EP4146845A1 - Procédé pour générer de l'énergie thermique et des produits chimiques de base par réaction aluminothermique - Google Patents

Procédé pour générer de l'énergie thermique et des produits chimiques de base par réaction aluminothermique

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Publication number
EP4146845A1
EP4146845A1 EP21727080.0A EP21727080A EP4146845A1 EP 4146845 A1 EP4146845 A1 EP 4146845A1 EP 21727080 A EP21727080 A EP 21727080A EP 4146845 A1 EP4146845 A1 EP 4146845A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
carbon dioxide
aluminum
reaction
water vapor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21727080.0A
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German (de)
English (en)
Inventor
Carsten Dentler
Norbert Windhab
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Energy 13 GmbH
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP4146845A1 publication Critical patent/EP4146845A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a method for the combined generation of thermal energy and basic chemicals by aluminothermic reduction of carbon dioxide and / or water vapor and optionally by additional reaction with compounds containing nitrogen and hydrogen, such as ammonia.
  • nitrogen and hydrogen such as ammonia.
  • the invention aims at the congruence of energy and material carrier in order to cushion the often sunlight, wind and tide-dependent cyclicity and variability of both electricity generation based on renewable energies or resources and electricity storage.
  • hydrogen and C0 2 are to be supplied to material, electrical and tractor use through use in the synthesis gas line.
  • Metal production is often integrated with different methods of the energy industry. Material as well as physical systems based on renewable energies must also cope with regional biomass production in the future and thus the nutrition of an increasing world population by intensifying existing agricultural areas or by increasing the Improve productivity in food production while producing biomass.
  • the material chemical strands of world food production today are predominantly of a de facto fossil nature.
  • the underlying carbon sources can be switched almost at will from a technical point of view, the biological production is based on sugar, lipids or protein and is therefore dependent on the net energetic inflow, e.g. by using the Haber-Bosch process to generate nitrogen sources for biological production.
  • Aluminum should be mentioned as a metal that is stable in storage, in terms of process technology and in the recycling cycle for molar but also weight-specific energy storage. In fact, aluminum is produced exclusively through smelting electrolysis. It is important that the industrial aluminum electrolysis with "optimal" operation becomes an emitter of greenhouse gases even through the conscious sacrifice of the carbon electrode through the production of CO and CO2. New processes such as the Elysis TM process report an additional paradigm shift that is important for the global use of the process.
  • Aluminum is used as a technical metal because of its low weight, its safe handling and especially its storage stability and because of the frequency of its occurrence in the earth's crust. Due to the extreme lattice energy, aluminum oxide is suitable as an outstanding transportable energy carrier. Heavier metals such as Ga, As, Sn or Zn, or their oxides, are far less easy to transport and, in certain units, are environmentally and in industrial use questionable or even volatile, are less common or cause economic creep damage because they rust like iron.
  • thermite process in which iron oxide is reduced and aluminum is oxidized, has been used as a welding process for over a hundred years. It is also known that burning aluminum cannot be extinguished with water, since hydrogen gas is formed when the water comes into contact with the aluminum. The use of aluminum to generate hydrogen is also described. However, the metal must be activated beforehand because it is normally protected by an oxide layer. Such a method is disclosed, for example, in WO 2010/076802 A9.
  • WO 2014/173991 A1 a method for generating thermal energy and carbon monoxide by aluminothermic reduction of carbon dioxide is known from WO 2014/173991 A1. This process is based on the knowledge that aluminum is particularly suitable as an energy carrier and can also be used to convert CO2 into CO.
  • ammonia has been suggested as a hydrogen supplier.
  • An overview of the current state of the art is given in an article entitled “Science and Technology of Ammonia Combustion” by Hideaki Kobayashi et al. in Proceedings of the Combustion Institute, 37 (2019), 109-133.
  • ammonia or other compounds containing nitrogen and hydrogen it is to be regarded as a disadvantage that undesired nitrogen oxides during the reaction arise and therefore complex multi-stage processes have to be developed even for internal combustion systems.
  • the present invention is based on the object of enabling the operation of a melt-flow electrolysis system for aluminum production with regenerative energies and at the same time generating basic chemicals without the inherent loss of dark reaction (night) and melt cooling (aluminum melt-flow electrolysis).
  • the yields of the potential disintegration paths of the carbon dioxide from the melt and a technical applicability were unknown to the person skilled in the art.
  • a further object of the present invention is to combine the operation of a melt flow electrolysis system for aluminum production with a highly effective C0 2 absorption in order to bind naturally occurring or anthropogenically produced C0 2.
  • a further object of the present invention is to combine the operation of a melt flow electrolysis system for the production of aluminum with the production of basic chemicals for the production of hydrocarbons.
  • a process for the generation of thermal energy and basic chemicals comprising at least the following measures: a) Generation of aluminum metal by fused-salt electrolysis in a fused-salt electrolysis system, preferably through the use of electricity obtained from renewable energy sources, such as photovoltaics, solar thermal, wind or tides, b) Use of aluminum metal, preferably part of the aluminum metal produced, to generate thermal energy Energy and chemical raw materials selected from the group consisting of carbon monoxide or hydrogen, by bringing carbon dioxide and / or water or a mixture containing a compound containing nitrogen and hydrogen and carbon dioxide and / or water into contact with the aluminum metal and in an aluminothermic reaction to form aluminum oxide and Carbon monoxide and / or hydrogen is converted, c) storage or chemical conversion of the carbon monoxide and / or hydrogen produced in the process, d) storage of the thermal energy produced in this process or conversion into other E forms of energy, and e) recycling of the aluminum oxide obtained in the process to the fused-salt electrolysis.
  • Vlaskin et al. describe in J. Power Sources, Vol 196, 20, 2011, p 8828-8835 a power generation plant operated with aluminum powder and with water as the oxidizing agent. Vlaskin et al. build their pilot plant strictly on the aluminum powder-water to hydrogen-fuel cell strategy. Use of the plant for the combined generation of energy and basic chemical chemicals is not disclosed.
  • the reaction is carried out in a bubble reactor.
  • the throughput limit is largely limited by the gas bubble rupture as the appearance of the educt phase at the reactor outlet, which can be set through geometries, parallelization, especially miniaturizing parallelization (piping, branching) on the reactor design and the critical kinetic parameters such as pressure and temperature.
  • the bubble reactor is heated and the aluminum is melted using a furnace.
  • flow-through reaction yields and selectivities can be regulated and depend on the timing and the local conditions.
  • Particularly elegant is the great variety in which the gas / metal reactants can be brought to react in a targeted manner in small and parallel reactor sections.
  • Step c) can then be fed back to the aluminum extraction conventionally as pure aluminum oxide after the aluminum oxide formed has been recycled, so the melt phase process is a special case particularly favored at the aluminum smelting site.
  • an industrially appropriately invested region can become a semi-self-sufficient participant in the economic cycle with high energy production and become a polypolistic production and storage location for carbon monoxide or hydrogen and the synthetic chemicals obtained or generated therefrom, such as synthetic fuels .
  • the method according to the invention combines the previous dilemma separation of chaotic-meteorological and “planetary” energy pulsation of the electricity resource and carbon utilization with the help of large-scale invested industries in terms of process technology and capacity logistical by optimizing the caloric losses.
  • typical components of a plant for carrying out the method according to the invention are therefore classic technical electrolytic gas smelting, turbines for generating electricity, for example high-pressure water steam turbines, but essentially a thermally coupled reactor volume for treating aluminum, preferably liquid aluminum directly electrolysis, with C0 2 and / or water vapor or other substantial water sources or with a mixture containing a compound containing nitrogen and hydrogen and carbon dioxide and / or water.
  • These reactions are then exothermic, drive the material production of the refined reaction gases through the energy capacity of the aluminum mass and, as "pump storage", fill the nightly energy requirements of the aluminum electrolysis, for example, which continues to be fired.
  • Detours with large material and energy losses in this, for example, local optimization via, for example, intermediate generation of hydrogen or hydrogen derivatives, are not necessary.
  • Aluminum scrap can also be used for a highly efficient regionalization of the process, e.g. in aluminum technology large-scale industrial centers and "urban mining” recycling centers, which themselves often generate electricity with incineration plants.
  • Aluminum is inert and is available in large quantities. Aluminum is used, for example, in the aerospace and automotive industries. As is typical for metals, aluminum waste, in contrast to plastics, textiles, plastics, microplastics and other non-environmentally absorbable, non-biogenic organic-chemical compounds, is particularly easy to recycle.
  • Aluminum scrap can be used in the form of aluminum powder, aluminum granules, aluminum strips, aluminum wire, aluminum bars or aluminum hollow bodies, preferably through continuous or discontinuous reactor feeds, optionally using locks.
  • the process according to the invention is characterized by great robustness with respect to the purity of the gas used.
  • other processes, especially those that use hydrogen, such as for fuel production or electricity generation in fuel cells are particularly dependent on the gas purity.
  • the method according to the invention can be used to generate heat through an aluminothermic reaction, the targeted reduction of C0 2 and / or water and thus the generation of basic Effect chemicals into making a wide variety of chemicals.
  • the basic chemicals obtained can be used in other geographical regions than the original energy generation and, due to their availability, establish local business models up to the international production of valuable products and can be used for the production of raw materials to secure local nutrition.
  • the generated thermal energy can preferably be fed to a useful consumer.
  • Practical consumers can be almost all technical and chemical energy converters.
  • Particularly useful consumers are low-pressure or high-pressure steam turbines for power generation, Stirling engines and other heat engines or direct power generators at temperature gradients, thermolysis reactors, in particular reactors for water thermolysis to hydrogen.
  • the resulting carbon monoxide / hydrogen is stored or used for chemical conversion.
  • the generated energy can be dissipated for energy conversion or heat or cold generation, e.g. for heating heat generation, by storing it or consuming it directly or indirectly.
  • the generated thermal energy can e.g. be fed to a low-pressure or preferably a high-pressure steam turbine in order to generate demand-timed electricity.
  • the aluminum is oxidized in a closed or flow-through apparatus particularly preferably by contact with a process clean gas mixture with a predominant flow of carbon dioxide and / or water vapor or by contact with the flow of a mixture containing a compound containing nitrogen and hydrogen and carbon dioxide and / or water.
  • the aluminum is preferably oxidized essentially in the absence of oxygen gas. Essentially this means that the controlled addition of small amounts of oxygen gas is not optimal, but is in principle still possible without it to impair the reaction described as such. However, better results are obtained in the absence of oxygen gas. It is therefore particularly preferable for the aluminum to be oxidized in the absence of oxygen gas.
  • the raw material aluminum is available as a metallic raw material on an industrial scale and represents an alternative to other energy sources.
  • Aluminum is inert and safe to store and transport. As an energy source, aluminum therefore has a significant advantage over crude oil, natural gas or coal, which are to be regarded as significantly more environmentally hazardous.
  • the raw material carbon dioxide can be obtained from atmospheric gas, come from combustion processes of all kinds or from other sources and thus be removed from the atmosphere.
  • the claimed method thus has the advantage that the associated energy generation does not produce carbon dioxide, but is actually consumed.
  • the resulting aluminum oxide is internal and does not pollute the environment.
  • compounds containing nitrogen and hydrogen are to be understood as meaning inorganic or organic compounds containing N and H.
  • these can also contain other elements, for example carbon, oxygen or sulfur.
  • Examples of compounds containing nitrogen and hydrogen are ammonia, urea, hydrazine, amines, imines or amides.
  • Compounds containing nitrogen and hydrogen can be present as polymers, for example as polyamides, polyimides or polyurethanes. They are preferably low molecular weight compounds. Ammonia and urea are preferably used, in particular ammonia.
  • the range of products of value obtained by the process according to the invention is highly congruent. Slagging and polymerisation or oiling are suppressed. Costly catalyst poisoning does not occur.
  • the variant of the method according to the invention in which, in addition to carbon dioxide and / or water, nitrogen and hydrogen-containing compounds are also used, has the advantage that only nitrogen and hydrogen and optionally carbon monoxide are formed during the reaction of the nitrogen and hydrogen-containing compound. The formation of nitrogen oxides is not observed.
  • the resulting reaction product, carbon monoxide and / or hydrogen is a dangerous gas.
  • This is diluted by the nitrogen that is produced at the same time.
  • the extraction, handling and storage of dangerous gases have been possible for a long time and in particular according to the process technologies used today in the chemical industry, while adhering to appropriate safety standards.
  • the risk potential of carbon monoxide and hydrogen is thus at the level of other chemical hazardous substances, which is at least currently, unlike the risks associated with nuclear energy, scientifically, socially and politically widely accepted.
  • the reaction products carbon monoxide and hydrogen can be used advantageously in many industrial processes. These reaction products can be used directly in many industrial processes for the production of high-energy hydrocarbon compounds, for example for the production of fuels such as kerosene.
  • the increased use of the method according to the invention would provide carbon monoxide and / or hydrogen for industrial purposes.
  • the combustion of hydrocarbons from the reaction products of carbon monoxide and hydrogen would in turn provide carbon dioxide, which can be fed back into the process according to the invention.
  • the main advantage of the invention The process therefore consists in a universal, decentralized and quickly applicable energy generation, without the additional CC> 2 pollution of the environment caused thereby, whereby the reaction product carbon monoxide can be fed into a material cycle and is connected to the economic cycle medium aluminum / carbon dioxide in a controlled manner.
  • An interesting component of the method according to the invention is the storage capacity, which increases with the size of the network. This reduces the need for overcapacity by avoiding the buffer and storage measures required to technically compensate for generation peaks, which result in high costs and high capital commitment. At the same time, oversupply losses can be avoided by using metallically stored energy to produce basic chemicals, which in turn can be used to produce basic goods such as fuels, biomass or food.
  • the process is net C0 2 -negative and thus adds value at the source.
  • the process can be carried out in small units by using the metal cycle medium and is therefore also suitable, for example, for “urban mining” approaches.
  • the method can provide additional energy storage capacity on a global scale without the need for unknown risks, the need to set up and expand an expensive and technically demanding accident insurance or capital-intensive and geopolitically sensitive gas storage logistics.
  • the technically and logistically well-known strand of synthetic fuels can be sustainably preserved for air traffic and traction in many areas and regions.
  • biomass utilization for sustainable protein and food chain materials will be intensified and the agricultural hub will be relieved.
  • the process can be carried out with a minimum of gas cleaning effort. Energy costs for compression and water preheating can also be minimized in large-scale applications.
  • step a) of the method according to the invention aluminum metal is produced by fusible flow electrolysis in a molten flow electrolysis system.
  • the method of step a) has been known for a long time.
  • the aluminum smelters work according to the Hall-Heroult process.
  • the reduction of aluminum oxide to pure aluminum takes place by means of fused-salt electrolysis.
  • Aluminum oxide which has a melting temperature of 2045 ° C, is mixed with cryolite in order to lower the melting temperature to approx. 950 ° C.
  • the aluminum produced by electrolysis has a melting point of 650 ° C.
  • step b) of the process according to the invention aluminum metal is used to generate thermal energy and carbon monoxide or hydrogen.
  • These basic chemical substances are obtained by oxidizing aluminum by bringing carbon dioxide and / or water or a mixture of nitrogen and hydrogen-containing compounds and carbon dioxide and / or water into contact with the aluminum metal and converting them to aluminum oxide and carbon monoxide or hydrogen in an aluminothermic reaction will.
  • Step b) can be carried out directly in the melt flow electrolysis system by bringing the liquid aluminum metal at the bottom of the system into contact with carbon dioxide or water vapor or a gaseous mixture of nitrogen and hydrogen-containing compound and water vapor and / or carbon dioxide.
  • carbon monoxide or hydrogen thermal energy is generated, which heats the reaction products and the electrolysis cell.
  • the heating of the electrolyte by the reaction heat leads to a saving of electrical energy in the electrolysis, since less electricity has to be used to heat the electrolyte.
  • the heat of reaction can be used to keep the electrolyte and the metal liquid in the event of a power failure or if the electrical power available for the electrolysis is reduced, so that the system does not have to be switched off.
  • part of the heat of reaction can also be used to generate electricity, for example by passing the gaseous reaction products through one or more turbine (s) and then processing them further.
  • the electricity generated can be made available to any consumers or can be used to continue operating the electrolysis in the event of a power failure or if the electrical power available for the electrolysis is reduced from external sources, so that the system does not have to be switched off.
  • step b) can be carried out in a separate reactor which is located in the vicinity of the melt flow electrolysis system.
  • aluminum metal which is solid or preferably liquid, is brought into contact with carbon dioxide and / or water vapor or with a gaseous mixture of nitrogen and hydrogen-containing compound and carbon dioxide and / or water vapor.
  • solid aluminum it usually has to be made to react by supplying ignition energy, as described, for example, in WO 2014/173991 A1.
  • Solid aluminum is usually in finely divided form in order to be able to carry out the desired reaction. With the preferred use of liquid aluminum, a separate ignition can be omitted, since the reaction starts as soon as the reactants come into contact.
  • step b) preference is given to using liquid aluminum metal which originates from the melt-flow electrolysis system in which step a) was carried out.
  • step b) the heat of reaction can be used to keep the electrolyte and the metal in the fused-melt electrolysis system liquid in the event of a power failure or when the electrical power available for the electrolysis is reduced, so that the system is not switched off must become.
  • part of the heat of reaction can be used to generate electricity, for example by passing the gaseous reaction products through one or more turbine (s) and then processing them further.
  • the generated electrical power can also be made available to any consumer or can be used to continue operating the electrolysis in the event of a power failure or if the electrical power available for electrolysis is reduced from external sources, so that the system does not have to be switched off .
  • carbon dioxide or water vapor can be used as the oxidizing agent for the aluminum.
  • a mixture of carbon dioxide and water vapor can also be used, or carbon dioxide and water vapor are reacted with the aluminum separately but in a reactor.
  • step b) the carbon dioxide and / or water used in a mixture with nitrogen and hydrogen-containing compound can be used as the oxidizing agent for the aluminum.
  • carbon dioxide and / or water vapor can be used as oxygen-containing compounds together with the nitrogen and hydrogen-containing compound, or the different reactants are reacted with the aluminum separately but in a reactor.
  • step c) of the method according to the invention the carbon monoxide generated in step b) and / or the hydrogen generated in step b) is stored or chemically converted. If storage is provided, the thermal energy contained in the reaction products carbon monoxide or hydrogen is fed to a utilization, for example the generation of water vapor through heat exchange. Storage is advisable if there are no suitable reaction partners or facilities for further processing of the basic chemical substances available on site.
  • the carbon monoxide generated in step b) and / or the hydrogen generated in step b) is preferably chemically converted on site.
  • a large number of chemical reactions are available in which these raw materials can be refined.
  • hydrogen can be used to hydrogenate organic compounds or in reduction reactions, for example in ammonia synthesis.
  • Carbon monoxide can be converted into methanol with water, for example.
  • step b) The combined production of carbon monoxide and hydrogen in step b) and the direct further processing of both basic materials in a Fischer-Tropsch reactor is therefore preferred.
  • the thermal energy contained in the reactants from step b) can advantageously be used.
  • the thermal energy generated in the aluminothermic reaction in step b) can be stored in step d) or converted into other forms of energy, for example into electrical energy. Variants of step d) have already been described above. Alternatively, the generated thermal energy can be used for heating or cooling purposes.
  • step e The aluminum oxide obtained by the aluminothermic reaction is returned to the fused-salt electrolysis (step e). It is advisable to introduce the aluminum oxide into the melt flow electrolysis system in which step a) has already been carried out. However, it is also possible to introduce the aluminum oxide produced in step e) into a melt-flow electrolysis system other than that in which step a) was carried out.
  • step b) was carried out in the melt flow electrolysis system of step a), the aluminum oxide is produced directly in the system, so that it is automatically returned.
  • a method is preferred in which at least part of the thermal energy released by the aluminothermic reaction in step b) is used to generate electrical energy.
  • step b) Heating the electrolyte and / or the aluminum is used in the melt flow electrolysis system.
  • melt flow electrolysis system is operated using temporarily fluctuating or temporarily absent electrical energy from an external source, and in which at least part of the thermal energy released by the aluminothermic reaction in step b) is used to to keep the electrolyte and / or the aluminum in the melt flow electrolysis system liquid.
  • melt flow electrolysis system is operated using temporarily fluctuating or temporarily absent electrical energy from an external source, and in which at least part of the electrical energy generated is used to reduce the fluctuation or the lack of electrical energy to reduce or compensate for electrical energy supplied to external sources.
  • a method is very particularly preferred in which both carbon monoxide and hydrogen are generated in step b), which are then chemically reacted with one another in a Fischer-Tropsch reaction.
  • step b) is carried out by bringing carbon dioxide and / or water vapor into contact with liquid aluminum metal.
  • step b) is carried out by bringing a mixture of nitrogen and hydrogen-containing compound and carbon dioxide and / or water into contact with liquid aluminum metal.
  • the method according to the invention in which carbon monoxide is generated, is coupled with a hydrogen generation method.
  • a hydrogen generation method can be any process, for example water electrolysis or an aluminothermic reaction of aluminum metal with water vapor. Again shows the relative low specific and molar Enthalpy the clear driving force of the described aluminothermic water reduction for hydrogen production.
  • the invention also relates to a method for generating thermal energy and carbon monoxide by the aluminothermic reaction of carbon dioxide, in which aluminum metal and carbon dioxide are reacted and converted to aluminum oxide and carbon monoxide, the method being characterized in that gaseous carbon dioxide and liquid aluminum metal with each other are brought into contact until a gaseous reaction product containing carbon monoxide, preferably with a carbon monoxide content of at least 30 percent by volume, is formed.
  • the invention also relates to a method for generating thermal energy and hydrogen by the aluminothermic reaction of water vapor, in which aluminum metal and water vapor are reacted and converted to aluminum oxide and hydrogen, the method being characterized in that water vapor and liquid aluminum metal with one another are brought into contact for a long time until a gaseous and hydrogen-containing reaction product, preferably with a hydrogen content of at least 30 percent by volume, has formed.
  • the invention also relates to a method for generating thermal energy and hydrogen by aluminothermic reaction of a mixture of nitrogen and hydrogen-containing compound with water vapor and / or carbon dioxide, in which aluminum metal and the compounds contained in the mixture are reacted and to form aluminum oxide, nitrogen and Hydrogen are reacted, the method being characterized in that the compounds contained in the mixture and liquid aluminum metal are brought into contact with each other until a gaseous and hydrogen-containing reaction product, preferably with a hydrogen content of at least 30 percent by volume, is formed.
  • the invention relates to the use of liquid aluminum metal for generating thermal energy and carbon monoxide and / or hydrogen by aluminothermic reaction of carbon dioxide and / or water or a mixture containing nitrogen and hydrogen-containing compound and carbon dioxide and / or water.
  • Very preferred is a process in which liquid aluminum is brought into contact with metered gaseous carbon dioxide or water vapor or a gaseous mixture containing nitrogen and hydrogen-containing compound and carbon dioxide and / or water vapor at a temperature> 660 ° C. in order to convert an educt mixture with a CO Content or with an H 2 content of more than 30% by volume, preferably more than 50% by volume and particularly preferred to obtain more than 66 vol .-% by controlling partial pressures and dwell time at the aluminum contact by contact length and / or contact duration.
  • the aluminothermic reaction in step b) of the process according to the invention can take place in the presence or preferably in the absence of oxygen gas.
  • the carbon dioxide used comes from combustion processes or is obtained from the atmosphere or seawater.
  • a condition for carrying out the aluminothermic reaction should be that it takes place in a closed apparatus in a stream of carbon dioxide.
  • the gases released during the reduction of the carbon dioxide are collected in a PTFE gas bag and analyzed by gas chromatography.
  • the experimental or reaction apparatus consisted of a quartz tube with a ceramic furnace. Liquid aluminum was oxidized with pure carbon dioxide (C0 2 , GA 370) in a specially made quartz tube (dimensions: approx. 60 cm length, 8 cm diameter) under controlled heating in a ceramic furnace. For this purpose, mg quantities of aluminum were liquefied in the quartz tube. After flushing with nitrogen, carbon dioxide was passed over the aluminum melt at a flow rate of approx. 100 ml / minute, with a strong exotherm The reaction caused the aluminum to spontaneously ignite, which lasted approx. 15 seconds and only went out again when the aluminum was evidently converted.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Electrochemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour générer de l'énergie thermique et des produits chimiques de base, comprenant les étapes qui consistent : a) à générer un métal à base d'aluminium par électrolyse en sel fondu dans une installation d'électrolyse en sel fondu, b) à utiliser le métal à base d'aluminium pour générer de l'énergie thermique et des produits chimiques de base sélectionnés dans le groupe comprenant du monoxyde de carbone ou de l'hydrogène, en mettant du dioxyde de carbone et/ou de l'eau et/ou un mélange comprenant un composé renfermant de l'azote et de l'hydrogène ainsi que du dioxyde de carbone et/ou de l'eau en contact avec le métal à base d'aluminium, de manière à obtenir de l'oxyde d'aluminium et du monoxyde de carbone et/ou de l'hydrogène au cours d'une réaction aluminothermique ; c) à stocker ou transformer chimiquement le monoxyde de carbone et/ou l'hydrogène généré ; d) à stocker l'énergie thermique ainsi générée et à la convertir en d'autres formes d'énergie et e) à remettre en circulation l'oxyde d'aluminium obtenu dans l'électrolyse en sel fondu. Le procédé selon l'invention permet de faire fonctionner des installations d'électrolyse en sel fondu pour la production d'aluminium avec de l'énergie renouvelable à puissance fluctuante dans le temps, sans qu'il soit nécessaire d'arrêter ces installations. Ce procédé permet en outre de coupler la génération d'énergie et la préparation de produits chimiques de base qui peuvent être utilisés dans un processus de circulation.
EP21727080.0A 2020-05-09 2021-05-05 Procédé pour générer de l'énergie thermique et des produits chimiques de base par réaction aluminothermique Pending EP4146845A1 (fr)

Applications Claiming Priority (2)

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DE102020002774.1A DE102020002774A1 (de) 2020-05-09 2020-05-09 Verfahren zur Erzeugung von thermischer Energie und von Grundchemikalien mittels aluminothermischer Reaktion
PCT/EP2021/000059 WO2021228429A1 (fr) 2020-05-09 2021-05-05 Procédé pour générer de l'énergie thermique et des produits chimiques de base par réaction aluminothermique

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US (1) US20230193493A1 (fr)
EP (1) EP4146845A1 (fr)
CN (1) CN115516139A (fr)
AU (1) AU2021269642A1 (fr)
CA (1) CA3182924A1 (fr)
DE (1) DE102020002774A1 (fr)
WO (1) WO2021228429A1 (fr)

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DE102021005550A1 (de) * 2021-11-09 2023-05-11 Carsten Dentler lntermediate des metallischen Aluminiums mit Kohlenstoffoxid, Verfahren zu deren Herstellung und deren Verwendung
CN114965879B (zh) * 2022-05-12 2023-10-24 中国铝业股份有限公司 一种铝电解过程二氧化碳排放量的确定方法及相关设备

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CA354058A (fr) 1933-02-20 1935-11-12 Thomas Stuart Alexander Systeme d'energie electrique
US7141149B2 (en) 2004-06-22 2006-11-28 Cii Carbon Llc Electrodes useful for molten salt electrolysis of aluminum oxide to aluminum
US8366966B2 (en) * 2006-10-25 2013-02-05 Engineuity Research And Development Ltd. Methods and systems for producing energy from carbon dioxide
US8418435B2 (en) * 2008-06-13 2013-04-16 Nagi Hatoum Method for production of power from aluminum
US8668897B2 (en) 2009-01-05 2014-03-11 Technion Research & Development Foundation Limited Compositions and methods for hydrogen generation
US8377599B2 (en) * 2009-12-16 2013-02-19 Arthur Davidson Methods, apparatuses, and systems for the extensible and recyclable use of solid matter in the supply chain for the generation of electricity
EP2796672A1 (fr) 2013-04-26 2014-10-29 Evonik Industries AG Procédé de production d'énergie thermique et de monoxyde de carbone par la réduction aluminothermique de dioxyde de carbone
CN107758613A (zh) * 2017-09-30 2018-03-06 中国科学院理化技术研究所 一种联合电解铝和铝水反应制氢的调峰储能系统
CN109795984B (zh) * 2017-11-16 2023-12-05 银隆新能源股份有限公司 可循环式综合利用电能电解铝的铝水制氢系统及方法
DE102018213018A1 (de) 2018-08-03 2020-02-06 Karlsruher Institut für Technologie Vorrichtung und Verfahren zur thermisch-elektrochemischen Energiespeicherung und Energiebereitstellung

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DE102020002774A1 (de) 2021-11-11
CA3182924A1 (fr) 2021-11-18
AU2021269642A1 (en) 2022-12-01
CN115516139A (zh) 2022-12-23
US20230193493A1 (en) 2023-06-22
WO2021228429A1 (fr) 2021-11-18

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