports a second flame that is formed by reacting the second reactive material present in the inlet zone. In the second flame a product gas is formed that contains hydrogen and carbon monoxide. Hydrogen and carbon monoxide are discharged from the reactor and can be used for various chemical reactions and / or for generation of energy. Moreover, thermal energy generated in the reactor can be used for generation of electrical energy and / or for different heating applications.

Description

[0001] Energy 13 GmbH

[0002] Attorney's File = 224eg01.wo

[0003] Description

[0004] Process for generation of thermal and radiant energy, hydrogen and carbon monoxide by oxidizing metal and organic compound

[0005] Technical Field

[0006] This invention relates to scalable metal-fuel concepts designed for oxidizing metal fuel and organic compound and generating hydrogen and carbon monoxide for industrial use.

[0007] Background of the Invention

[0008] This invention concerns the growing interest of transporting and storing energy, especially renewable helio-ecological energy and using metals for energy production without generation of carbon dioxide.

[0009] This invention addresses the need for energy in a helio-energy driven circular economy with optimized volumetric energy density transport and efficient release of energy.

[0010] Industrial branch standards in fact even grew into global use of charcoal carbon by itself as caloric or chemical feedstock in metallurgical processes practised until today. In such processes minerals especially oxides are reduced to manufacture specific metallurgical phases, such as steel or steel alloys and the reduction of electricity by graphite electrodes in classic aluminium smelters. On the shoulders of the fossil carbon sources whether gas, refined crude oil or anthracite, all kinds of gasification and liquidation generated an interconnectivity of different manufacturing processes. Guided by the global or local energy prizes this interconnectivity allowed the chemical industry to switch their processes several times after the second world war or under political or block embargoes. As a consequence, even hydrogen and food feedstock or fertilizer were made available on that technical-economic basis and more direct procedures, such as electricity-to- fertilizers or hydrogen-to-metals, stepped back.

[0011] The urgent need for energy transport and hydrogen and / or carbon monoxide to yield or to produce metals or other chemicals regionally in the pure or technical form. As an energy source selected metals are proposed which represent a high enthalpic energetic state in a thermodynamic sense and together with their mineral oxides in turn would represent a high volumetric energy density to store and release energy.

[0012] This invention demonstrates a new optimized solution for the generation of thermal and radiant energy and hydrogen and carbon monoxide by providing a high volumetime yield conversion of stock metal yielding electricity on demand by using an easy and safe transport-infrastructure (global metal / metal-oxide cycle) and to use this process by producing hydrogen and carbon monoxide continuously at the same time.

[0013] Prior art

[0014] Processes of using metals as fuel are generally known.

[0015] WO 2014 / 173991 A1 proposed a full developed chemical-industrial hyperbranch of circles using aluminium as an energy storage material which is reacted with CO2 to generate thermal energy for caloric grid-energy production and at the same time for converting CO2to CO which is used as a base chemical for synthesis of chemicals. Metal burners using air or oxygen gas with no chemical feedstock transformation are generally known.

[0016] In DIS-Vertrags Nr. 150401 Programm Solarchem ie / Wasserstoff; Bundesamt fur Energie BFE Schlussbericht Juni 2004; Aluminium als Brennstoff und Speicher; J. Wochele, Dr. Chr. Ludwig; Paul-Scherer-lnstitut CH-5232 Villigen results about the Aluminum-Alumina cycle as renewable electric energy storage are reported. Key hurdles for air or oxygen combustion of Aluminum metal to its oxide are disclosed. In this report a flame reactor was proposed and established which has been developed from an aluminum oxidizer. Most interestingly in this analysis it was stated that the biggest loss in such energy cycle would be the carbon electrode itself, so the today established industrial introduction of low abrasive electrodes would yield a reasonable energy-storage-energy cycle per se.

[0017] Another group, Trowell, focuses on reacting aluminum in contact with water to release the reaction enthalpy in the form of heat and hydrogen. The result would be instant access to clean power, with no release of greenhouse gases. In a 2018 talk Trowell explains the underlying reactions and potential applications of this technology concept. While laboratory work has shown that the use of metal fuels with heat engines is technically feasible, no one has yet demonstrated the conversion in practice. One concept has been disclosed, for example, by BERGTHORSON, J.M. ET AL.: "Metal-Water Combustion for Clean Propulsion and Power Generation", APPLIED ENERGY, vol. 186, 1 January 2017 (2017-01-01 ), pages 13 - 27, XP055746514

[0018] The next step toward turning the lab findings into usable technology, therefore, will be to build a prototype conversion and couple it to a heat engine, again with a focus to optimize particle conversion at lower temperatures by proposing specialty metal powders including nano-spheres; compare https: / / www.mcgill.ca / newsroom / - channels / news / could-metal-particles-be-clean-fuel-future, published 2015. Bergthorson states that developing metal recycling processes that don’t involve CO2emissions is also critical; compare https: / / www.mcgill.ca / newsroom / channels / - news / could-metal-particles-be-clean-fuel-future-257172.

[0019] For continuous use all academic or published industrial methods typically only show principles, hurdles and optimize few aspects of a continuous metal-fuel combustion. Fewer technical or academic theoretical considerations show solutions for metal-fuel reactors towards bulk material use and technically scalable processes.

[0020] Oxygen burners using special micronized Aluminium yield a stable continuous flame (F. Halter et al. in Applications in Energy and combustion Science, Vol. 13, https: / / doi.org / 10.1016 (2023)). Al, Mg and the Alkali metals and their alloys are reported to show self-sustained air-oxygen reactions from gas propelled powder transport. The reported temperatures indicate the importance of the self sustained kinetic within the flame geometry.

[0021] Jean Samuel et al. disclose in Experimental, Thermal And Fluid Science, vol. 153, 111130 (2023) (Elsevier, Amsterdam) investigations about the thermal structure of an aluminium-methane / air hybrid flame. In this article hybrid aluminium / methane / -air flames have been stabilized in a laminar Bunsen-type burner and different flame properties as well as their dependence from the composition of the flammable mixture are reported.

[0022] WO 2021 / 228429 A1 discloses the advantage of a liquid metal fuel present in all Al smelting architectures to be dispersed into a reactor with precursor gases containing H2O or CO2and yields reasonable turnover together with the heat introduced by the liquid aluminium into the system.

[0023] As cited above there is lot of scientific and theoretical hypothesis work about reaction of Al with air, O2. But most of these articles describe no technical burner or converter that facilitates a stable flame under continuous dosing of solid Al and which does not plug and in air or oxygen only with the use of a micronized Aluminium preparation. The use of Al as energy storing material and oxidation with air for heat generation in a pilot scale burner has been investigated in Paul Scherer Institute in Switzerland (compare J. Wochele, Chr. Ludwig; Aluminium als Brennstoff und Speicher. Bundesamt fur Energie BFE (2004); https: / / infoscience.epfl.ch / record / 165265).

[0024] Even after several steps of optimization the burner blocked although the oxidation of Al with an oxygen containing gas like air is understood to be easier to be conducted than the oxidation without oxygen.

[0025] Also, the particle size has an influence on the implementation of full oxidation of aluminium mass. For example, Dilip Srinivas Sundaram, Puneesh Puri, Vigor Yang; A general theory of ignition and combustion of nano- and micron-sized aluminum particles. Combustion and Flame Volume 169, July 2016, Pages 94-109. https: / / doi.Org / 10.1016 / j.combustflame.2016.04.005 report that oxidation time increases significantly with particle size. Moreover, it is general knowledge that higher volume specific surface of smaller particles supports a decrease of ignition temperature.

[0026] Experiments have shown that particulate metals when transported through lines tend to agglomerate and to line-blocking. For generating self-sustained flames a continuous transport of fuel is indispenable.

[0027] The objective of the present invention is the provision of a process of converting selected metals in the presence of selected reactants which allows a sustained flame, which produces thermal and radiant energy, hydrogen and carbon monoxide and which is easy to implement.

[0028] Another objective of the present invention is the provision of a process for generation of self-sustained flames with low tendency for agglomeration of the metal fuel in the feed lines. Still another objective of the present invention is the provision of a process for transforming chemical energy into thermal and radiant energy and to generate at the same time hydrogen and carbon monoxide.

[0029] Another objective of the present invention is a process that is carried out effectively converting selected metals in an atmosphere comprising selected reactants by providing a self-sustained flame and generating hydrogen and / or carbon monoxide.

[0030] Summary of the invention

[0031] Surprisingly it has been found that these objectives can be solved by a process using selected combinations of reactants comprising selected metals and organic compounds and / or selected oxidants as fuel in which process two flames are generated. A first flame is used to generate heat and radiation or in addition a product gas containing H2O, CO and CO2and / or hydrogen and CO. The first flame generates and supports a second flame that may use the products formed by the action of the first flame and optionally at least one additional ingredient selected from the group CO2and H2O to react with a main metal fuel in a second flame resulting in a product gas flow comprising metal oxide, hydrogen and carbon monoxide as main components.

[0032] The present invention relates to a process for generation of thermal and radiant energy, hydrogen and carbon monoxide by oxidizing a metal by using a reactor having a reaction chamber with an inlet zone for reactive materials, a central zone and an outlet zone for a product gas, said process comprising at least the steps: a) introducing a first reactive material into the inlet zone for generating a first flame said first reactive material being selected from the group consisting of

[0033] 11 ) a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen and oxygen or an oxygencontaining gas, or

[0034] 12) a mixture comprising a first metal fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals, an organic compound containing carbon and covalently attached thereto hydrogen and oxygen or an oxygen-containing gas, or

[0035] 13) a mixture comprising said first metal fuel, an organic compound containing carbon and covalently attached thereto hydrogen, oxygen or an oxygen-containing gas and H2O and / or CO2and / or NH3and optionally inert gas, or

[0036] 14) a mixture of said first metal fuel and oxygen or an oxygen-containing gas, b) introducing a second reactive material into the inlet zone for generating a second flame said second reactive material being selected from the group consisting of

[0037] 15) a metal main fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals, or

[0038] 16) a mixture comprising said metal main fuel and H2O and / or CO2and / or NH3and optionally inert gas, or

[0039] 17) a mixture comprising said metal main fuel, an organic compound containing carbon and covalently attached thereto hydrogen and oxygen and / or an oxygen-containing gas, or

[0040] 18) a mixture comprising said metal main fuel and an organic compound containing carbon and covalently attached thereto hydrogen, c) generating a first flame by reacting the first reactive material present in the inlet zone, d) generating and supporting a second flame by reacting the second reactive material present in the inlet zone using the first flame which is directed towards the second reactive material present in the inlet zone thereby forming a product gas containing hydrogen and carbon monoxide, and e) discharging the product gas from the reactor, wherein in the inlet zone the following combinations of first and second reactive materials are provided: 1 ) for generation of the first flame mixture i1 ) and for generation of the second flame metal main fuel i5), or 2) for generation of the first flame mixture i1 ) and for generation of the second flame mixture i6), or

[0041] 3) for generation of the first flame mixture i2) and for generation of the second flame mixture i6), or

[0042] 4) for generation of the first flame mixture i2) and for generation of the second flame metal main fuel i5), or

[0043] 5) for generation of the first flame mixture i3) and for generation of the second flame mixture i6), or

[0044] 6) for generation of the first flame mixture i3) and for generation of the second flame metal main fuel i5), or

[0045] 7) for generation of the first flame mixture i4) and for generation of the second flame mixture i7), or

[0046] 8) for generation of the first flame mixture i4) and for generation of the second flame mixture i8).

[0047] In the process of this invention selected combinations of reactants are used in the reactions forming the first and the second flame.

[0048] Preferred is a process using embodiments 1 , 2 or 3, very preferred embodiment 3.

[0049] In an embodiment 1 for generation of the first flame a mixture i1 ) (= mixture comprising organic compound and oxygen or an oxygen-containing gas) is used and and for generation of the second flame metal main fuel i5) is used.

[0050] In this embodiment an organic compound is combusted in an oxygen-containing atmosphere and CO2, CO and H2O are formed in the first flame. In the second flame metal main fuel is present which reacts with the CO2and the H2O from the first flame to generate hydrogen, CO and oxidized metal.

[0051] In an embodiment 2 for generation of the first flame a mixture i1 ) (= mixture comprising organic compound and oxygen or an oxygen-containing gas) is used and and for generation of the second flame a mixture i6) (= mixture comprising metal main fuel and H2O and / or CO2and / or NH3and optionally inert gas) is used.

[0052] In this embodiment an organic compound is combusted in an oxygen-containing atmosphere and CO2, CO and H2O are formed in the first flame. In the second flame metal main fuel is present which reacts with the CO2and the H2O from the first flame and added as mixture i6) to generate hydrogen, CO and oxidized metal.

[0053] Embodiment 2 is similar to embodiment 1 except that H2O and / or CO2are added to the second reactive material.

[0054] In an embodiment 3 for generation of the first flame a mixture i2) (= first metal fuel, organic compound and oxygen or oxygen-containing gas) is used and for generation of the second flame a mixture i6) (= metal main fuel and H2O and / or CO2and / or NH3and optionally inert gas) is used.

[0055] In this embodiment in the first flame an organic compound is combusted in an oxygen-containing atmosphere and CO2, CO and H2O are formed which are reduced totally or in part by the first metal fuel to result in oxidized metal, hydrogen and CO. In the second flame metal main fuel is present which reacts with the H2O and CO2present in the reaction mixture to generate hydrogen, CO and oxidized metal. The H2O and CO2present in the reaction mixture for the second flame is added with the second reactive material and may be also added as non-reacted consituents in the product gas from the first flame. The combined product gases from the first and the second flame contain hydrogen and CO.

[0056] In an embodiment 6 for generation of the first flame a mixture i2) (= first metal fuel, organic compound and oxygen or oxygen-containing gas) is used and for generation of the second flame metal main fuel i5) is used.

[0057] In this embodiment an organic compound is combusted in the first flame in an oxygen-containing atmosphere forming CO, CO2and H2O which are reduced totally or in part by the first metal fuel to result in oxidized metal, hydrogen and CO. In the second flame metal main fuel is present which reacts with H2O and CO2present in the reaction mixture to generate hydrogen, CO and oxidized metal. The H2O and CO2present in the reaction mixture for the second flame is added as non-reacted constituents in the product gas from the first flame. The combined product gases from the first and the second flame contain hydrogen and CO.

[0058] Embodiment 6 is similar to embodiment 5 except that there is no addition of H2O and / or CO2to the second reactive material.

[0059] In an embodiment 5 for generation of the first flame a mixture i3) (= first metal fuel, organic compound, oxygen or oxygen-containing gas, H2O and / or CO2and / or NH3 and optionally inert gas) is used and for generation of the second flame a mixture i6) (= metal main fuel and H2O and / or CO2and / or NH3and optionally inert gas) is used.

[0060] In this embodiment an organic compound is combusted in the first flame in an oxygen-containing atmosphere forming CO, CO2and H2O which are reduced totally or in part by the first metal fuel to result in oxidized metal, hydrogen and / or CO. In the second flame metal main fuel is present which reacts with the H2O and CO2present in the reaction mixture to generate hydrogen and CO and oxidized metal. The H2O and CO2present in the reaction mixture for the second flame is added with the second reactive material and may also be added as a product gas from the first flame.

[0061] In an embodiment 6 for generation of the first flame a mixture i3) (= first metal fuel, organic compound, oxygen or oxygen-containing gas, H2O and / or CO2and / or NH3 and optionally inert gas) is used and for generation of the second flame metal main fuel i5) is used.

[0062] In this embodiment an organic compound is combusted in the first flame in an oxygen-containing atmosphere forming CO, CO2and H2O which are reduced totally or in part by the first metal fuel to result in oxidized metal, hydrogen and / or CO. In the second flame metal main fuel is present which reacts with the H2O and CO2present in the reaction mixture to generate hydrogen and CO and oxidized metal. The H2O and CO2present in the reaction mixture for the second flame is added as a product gas from the first flame

[0063] Embodiment 6 is similar to embodiment 5 except that there is no addition of H2O and / or CO2and / or NH3and optionally inert gas to the second reactive material.

[0064] In an embodiment 7 for generation of the first flame a mixture i4) (= first metal fuel and oxygen or oxygen-containing gas) is used and and for generation of the second flame mixture i7) (= metal main fuel, organic compound and oxygen or oxygencontaining gas) is used.

[0065] In this embodiment the first metal fuel is combusted in the first flame in an oxygencontaining atmosphere resulting in oxidized metal. In the second flame the organic compound is combusted in an oxygen-containing atmosphere and CO, CO2and H2O are formed which in turn are reduced by the metal main fuel present in the second flame metal to result in hydrogen, CO and oxidized metal. The first flame in this embodiment supports the second flame by the heat produced in the reaction between first metal fuel and oxygen. In a preferred variant the second flame is supplied with oxygen that is not used in the first flame.

[0066] In an embodiment 8 for generation of the first flame a mixture i4) (= first metal fuel and oxygen or oxygen-containing gas) is used and and for generation of the second flame mixture i8) (= metal main fuel and organic compound) is used.

[0067] In this embodiment the first metal fuel is combusted in the first flame in an oxygencontaining atmosphere resulting in an oxidized metal. In the second flame the organic compound is decomposed to form hydrogen and dehydrogenated product. If oxygen from the first flame is present in the second flame the organic compound is combusted and CO, CO2and H2O are formed which in turn are reduced by the metal main fuel present in the second flame metal to result in hydrogen, CO and oxidized metal. The first flame in this embodiment supports the second flame by the heat produced in the reaction between first metal fuel and oxygen. In the preferred version the second flame is supplied with unreacted oxygen from the first flame.

[0068] Embodiment 8 is similar to embodiment 7 except that no oxygen or oxygencontaining gas is added to the second reactive material for the second flame.

[0069] The process of this invention can be carried out in a reactor for oxidizing a metal and for generating hydrogen and carbon monoxide comprising the elements:

[0070] A) a reaction chamber,

[0071] B) at least one feed line for introducing an organic compound containing carbon and covalently attached thereto hydrogen into the reaction chamber or into a mixing device arranged upstream to the reaction chamber and discharging into the reaction chamber,

[0072] C) at least one feed line for introducing a first metal fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals into the reaction chamber or into a mixing device arranged upstream to the reaction chamber and discharging into the reaction chamber,

[0073] D) at least one metering device for metering the amount of organic compound or of first metal fuel or of organic compound and first metal fuel introduced into the reaction chamber said metering device being arranged upstream the reaction chamber in the feed line for organic compound or for particulate metal of for the mixture of organic compound and particulate metal,

[0074] E) at least one feed line for introducing oxygen or oxygen-containing gas into the reaction chamber or into the mixing device arranged upstream to the reaction chamber and discharging into the reaction chamber,

[0075] F) at least one feed line for introducing a metal main fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals into the reaction chamber or into a mixing device arranged upstream to the reaction chamber and discharging into the reaction chamber,

[0076] G) optionally at least one feed line for introducing H2O and / or CO2and / or NH3into the reaction chamber or into a mixing device arranged upstream to the reaction chamber and discharging into the reaction chamber,

[0077] H) at least one metering device for metering the amount of metal main fuel or of H2O and / or CO2and / or NH3introduced into the reaction chamber said metering device being arranged upstream the reaction chamber in the feed line for for metal main fuel or for the mixture of metal main fuel and of H2O and / or CO2and / or NH3, and

[0078] I) optionally at least one ignition device to ignite the first reactive material present in the reaction chamber thereby generating a first flame in the reaction chamber.

[0079] Detailed Description of the Invention

[0080] The invention comprises a scalable process for the generation of thermal and radiant energy which is transformed into power for local or grid use. Moreover, the process of this invention generates carbon monoxide and hydrogen, which are essential base chemicals for decarbonized processes including raw materials and goods such as steel, syngas, synfuel, food chain ingredients as well as chemicals. For this high conversion rates and continuous or quasi continuous operations are needed as well as fast start and shut down typical for large industrial reactors and ovens.

[0081] Standard methods in scaling and gas separation can now be applied using the breakthrough of the invention for high yield and high durability. The CO-toxicity and the hydrogen safety limits are known and well managed in large industrial settings. The fuel and the circulated materials in this economy are extremely inert and stable in human environment and environmentally friendly. The technology can be handled in all regions of the world and in all economies from local small equipment to large conglomerates and metropoles. The process of this invention is preferably a continuous process. But the process can also be operated in a batchwise manner.

[0082] The process of this invention can be performed at under-pressure, at ambient pressure or at elevated pressure. Typical pressures within the reactor are in a range between 0.8 and 200 bar, preferably between 1 and 100 bar, more preferred between 1 and 50 bar und especially preferred between 1 and 10 bar. Most preferred the process is operated at ambient pressure (about 1 bar).

[0083] The reactor and the process of this invention are scalable within a broad range. Typical scales range from 10 kW to 10 GW, preferably from 50 kW to 1 GW of electrical energy produced from the heat generated by the process or the reactor, respectively.

[0084] In the process of this invention an organic compound containing carbon and covalently attached thereto hydrogen, a first metallic fuel and a metallic main fuel selected from silicon, magnesium, iron, aluminum or alloy containing these metals, oxygen or an oxygen-containing gas and optionally H2O and / or CO2 and / or NH3and optionally inert gases are introducted into a reaction chamber of a reactor. One or more of these feed stream(s) can optionally be diluted with inert gases, for example by nitrogen or argon or one or more separate feed stream(s) of inert gas can be used.

[0085] The single components forming the first and second reactive material are introduced into the reaction chamber. This can be performed by using single feed streams or by using feed streams of a combination of two or more of these components.

[0086] In a preferred embodiment of the process of this invention a mixture of an organic compound containing carbon and covalently attached thereto hydrogen combined with oxygen or an oxygen-containing gas or a mixture of an organic compound and first metal fuel selected from silicon, magnesium, iron, aluminum or alloy containing these metals is producted. This feed stream can optionally be diluted with inert gases, for example by nitrogen or argon. By choosing this mixture of reactants a pumpable or sprayable mixture of metal and oxygen or of metal and organic compound is provided that can be easily transported into the reaction chamber. Solid metals often create problems as these tend to agglomerate and to block feed lines.

[0087] In a preferred embodiment of the process of this invention oxygen, oxygencontaining gas, H2O and / or CO2 and / or NH3 and optionally inert gas is combined with the mixture comprising the first metal fuel and organic compound. This combination may take part in the reaction chamber by feeding separate streams of oxygen, oxygen-containing gas, H2O and / or CO2 and / or NH3and optionally inert gas and organic compound-first metal fuel mixture into the reaction chamber. In an alternative embodiment oxygen, oxygen-containing gas, H2O and / or CO2 and / or NH3and optionally inert gas and organic compound-first metal fuel mixture are introduced into a mixing device that is arranged upstream the reaction chamber. After mixing the oxidant-organic compound-metal combination the resulting mixture is fed into the reaction chamber.

[0088] The mixture of organic compound, first metal fuel and oxygen or oxygen-containing gas in the reaction chamber is reacted in a first flame to generate heat, electromagnetic radiation, oxidized metal, H2O and CO2. Depending on the amount of oxygen and first metal fuel present in the first flame hydrogen and carbon monoxide may also be formed.

[0089] In some embodiments the mixture of first metal fuel and oxygen or oxygencontaining gas in the reaction chamber is reacted in a first flame to generate heat, electromagnetic radiation and oxidized metal. Depending on the amount of oxygen and first metal fuel present in the first flame some of the oxygen may be transferred to the second flame.

[0090] The quantity of oxygen in the first flame is generally selected in a manner that at least a part of the total amount or all of the carbon and hydrogen present in the organic compound, if present, and at least a part or the total amount of the first metal fuel , if present, is oxidized. Larger amounts of oxygen are also possible. This surplus of oxygen is transferred to the second flame supporting the reactions in this second flame. The amount of oxygen should not exceed the amount necessary for complete oxidation of the metal present in the first and second flame. Thus, the amount of oxidant should be selected in a manner that all oxygen contained in the oxidant is finally bound in the metal oxide.

[0091] Between organic compound and metal on the one side and oxygen on the other side the following reactions play an important role: The organic compound is decomposed into hydrogen, carbon and optionally other pyrolysis products and these elements and pyrolysis products are oxidized by forming water and carbon oxides. Metal is oxidized by the oxygen, the water and the carbon oxides resulting in metal oxide, hydrogen and carbon monoxide. The overall process should be conducted in a manner that only minor portions of carbon dioxide is formed but that most of the carbon from the organic compound or from added CO2 is emitted as carbon monoxide.

[0092] In the process of this invention the first and second reactive materials are caused to react. This can be performed by igniting the first reactive mixture using an ignition device, such as an electric arc, a laser or a plasma generator. As an alternative hot reactor wall may be used to ignite the reactive mixtures or said mixtures when introduced into the reaction chamber have already a temperature to cause spontaneous combustion. In case there is already a reaction going on in the reaction chamber there is nothing to do. The reactive mixtures will be ignited by the heat generated in the reaction chamber.

[0093] In the process of this invention a product gas is generated. This contains besides gaseous components solids, for example metal oxide formed by reaction of the metal fuel with oxygen or other oxidants. Liquid components may also be present, for example traces of unreacted metal fuel. The term “product gas” as used in this description means a flowable mixture of gaseous and solid components. Different ignition devices can be used for igniting the first reactive material. Ignition devices are known to the skilled artisan.

[0094] Examples of ignition devices are electric arcs arranged in the inlet zone at the end of the feed line(s), inductive heaters or lasers arranged outside the reactor, the radiation of the laser being coupled into the reaction chamber through one or more windows in the reactor jacket or the inductive heater generating heat acting on the space region at the end of the feed line(s).

[0095] The first metal fuel and the main metal fuel used in the process of this invention is solid or liquid. Preferably, the metal fuel is a particulate metal, very preferred a metal powder. This powder may have a mean particle size in the range between 1 and 500 pm, but also particle sizes of smaller than 1 pm or greater than 500 pm are possible. The particle size can be determined by Laser diffraction.

[0096] The heat of reaction between organic compound and / or metal fuel on the one side and oxygen on the other side will allow a substantial micronization and vapourisation of the metal fuel to improve conversion to a satisfactory steady state flame process. Statistical thermodynamic consideration shows that such heat of reaction of the reaction between metal fuel and oxygen results in a flame with core temperatures of 2000 °C and above. In our experiments flame core temperatures above 2700 °C were obtained consistent with our thermodynamic considerations. This results in a self sustained flame zone.

[0097] In self-sustained flames comprising organic compound and oxygen flame core temperatures of 800 °C and above are obtained.

[0098] In a preferred embodiment of the process of this invention the first metal fuel consists of metal particles with diameters of less than 100 pm, more preferred of less than 50 pm. In another preferred embodiment of the process of this invention the main metal fuel consists of metal particles with diameters of up to 1 cm, preferably of less than 1 mm, and most preferred of less than 500 pm.

[0099] As an organic compound any organic chemical containing carbon, covalently bound hydrogen and optionally other elements can be used. Examples of organic compounds are alcohols, e.g. fatty alcohols, aldehydes, amines, amides, esters, carboxylic acids, e.g. fatty acids, ketones, aromatic compounds and preferably hydrocarbons. Organic compounds may be monomers, oligomers or polymers. Organic compounds may be saturated or unsaturated or aromatic. Organic compounds may contain - besides carbon and hydrogen atoms - oxygen, nitrogen, sulfur or phosphorous atoms. Mixtures of different hydrogen-containing organic compounds can be used.

[0100] Preferably, gaseous or liquid organic compounds, very preferred liquid or gaseous hydrocarbons are used.

[0101] Under a gaseous compound in this description is understood a compound that is gaseous at atmospheric pressure (101 .3 kPa) and at 25°C.

[0102] Under a liquid compound in this description is understood a compound that is liquid at atmospheric pressure (101.3 kPa) and at 25°C.

[0103] Hydrocarbons may be aliphatic, cycloaliphatic or aromatic. Aliphatic or cycloaliphatic hydrocarbons may be saturated or may possess one or more ethylenically unsaturated bonds.

[0104] Examples of gaseous hydrocarbons are methane, ethane, propane, butane, ethylene, propylene or acetylene. Mixtures of two or more of these hydrocarbons may be used. Examples of liquid hydrocarbons are pentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzene, toluene or xylene. Mixtures of two or more of these hydrocarbons may be used, such as gasoline, petroleum or diesel fuel.

[0105] As an oxidant oxygen, oxygen-containing gas, H2O and / or CO2can be used.

[0106] Preferably gaseous oxidants are used.

[0107] Oxygen-containing gases are mixtures of oxygen with other gases, preferably mixtures of oxygen with inert gases or are gases comprising chemically-bound oxygen, such as NOX.

[0108] Examples of oxidants are oxygen, air, mixtures of oxygen and inert gases, nitrogen oxides, water and carbon dioxide.

[0109] In a preferred embodiment of the process of this invention the hydrocarbon is liquid at 25°C and atmospheric pressure, preferably an aliphatic hydrocarbon being liquid at 25°C and at atmospheric pressure or the hydrocarbon is gaseous at 25°C and at atmospheric pressure, preferably an aliphatic hydrocarbon being gaseous at 25°C and at atmospheric pressure.

[0110] The amount of organic compound or of first metal fuel used in the process is chosen to result in combination with oxygen in a flammable mixture that generates a first flame resulting in heat and electromagnetic radiation in the reaction chamber to cause at least a portion of the first metal fuel and the main metal fuel to melt or to evaporate in order to initiate and support the formation of the second flame.

[0111] The amount of main metal fuel used in the process is chosen to result in the reduction of a significant amount, preferably of the total amount of CO2and H2O present in the second flame to CO and hydrogen. If NH3is present in the first or second flame this is decomposed by the thermal energy of these flames into hydrogen and nitrogen or nitrogen compounds, such as NOX.

[0112] If organic compound, oxygen, first metal fuel or metal main fuel and CO2 and / or H2O are present in a reactive material competing reactions between metal and CO2and / or H2O added to the reactive mixture and metal and CO2and / or H2O formed by combustion of the organic compound can occur. In these cases the amount of metal fuel must be increased compared to embodiments without CO2and / or H2O added to the reactive mixture.

[0113] In general the molar ratio between the hydrogen of organic compound and the metal fuel (atomic H / metal ratio) is 5 or below, preferably between 0.5 and 5 and more preferred between 1.0 and 2.0.

[0114] In general the molar ratio between the carbon of organic compound and the metal fuel (atomic C / metal ratio) is 3 or below, preferably between 0.1 and 3 and more preferred between 0.5 and 1.5.

[0115] If an organic compound and oxygen or oxygen-containing gas are present in a reactive mixture, for example in a mixture comprising hydrocarbon and oxygen or an oxygen-containing gas, preferably a molar ratio between the carbon and the oxygen (atomic C / O ratio) is 0.25 and 50, more preferred from 0.25 to 20 and most preferred from 0.25 to 5.

[0116] If an organic compound and oxygen or oxygen-containing gas are present in a reactive mixture, for example in a mixture comprising hydrocarbon and oxygen or an oxygen-containing gas, preferably a molar ratio between the hydrogen from the organic compound and the oxygen (atomic H / O ratio) is0.25 and 50, more preferred from 0.25 to 20 and most preferred from 0.25 to 5. In a preferred embodiment of the process of this invention the amount of organic compound in the mixtures i2), i3), i7) and i8) is chosen to produce a pumpable or sprayable mixture of organic compound and metal, preferably a slurry comprising liquid organic compound and particulate metal.

[0117] In still another preferred embodiment of the process the metal fuel is selected from magnesium, aluminium or an alloy containing aluminium and magnesium, preferably particulate aluminium is used.

[0118] In a preferred embodiment of the process of the invention the reaction chamber has a cylindrical shape forming an inlet zone for reactants, a central zone and an outlet zone for a product gas, and the components of the first reactive material and of the second reactive material as single components or as a mixture of two or more thereof are introduced into the inlet zone via feed lines that are arranged parallel, tangential or perpendicular to the cylinder axis.

[0119] In a preferred version of this embodiment the organic compound, the components of the first reactive material and of the second reactive material as single components or as a mixture comprising two or more of these components are introduced into the inlet zone of the reaction chamber via a plurality of pipes tangentially extending through the cylindrical reactor jacket, as a result of which a vortex is formed in the reaction chamber which moves in the direction towards the outlet zone.

[0120] A combination of parallel, tangential and / or perpendicular arranged feed lines may be used.

[0121] First metal fuel and metal main fuel can be used in the form of droplets, powder, granules, strips, wires, ingots, tinsels or strands, preferably through continuous or discontinuous reactor feeds, optionally using airlocks. Preferred are powders or tinsels of metals or metal alloys.

[0122] Preferably the first metal fuel is introduced into the reaction chamber in the form of droplets, powder, chips or pellets, very preferred in the form of droplets or powder. Preferably the metal main fuel is introduced into the reaction chamber in the form of droplets, powder, chips, pellets, ingots, tinsels or metal rods, very preferred in the form of powder, chips or pellets.

[0123] First metal fuel and metal main fuel can by prepared from the corresponding oxides by melt electrolysis, preferably by using electricity from regenerative sources, such as photovoltaics or wind energy. Metallic fuel can also be used as metal scrap, preferably as Aluminium scrap.

[0124] The oxidation of the metal main fuel in a flow-through reactor is particularly preferred to occur in a gas mixture with a predominant flow of H2O and / or CO2 which optionally contains NH3and / or inert gas.

[0125] If no organic compound containing carbon and covalently attached thereto hydrogen is present in the second flame the oxidation of the metal main fuel preferably occurs in the substantial absence of oxygen gas. In essence, this means that the controlled addition of small amounts of oxygen gas, while not optimal, is still possible in principle without affecting the reaction as described. However, better results are obtained in the absence of oxygen gas. Particularly preferably, therefore, the oxidation of metal main fuel in the absence of organic compound containing carbon and covalently attached thereto hydrogen is carried out in the absence of oxygen gas. Optionally inert gases can be present in the gas mixture in order to dilute the oxygen-containing gas.

[0126] If organic compound containing carbon and covalently attached thereto hydrogen is present in the second flame the oxidation of the metal main fuel preferably occurs in the presence of oxygen gas. Preferably therefore, the oxidation of metal main fuel in the presence of organic compound containing carbon and covalently attached thereto hydrogen is carried out in the presence of of oxygen gas in such an amount that part or all of the carbon and hydrogen present in the organic compound is oxidized to form H2O and CO2 and / or CO. Optionally inert gases can be present in the gas mixture in order to dilute the oxygen-containing gas.

[0127] The metals or metal alloys used as first metal fuel or metal main fuel in the process of this invention are available as a metallic raw material on an industrial scale and represent an alternative to other transportable energy sources. The metals or metal alloys are inert and non-hazardous to store and transport. This gives these metals or metal alloys a significant advantage as an energy source over crude oil, natural gas or coal, which are considered to be much more hazardous to the environment from their exploitation, their refinement, distribution and transport as well as their downstream use.

[0128] Formation of the first and second reactive materials can be carried out using separate feed streams. Thus, the various reactants can be introduced via separate feed lines into the reaction chamber. In an alternative embodiment some or all of the various reactants of the first or second reactive materials can be introduced as mixtures via one or more feed lines into the reaction chamber.

[0129] In a preferred embodiment of the process of this invention the reaction of the metal fuel in forming the first and second flame generates a reaction heat with a flame core temperature of 2200 °C and above. This temperature will guarantee an ignition of the metal fuel and formation as well as propagation of the flame(s).

[0130] In another preferred embodiment of the process of this invention the reaction of the organic compound in forming the first and second flame generates a reaction heat with a flame core temperature of 800 °C and above. This temperature will guarantee an ignition of the organic compound and formation as well as propagation of the flame(s).

[0131] In a preferred embodiment the reaction in the first flame and the second flame generates temperatures to cause the first metal fuel and at least a portion of the metal main fuel to evaporate. This can be achieved, for example, by controlling the throughput of organic compound, metal fuel and oxygen or by using a selected molar ratio of organic compound, metal fuel and oxygen in the reaction zone. Preferably temperatures of 2200°C or higher are generated, more preferred temperatures of 2700°C or higher. The temperatures in the reaction zone are measured by using a radiation thermometer.

[0132] In a preferred embodiment of the process of this invention a reactor is used having a reaction chamber with an inlet zone for reactants, a central zone and an outlet zone for a product gas, said process comprising at least the measures: a) providing metal main fuel in the inlet zone of the reaction chamber, b) introducing H2O and / or CO2and / or NH3and optionally inert gas into the inlet zone of the reaction chamber, c) introducing an organic compound containing carbon and covalently attached thereto hydrogen, first metal fuel and oxygen or oxygen-containing gas into said inlet zone using one or more feed lines ending in said inlet zone providing a mixture of said organic compound, first metal fuel and oxygen at the end of said feed line(s), d) generating a first flame by oxidizing the mixture of organic compound, first metal fuel and oxygen at the end of said feed line(s) which first flame is directed towards the metal main fuel present in the inlet zone, e) generating a reaction zone by the action of said first flame by melting and / or evaporating a portion of said metal main fuel thereby causing said metal main fuel to react with the H2O and / or the CO2or with the H2O, CO2and / or NH3to generate a second flame resulting in a product gas containing hydrogen, carbon monoxide and oxidized metal or hydrogen, carbon monoxide, nitrogen and oxidized metal and optionally inert gas(es), and f) discharging the product gas from the reactor.

[0133] In a preferred variant of this process this comprises after step e) at least the additional steps: e1 ) discharging the product gas from the reaction chamber exit zone via a discharge line and introducing the product gas into a separation device for solids and liquids, preferably a cyclone, e2) separating the solids and liquids from the product gas in the separation device, thereby producing a purified product gas having no or a reduced solids and liquids content, e3) discharging the purified product gas from the separation device, and e4) transferring thermal and radiant energy generated in the reaction chamber, in the product gas and / or in the purified product gas into a heat transfer medium and using this thermal energy for generation of electrical energy and / or for heating purposes.

[0134] In another preferred embodiment of the process of this invention hydrogen and carbon monoxide are generated from an organic compound containing carbon and covalently attached thereto hydrogen or from a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen and H2O and / or CO2and / or NH3and optionally inert gas in a reactor having at least one first reaction space with an inlet zone for reactants, a reaction zone for reacting a first reactive material and an outlet zone for an exhaust gas produced by the reaction and at least one second reaction space with an inlet zone for reactants, a reaction zone for reacting a second reactive material and an outlet zone for a product gas which first and second reaction spaces are separated from each other, wherein the first reactive material comprises an organic compound and oxygen or an oxygencontaining gas or an organic compound, oxygen or an oxygen-containing gas, a first metal fuel and H2O and / or CO2and / or NH3and optionally inert gas, the second reactive material comprises a main metal fuel and H2O and / or CO2and / or NH3and optionally inert gas, and wherein in the first reaction space thermal and radiant energy are generated and as reaction products H2O, CO and CO2or oxidized metal, H2O, CO and CO2or oxidized metal CO and hydrogen are formed, and in the second reaction space the H2O and CO2are reduced by the main metal fuel to result in CO, hydrogen and oxidized metal. In another preferred embodiment of the process of this invention hydrogen and carbon monoxide are generated from a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen, metal main fuel and optionally oxygen or an oxygen-containing gas in a reactor having at least one first reaction space with an inlet zone for reactants, a reaction zone for reacting a first reactive material and an outlet zone for an exhaust gas produced by the reaction and at least one second reaction space with an inlet zone for reactants, a reaction zone for reacting a second reactive material and an outlet zone for a product gas which first and second reaction spaces are separated from each other, wherein the first reactive material comprises a first metal fuel and oxygen or an oxygen-containing gas and the second reactive material comprises an organic compound containing carbon and covalently attached thereto hydrogen, metal main fuel and oxygen or an oxygen-containing gas, and wherein in the first reaction space thermal and radiant energy are generated and as reaction product oxidized metal is formed, and in the second reaction space H2O and CO are generated by reduction of H2O and CO2with the metal main fuel, said H2O and CO2are formed by combustion of the organic compound with oxygen.

[0135] In a preferred variant of this process the first reaction space and the second reaction space are separated from each other by a predetermined distance without a wall between the reaction spaces so that the thermal energy generated in the first reaction space can interact upon the reactants in the second reaction space or the first reaction space and the second reaction space are separated from each other by a wall so that the thermal and radiant energy generated in the first reaction space can interact via said wall upon the reactants in the second reaction space.

[0136] In still another preferred variant of this process the reduction of the H2O in the second reaction space is promoted by using electrical power to split the hot H2O into hydrogen and oxygen. In a further preferred variant of this process the reactor has at least one first reaction space with an inlet zone for reactants, a reaction zone for the oxidation reaction and an outlet zone for an exhaust gas produced by the oxidation reaction, and said reactor has at least one second reaction space with an inlet zone for reactants, a reaction zone for reacting the reactants and an outlet zone for a product gas, wherein the first reaction space and the second reaction space are separated from each other by a predetermined distance without a wall between the reaction spaces or wherein the first reaction space and the second reaction space are separated from each other by a wall, and wherein the first reaction space surrounds the second reaction space or wherein the second reaction space surrounds the first reaction space.

[0137] In these process variants the hydrogen-containing chemical introduced into the at least one second reaction space is preferably selected from the group consisting of H2O, NH3, hydrocarbons, alcohols, aldehydes, carboxylic acids or mixtures of two or more thereof, more preferred H2O, mixtures of CO2 and H2O, methane, ethane, ethylene, methanol, ethanol, formaldehyde, acetaldehyde, formic acid, acetic acid, fatty acids, fatty alcohols, aromatic compounds, methylcyclohexane or said compounds or mixtures diluted with inert gases.

[0138] The reaction products hydrogen and carbon monoxide can be used advantageously in many industrial processes. Hydrogen can be used in many reduction processes, for example to produce metals, such as iron, from metal oxides, or to carry out hydrogenations of organic compounds. Hydrogen can also be used as a fuel or as a source of thermal energy. Mixtures of carbon monoxide and hydrogen can be used in many industrial processes to produce energy-rich hydrocarbon compounds, such as for the production of fuels, such as kerosene. Increased use of the process of the invention would provide carbon monoxide and / or hydrogen fuel for industrial purposes. The combustion of hydrocarbons from the reaction products of carbon monoxide and hydrogen would in turn provide carbon dioxide, which can again be fed to the process according to the invention or when coming from this process is at least CO2-footprint neutral. The essential advantage of the process according to the invention thus consists in a universally, decentrally and rapidly applicable energy generation, without additional CO2pollution of the environment caused thereby, whereby the reaction products hydrogen and carbon monoxide can be fed to a material cycle.

[0139] In a preferred embodiment the thermal and radiant energy generated in the process of this invention is extracted and transferred into a heat transfer medium. This recovered thermal energy may be used for generation of electrical energy and / or for heating.

[0140] The thermal and radiant energy generated in the reaction space, contained in the product gas and / or in the purified product gas is transferred into a heat transfer medium. This is preferably achieved by means of one or more heat exchangers connected with the reactor jacket and / or one or more heat exchangers connected with the discharge line between the reaction space exit zone and the separation device and / or one or more heat exchangers connected with a line removing the purified product gas from the separation device and / or arranged downstream the reactor.

[0141] Heat transfer media used in the heat exchanger(s) are known to the skilled artisan. Examples of heat transfer media are water, glycols, glycerine, molten metals, molten salts or thermal oils, such as silicones or high-boiling hydrocarbons. Preferred heat transfer media are water, thermal oils or molten salts.

[0142] The thermal energy contained in the heat transfer media can be supplied to an exploiting consumer. Exploiting consumers can be almost all technical and chemical energy converters. In particular, low-pressure or high-pressure steam turbines for power generation, Stirling engines and other heat engines or direct power generators on temperature gradients, thermolysis reactors, in particular reactors for water thermolysis to hydrogen can be mentioned as exploiting consumers. The hydrogen or hydrogen / carbon monoxide generated in the process of this invention is stored or fed to a chemical conversion. The generated energy can be dissipated for energy conversion or heat or cold generation, e.g. for heating, by storing it or consuming it directly or indirectly. The thermal energy generated can, for example, be fed to a low-pressure or, preferably, a high-pressure steam turbine in order to generate electricity.

[0143] In a specific embodiment of the process and the reactor of this invention a portion of the heat generated in the process is backfeeded to the reactants introduced into the reactor. This includes backfeeding of partially reacted mixtures. These measures result in an increase of temperature of the feed streams.

[0144] Description of the Drawing

[0145] Figure 1 shows a reactor for carrying out the process of this invention.

[0146] The reactor illustrated in Figure 1 is a modified embodiment of a reactor disclosed in an article of Brilhac et al. Heat generation from swirl-stabilized aluminum-air flames. Fuel, Volume 381 , Part C, 2025.

[0147] The reactor of Figure 1 contains a reaction chamber (5) with an inlet zone (7) for reactants, a central zone (8) and an outlet zone (3) for product gas stream comprising solids and liquids. Inlet zone (7) contains feed lines (1 , 4, 15). Feed line (1 ) is a charging transport line for the first metal fuel, for example aluminium powder, and / or for organic compound and / or oxygen or oxygen-containing gases. Feed line (4) is a charging line for gaseous oxidant, for example air, oxygen, water vapour, carbon dioxide or ammonia optionally diluted with inert gas for the first flame (2). Feed line (15) is a charging line for metal main fuel and / or organic hydrogencontaining compound and / or other components for the second flame (9), for example air, oxygen, water vapour, carbon dioxide or ammonia optionally diluted with inert gas. Instead of one feed line (1 ), (4) and (15) the reactor can contain several feed lines (1), (4) and (15) which can charge different reactants or inert gases into the inlet zone (7).

[0148] Close to the ends of feed lines (1 , 4) an ignition device (6) is positioned. Ignition device (6) ignites the reactants transported through feed lines (1 , 4) resulting in a first flame (2).

[0149] This first flame (2) in turn ignites the reactants transported through feed line (15) resulting in the second flame (9) generated in inlet zone (7) and directed towards central zone (8).

[0150] The reactor is formed by a cylindrical reactor wall, for example a reactor jacket containing a window (17) for inspecting the reaction taking place in the interior of the reactor.

[0151] The reactor wall is equipped with one or more heat exchangers (14) having an inlet line (13a) and an exit line (13b) for heat carrier medium, e.g. water, steam or oil. .The reactor contains an outlet zone (3) for discharging the product gas from the reactor. Outlet zone (3) is connected with a separating unit for solids and liquids (12), for example with a cyclone. In unit (12) solids and liquids are removed from the product gas and a purified product gas is formed which exits the reactor via discharge line (11 ). Additional heat exchangers (not shown) may be installed for extraction of thermal energy from the gaseous, solid and liquid components of the product gas and / or from the purified product gas to a heat carrier medium. The reactor is also equipped with means (16) for temperature control and gas sensors for process analytics and control.

[0152] The following examples describe the invention without limiting it to the examples. Examples’ setup:

[0153] An experimental setup, based on the one described in Brilhac et al. Heat generation from swirl-stabilized aluminum-air flames. Fuel, Volume 381 , Part C, 2025, and modified as follows, was used for all examples.

[0154] The device is an axisymmetric burner.

[0155] The burner inlet zone is comprised of one primary axial injection line (which refers to (1 ) in Fig 1) and four secondary tangential injection lines (referring to (4) in Fig 1 ), resulting in a swirled flow exiting the burner head when all injection lines are used. The burner inlet zone leads to a cylindrical combustion chamber (0.6 m long and 0.105 m in diameter). It consists of a double-walled, water-cooled pipe with an optical access for flame observation (referring to (17) in Fig 1 ). Additionally, temperature and mass flow measurements at the inlet and outlet of the water circuit allows to determine the heat recovery rate.

[0156] At the start of the chamber (8 cm downstream of the transition from the burner head to the combustion chamber), and in addition to what was described in the article above, four tertiary injection lines (referring to (15) in Fig 1 ) are used. The tertiary injection lines form a 20° angle with the tangent of the outside chamber wall, in a coswirl configuration regarding the orientation of the secondary injection lines. When in use, the flow from the tertiary injection lines partially impinge on the flow exiting the burner head, while partially sustaining the swirled flow.

[0157] The chamber opens onto an outlet pipe with a free exhaust.

[0158] Gases can be injected from bottles through all injection lines. Gas injections are controlled using thermal mass flow controllers from Brooks Instrument. The flow controllers are set once at the start of the experiment, but pressure fluctuations in the chamber lead to fluctuations during experiment. Aluminum particles supplied by MonDroguiste, sieved to a 20-36 pm size range, can be injected through the primary injection line (referring to (1 ) in Fig 1 ) and though two of the four tertiary injection lines (referring to (15) in Fig 1 ) with the help of a dosed carrier gas, with aluminum mass flow rate measured with an electronic balance. The ignition system (referring to (6) in Fig 1 ) consists of an oxy-acetylene flame, which is only used on startup.

[0159] A tube with a diameter of 1 / 8" that is connected to a vacuum tank is employed to collect the gases exiting the combustion chamber for chromatographic analysis (GC). The GO is equipped with a dual column (MS-5A + Porapak Q).

[0160] Example 1

[0161] In this example, the first flame is a mixed aluminum-methane-air flame, achieved in two steps. First, a methane-air mixture was injected through the primary injection line (referring to (1 ) in Fig 1 ), and synthetic air was injected through the four secondary lines (referring to (4) in Fig 1 ). Flow rates were set to: CH4: 6.91 L / min, O2: 13.85 L / min, N2: 52.11 L / min, resulting in overall stoichiometric conditions: XCH4= 0.095, X02= 0.190, XN2= 0.715.

[0162] The mixture was ignited, resulting in a stable methane-air flame.

[0163] After stabilization (around 10 seconds), and aluminum-air mixture was mixed into the methane-air stream being injected through the primary line (1 ).

[0164] The added flow rates were O2: 3.08 L / min, N2: 11 .50 L / min, Al: 0.3 kg / h, which was also stoichiometric. Overall, inlet gas composition was: XCH4= 0.079, Xo2= 0.193, XN2= 0.728.

[0165] Aluminum particles were ignited upon entering the stable methane air-flame (as evidenced by a very bright white flame), resulting in the final aluminum-methane-air first flame. After the final first flame was stabilized (around 40 seconds), Al particles (2 kg / h) carried in N2gas (40 L / min) were injected using two of the four tertiary injection lines (referring to (15) in Fig 1 ), while a hot mixture of H2O vapor (667 g / h) and CO2gas (814 g / h) at 120 °C was injected using the two remaining tertiary lines (also referring to (15)).

[0166] The Al-N2and H2O - CO2streams impinged on the end of the first flame, quickly heating up. This leaded to the ignition of Al particles, which reacted with H2O and CO2gases both from the injected hot stream and from the products of the first flame. A larger, bright, white flame was observed.

[0167] After stabilization of the double-flame (around 60 seconds), a gas sample was retrieved from the exhaust gases. Analysis showed the following composition (only fractions over 0.01 are shown): XCo2=0.026, hard to realize XH2o=0.020, Xco=0.067, XH2=0.16, XN2=0.72.

[0168] Measured heat recovery in water stream was 7.1 kW.

[0169] Surprisingly, the combination of the two flames allows to use both the methane (injected in the first flame) and the H2O - CO2 mixture (injected in the second flame) to react with aluminum and produce a mixture containing significant amounts of CO and H2gases, as well as heat.

[0170] Example 2:

[0171] The same experiment as in Example 1 was done with C2H6injected instead of CH4for the first flame.

[0172] The aluminum-ethane-air mixture’s flow rates were: C2H6: 3.72 L / min, O2: 16.09

[0173] L / min, N2: 60.52 L / min, Al: 0.3 kg / h; resulting in the following gas composition:

[0174] C2H6= 0.046, Xo2= 0.200, XN2= 0.753. The Al-N2and H2O-CO2mixtures injected for the second flame remained unchanged.

[0175] Exhaust gas analysis showed the following composition: Xco2=0.028, hard to realize XH2O=0.019, XCO=0.071 , XH2=0.15, XN2=0.73.

[0176] Measured heat recovery in water stream was 6.8 kW.

[0177] Similar conclusions can be drawn as for the methane case.

[0178] Example 3

[0179] A methane-air mixture was injected through the primary injection line (referring to (1 )), and synthetic air was injected through the four secondary injection lines (referring to (4)).

[0180] Flow rates were set to: CH4: 6.93 L / min, O2: 13.85 L / min, N2: 52.11 L / min, resulting in overall stoichiometric conditions: XCH4= 0.095, Xo2= 0.190, XN2= 0.715.

[0181] The mixture was ignited, resulting in a stable methane-air flame.

[0182] After the first flame was stabilized (around 10 seconds), Al particles (1 kg / h) carried in N2gas (20 L / min) were injected using lines two of the tertiary injection lines (referring to (15) in Fig 1 ). The remaining two tertiary lines were not used.

[0183] Al particles, impinging on the end of the first flame, were ignited which resulted in a clearly differentiable second flame, showcasing the very bright combustion of aluminum particles.

[0184] After stabilization of the double-flame (around 60 seconds), a gas sample was retrieved from the exhaust gases. Analysis showed the following composition (only fractions over 0.01 are shown): XCO2=0.016, hard to realize XH2o=0.020, Xco=0.055, X 2=0.12, XN2=0.78.

[0185] Measured heat recovery in water stream was 4.2 kW.

[0186] The low (< 1%) amount of CH4and O2gases in the outlet shows almost complete combustion of methane in the first flame. Surprisingly, the evidence of significant H2 and CO gases in the exhaust proves that the first methane-air flame produces a hot mixture of H2O and CO2gases, with a sufficiently high temperature to enable the stabilization of the second flame, where Aluminum particles react with H2O and CO2 gases produced in the first flame to form H2 and CO.

[0187] Example 4

[0188] The same experiment as in Example 3 was done with C2H6injected instead of CH4for the first flame.

[0189] The ethane-air mixture’s flow rates were: C2H6: 4.06 L / min, O2: 14.20 L / min, N2: 53.42 L / min, resulting in overall stoichiometric conditions: C2He= 0.057, Xo2= 0.198, XN2= 0.745. The AI-N2 mixture injection for the second flame remains unchanged.

[0190] Exhaust gas analysis showed the following composition: Xco2=0.013, hard to realize XH2O=0.014, XCO=0.070, XH2=0.11 , XN2=0.79.

[0191] Measured heat recovery in water stream was 4.1 kW.

[0192] Similar conclusions can be drawn as from the methane case.

Claims

Patent Claims 224eg01 .wo1 . A process for generation of thermal and radiant energy, hydrogen and carbon monoxide by oxidizing a metal by using a reactor having a reaction chamber with an inlet zone for reactive materials, a central zone and an outlet zone for a product gas, said process comprising at least the steps: a) introducing a first reactive material into the inlet zone for generating a first flame said first reactive material being selected from the group consisting of11 ) a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen and oxygen or an oxygencontaining gas, or12) a mixture comprising a first metal fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals, an organic compound containing carbon and covalently attached thereto hydrogen and oxygen or an oxygen-containing gas, or13) a mixture comprising said first metal fuel, an organic compound containing carbon and covalently attached thereto hydrogen, oxygen or an oxygen-containing gas and H2O and / or CO2and / or NH3and optionally inert gas, or14) a mixture of said first metal fuel and oxygen or an oxygen-containing gas, b) introducing a second reactive material into the inlet zone for generating a second flame said second reactive material being selected from the group consisting of15) a metal main fuel selected from the group consisting of silicon, magnesium, iron, titanium, zinc, aluminum or alloy containing two or more of these metals, or16) a mixture comprising said metal main fuel and H2O and / or CO2and / or NH3and optionally inert gas, or17) a mixture comprising said metal main fuel, an organic compound containing carbon and covalently attached thereto hydrogen and oxygen and / or an oxygen-containing gas, or18) a mixture comprising said metal main fuel and an organic compound containing carbon and covalently attached thereto hydrogen, c) generating a first flame by reacting the first reactive material present in the inlet zone, d) generating and supporting a second flame by reacting the second reactive material present in the inlet zone using the first flame which is directed towards the second reactive material present in the inlet zone thereby forming a product gas containing hydrogen and carbon monoxide in the second, and e) discharging the product gas from the reactor, wherein in the inlet zone the following combinations of first and second reactive materials are provided:1 ) for generation of the first flame mixture i1 ) and for generation of the second flame metal main fuel i5), or2) for generation of the first flame mixture i1 ) and for generation of the second flame mixture i6), or3) for generation of the first flame mixture i2) and for generation of the second flame mixture i6), or4) for generation of the first flame mixture i2) and for generation of the second flame metal main fuel i5), or5) for generation of the first flame mixture i3) and for generation of the second flame mixture i6), or6) for generation of the first flame mixture i3) and for generation of the second flame metal main fuel i5), or7) for generation of the first flame mixture i4) and for generation of the second flame mixture i7), or8) for generation of the first flame mixture i4) and for generation of the second flame mixture i8).

2. The process according to claim 1 , wherein in the inlet zone the following combinations of first and second reactive materials are provided:1 ) for generation of the first flame mixture i1 ) and for generation of the second flame metal main fuel i5), or2) for generation of the first flame mixture i1 ) and for generation of the second flame mixture i6), or3) for generation of the first flame mixture i2) and for generation of the second flame mixture i6).

3. The process according to claim 1 or 2, wherein a reactor is used having a reaction chamber with an inlet zone for reactants, a central zone and an outlet zone for a product gas, said process comprising at least the measures: a) providing metal main fuel in the inlet zone of the reaction chamber, b) introducing H2O and / or CO2and / or NH3and optionally inert gas into the inlet zone of the reaction chamber, c) introducing an organic compound containing carbon and covalently attached thereto hydrogen, first metal fuel and oxygen or oxygen-containing gas into said inlet zone using one or more feed lines ending in said inlet zone providing a mixture of said organic compound, first metal fuel and oxygen at the end of said feed line(s), d) generating a first flame by oxidizing the mixture of organic compound, first metal fuel and oxygen at the end of said feed line(s) which first flame is directed towards the metal main fuel present in the inlet zone, e) generating a reaction zone by the action of said first flame by melting and / or evaporating a portion of said metal main fuel thereby causing said metal main fuel to react with the H2O and the CO2or with the H2O, CO2and / or NH3to generate a second flame resulting in a product gas containing hydrogen, carbon monoxide and oxidized metal or hydrogen, carbon monoxide, nitrogen and oxidized metal and optionally inert gas(es), and f) discharging the product gas from the reactor.

4. The process according to claim 3, wherein this comprises after step e) at least the additional steps: e1 ) discharging the product gas from the reaction chamber exit zone via a discharge line and introducing the product gas into a separation device for solids and liquids, preferably a cyclone, e2) separating the solids and liquids from the product gas in the separation device, thereby producing a purified product gas having no or a reduced solids and liquids content, e3) discharging the purified product gas from the separation device, and e4) transferring thermal and radiant energy generated in the reaction chamber, in the product gas and / or in the purified product gas into a heat transfer medium and using this thermal energy for generation of electrical energy and / or for heating purposes.

5. The process according to any of claims 1 to 4, wherein the components forming the first reactive material or forming the second reactive material are introduced into the inlet zone as separate feed streams or two or more of the components forming the first reactive material or the second reactive material are combined upstream to the inlet zone of the reaction chamber and this mixture is transferred into the inlet zone of the reaction chamber.

6. The process according to at least one of claims 1 to 5, wherein the organic compound is a hydrocarbon or a mixture of hydrocarbons that is liquid at 25°C and atmospheric pressure, preferably an aliphatic hydrocarbon or a mixture of aliphatic hydrocarbons being liquid at 25°C and at atmospheric pressure, or in that the organic compound is a hydrocarbon or a mixture of hydrocarbons that is gaseous at 25°C and at atmospheric pressure, preferably an aliphatic hydrocarbon or a mixture of aliphatic hydrocarbons being gaseous at 25°C and at atmospheric pressure.

7. The process according to at least one of claims 1 to 6, wherein the molar ratio between the carbon of the organic compound containing carbon and covalentlyattached thereto hydrogen and the first metal fuel or the main metal fuel is between 0.1 and 3, preferably between 0.5 and 1.

58. The process according to at least one of claims 1 to 7, wherein the molar ratio between the hydrogen of the organic compound containing carbon and covalently attached thereto hydrogen and the first metal fuel or the main metal fuel is between 0.5 and 5, preferably between 1.0 and 2.0.

9. The process according to at least one of claims 1 to 8, wherein the first metal fuel and the metal main fuel is selected from the group consisting of magnesium, aluminium or an alloy containing aluminium and magnesium, preferably aluminium.

10. The process according to at least one of claims 1 to 9, wherein the reaction chamber has a cylindrical shape forming an inlet zone for feed streams for the first reactive material and / or for the second reactive material, a central zone and an outlet zone for a product gas, and wherein the feed streams are introduced into the inlet zone via feed lines that are arranged parallel or perpendicular to the cylinder axis.11.The process according to at least one of claims 1 to 10, wherein the feed streams for the first reactive material and / or for the second reactive material are introduced into the inlet zone of the reaction chamber via a plurality of pipes tangentially extending through the cylindrical reactor jacket, as a result of which a vortex is formed in the reaction chamber which moves in the direction towards the outlet zone.

12. The process according to at lest one of claims 1 to 11 , whereinthe metal main fuel is introduced into the reaction chamber in the form of droplets, powder, chips, pellets, ingots, tinsels or metal rods.

13. The process according to at least one of claims 1 to 12, wherein the first metal fuel is introduced into the reaction chamber in the form of droplets or powder andwherein the metal main fuel is introduced into the reaction chamber in the form of powder, chips or pellets.

14. The process according to claims 12 or 13, wherein the powder consists of metal particles with mean diameter of less than 100 pm.

15. The process according to at least one of claims 1 to 14, wherein hydrogen and carbon monoxide are generated from an organic compound containing carbon and covalently attached thereto hydrogen or from a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen and H2O and / or CO2and / or NH3and optionally inert gas in a reactor having at least one first reaction space with an inlet zone for reactants, a reaction zone for reacting a first reactive material and an outlet zone for an exhaust gas produced by the reaction and at least one second reaction space with an inlet zone for reactants, a reaction zone for reacting a second reactive material and an outlet zone for a product gas which first and second reaction spaces are separated from each other, wherein the first reactive material comprises an organic compound and oxygen or an oxygen-containing gas or an organic compound, oxygen or an oxygen-containing gas, a first metal fuel and H2O and / or CO2and / or NH3and optionally inert gas, the second reactive material comprises a main metal fuel and H2O and / or CO2and / or NH3and optionally inert gas, and wherein in the first reaction space thermal and radiant energy are generated and as reaction products H2O, CO and CO2or oxidized metal, H2O, CO and CO2or oxidized metal CO and hydrogen are formed, and in the second reaction space the H2O and CO2are reduced by the main metal fuel to result in CO, hydrogen and oxidized metal.

16. The process according to at least one of claims 1 to 14, wherein hydrogen and carbon monoxide are generated from a mixture comprising an organic compound containing carbon and covalently attached thereto hydrogen, metal main fuel and optionally oxygen or an oxygen-containing gas in a reactor havingat least one first reaction space with an inlet zone for reactants, a reaction zone for reacting a first reactive material and an outlet zone for an exhaust gas produced by the reaction and at least one second reaction space with an inlet zone for reactants, a reaction zone for reacting a second reactive material and an outlet zone for a product gas which first and second reaction spaces are separated from each other, wherein the first reactive material comprises a first metal fuel and oxygen or an oxygen-containing gas and the second reactive material comprises an organic compound containing carbon and covalently attached thereto hydrogen, metal main fuel and oxygen or an oxygen-containing gas, and wherein in the first reaction space thermal and radiant energy are generated and as reaction product oxidized metal is formed, and in the second reaction space H2O and CO are generated by reduction of H2O and CO2with the metal main fuel, said H2O and CO2are formed by combustion of the organic compound with oxygen.

17. The process according to claim 15 or 16, wherein the first reaction space and the second reaction space are separated from each other by a predetermined distance without a wall between the reaction spaces so that the thermal and radiant energy generated in the first reaction space can interact upon the reactants in the second reaction space or the first reaction space and the second reaction space are separated from each other by a wall so that the thermal and radiant energy generated in the first reaction space can interact via said wall upon the reactants in the second reaction space.

18. The process according to at least one of claims 15 to 1718, wherein the reduction of the H2O in the second reaction space is promoted by using electrical power to split the hot H2O into hydrogen and oxygen.

19. The process according to at least one of claims 15 to 18, wherein the first reaction space and the second reaction space are separated from each other by a predetermined distance without a wall between the reaction spaces or whereinthe first reaction space and the second reaction space are separated from each other by a wall, and wherein the first reaction space surrounds the second reaction space or wherein the second reaction space surrounds the first reaction space.

20. The process according to at least one of claims 1 to 19, wherein the organic compound containing carbon and covalently attached thereto hydrogen is selected from the group consisting of hydrocarbons, alcohols, carboxylic acids or mixtures of two or more thereof, more preferred methane, ethane, ethylene, methanol, ethanol, formaldehyde, acetaldehyde, formic acid, acetic acid, fatty acids, fatty alcohols, aromatic compounds, methylcyclohexane or mixtures of two or more thereof.

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