EP2823088A1 - Système de méthanisation basé sur une centrale électrique - Google Patents

Système de méthanisation basé sur une centrale électrique

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Publication number
EP2823088A1
EP2823088A1 EP13714880.5A EP13714880A EP2823088A1 EP 2823088 A1 EP2823088 A1 EP 2823088A1 EP 13714880 A EP13714880 A EP 13714880A EP 2823088 A1 EP2823088 A1 EP 2823088A1
Authority
EP
European Patent Office
Prior art keywords
electrolysis unit
methanation
power plant
water
state
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.)
Withdrawn
Application number
EP13714880.5A
Other languages
German (de)
English (en)
Inventor
Marc Hanebuth
Uwe Lenk
Nicolas Vortmeyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Priority to EP13714880.5A priority Critical patent/EP2823088A1/fr
Publication of EP2823088A1 publication Critical patent/EP2823088A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00—Apparatus for generating gases
    • 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
    • C01B3/061—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 metal oxides with water
    • 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
    • C01B3/105—Cyclic methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/02—Combustion or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/38—Applying an electric field or inclusion of electrodes in the apparatus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/58—Control or regulation of the fuel preparation of upgrading 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
    • Y02E60/32—Hydrogen storage
    • 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

Definitions

  • the present invention relates to a power plant-based methanation system which, in addition to a fossil-fired power plant, has an electrolysis unit and a methanization reactor. Furthermore, the invention relates to methods for operating such a methanation system.
  • the method proves to be disadvantageous because the electrolysis unit can only be operated at times of sufficient electricity supply, or in an inefficient manner the methane or methanol produced must be burned again to supply electricity to operate the electrolysis unit.
  • the electrolysis unit can only be operated at times of sufficient electricity supply, or in an inefficient manner the methane or methanol produced must be burned again to supply electricity to operate the electrolysis unit.
  • the present invention is therefore based on the object to avoid the disadvantages of the prior art.
  • the invention has for its object to enable a substantially continuous production of synthetic methane.
  • the synthetic methane production at times of oversupply of electrical Energy in the public power supply networks as well as at times of increased demand for electrical energy in the same.
  • a substantially continuous methane production is to be made possible, which is at least partially independent of the electricity supply in the public power supply networks.
  • the energy should be provided in the first place by the time ⁇ offered surplus electricity in the public power supply networks.
  • a power plant-based methanation system which, in addition to a fossil-fueled power plant, has an electrolysis unit and a methanization reactor, wherein the power plant and the electrolysis unit are designed to supply the methanization reactor with starting materials for a methanization reaction, and wherein the Elektrolysierillon ⁇ well Betrie ⁇ can as in a charge and in a discharge ben be in which charging state supplies the Elektrolysiertechnik with electric current and at the same time a chemical energy storage device is charged, and in which discharge of the chemical energy storage discharged ,
  • the invention object is achieved by a method for operating a Methanleiterssystems previously described ge ⁇ solves having a fossil-fired power plant a electric ⁇ lysierritt and a methanation reactor, said power plant and the Elektrolysierritt thereto are oriented forms ⁇ , the methanization reactor with raw materials for to provide a methanation reaction, wherein the
  • the invention object is achieved by a method for loading ⁇ operating a Methanmaschinessystems previously described ge ⁇ dissolves, which has a Elektrolysiermati addition to a fossil-fired power plant and a methanation reactor up, wherein the power plant and the Elektrolysierussi are adapted to the methanation reactor with output ⁇ materials to provide for a methanation reaction, wherein the Elektrolysierritt in a first step a mixture of water and CO2 is supplied from the power plant, the electrolytically ⁇ table or chemically according to hydrogen and CO2 converted is ⁇ converts in a second step in the Elektrolysiertechnik, and wherein in a third step, the mixture of hydrogen together with the CO2 is fed to the methanation reactor as starting materials.
  • the power plant based Methanisie ⁇ tion system in addition to a methanization reactor for the production of synthetic methane, a fossil-fired power plant, which can also provide starting materials for the methanation reaction in addition to the provision of electrical power.
  • Such starting materials are in particular ⁇ sondere CO and CO2 that result from the combustion reaction in the fossil fuel-fired power plant.
  • the methanation system according to the invention has an electrolysis unit which can be operated both in a charging state and in a discharging state. In the state of charge, the electrolysis unit is supplied with electric power either from the fossil-fueled power plant or, preferably, from the public power supply networks when excess power is available.
  • a chemical energy store is charged, which is discharged again during the discharge state, and thus the energy required for a Thanization required to produce the corresponding starting material energetically supplied.
  • Charger status and discharge status can be connected directly in time.
  • the state of charge is thus to be understood as a charging process, during which the electrolysis unit receives electrical energy and a chemical energy store is charged.
  • the discharge is to be understood as a discharge process, in which the charged chemical energy storage is discharged again to provide energy for the electrolysis ready to stel ⁇ len.
  • the Elektrolysierech can thus be ⁇ be driven both by absorbing electricity in the state of charge as well with the release of chemical energy in the discharge for the electrolysis.
  • the provision of synthetic methane at times of oversupply of electric power in public power grids, as well as increased demand for power from them, is made possible in substantially continuous operation.
  • the continuous operation in turn makes the intermediate storage of the raw materials are unnecessary, thereby Her ⁇ position can be done very economically at high capacity utilization of the plant.
  • the Elektrolysierritt stored in the charge state of at least part of the supplied electrical energy as chemical energy in a chemi ⁇ 's energy storage. Accordingly, the chemical occurs see saving captured during the charge state of the electrical energy not only indirectly in the form of synthe ⁇ table produced methane in the methanation reactor, but also the chemical storage is done in the
  • Electrolysis unit itself. By setting suitable reaction conditions, this chemical energy can be reused in a suitable form, thus allowing the energization of subsequent processes. In particular, the provision of the cached chemical Energy will see the operation of the methanation unit during the discharge state of the electrolysis unit.
  • the synthetic methane production is supplied with starting materials from the fossil-fired power plant directly or indirectly and with starting materials from the electrolysis purity ⁇ . Since both the fossil-fueled power plant and the electrolysis unit can provide these starting materials substantially continuously, the methanation reaction in the methanation reactor can also be substantially continuous. As a result, synthetic methane can be produced substantially independently of the electricity demand in the public power supply networks without being limited exclusively to the supply of electric power from the fossil-fired power plant.
  • the electrolysis unit is merely supplied with excess current from the public power supply networks during the charging state. Accordingly, supply of the electrolysis unit with electrical power from the fossil-fired power plant could be completely dispensed with. However, since the supply of electricity in public power supply networks during a day at times sharp fluctuations may be exposed, it may also be necessary execution as having to retrieve electric power from the fossil-fired power station during the charging state of the electrolyzer ⁇ sierritt.
  • fossil-fueled power plant should be understood in its broadest meaning.
  • fossil-fueled power plants also include incineration plants for waste recycling.
  • the electrolysis unit in both the charging and in the discharge state by at least one starting material
  • the electrolysis unit is suitable for the substantially continuous provision of starting materials for the methanation reaction.
  • the Elektrolysiertechnik is to be generated according to a Wei ⁇ ter realise able during charge and during discharge state molecular hydrogen. This can be implemented in the methanization reactor under suitable reaction conditions with the CO 2 or CO, or a mixture of these two substances, which arise as combustion products in the power plant process, to synthetic methane.
  • the electrolysis unit requires a supply with an air flow for operating a gas electrode or for discharging the oxygen formed during the state of charge.
  • the electrolysis unit has a connection via which the air flow can be introduced into the electrolysis unit.
  • the air flow is particularly suitable to dissipate heat from the Elektrolysiertechnik. Exporting ⁇ has shown the air flow can also be designed as a general gas flow.
  • Elektrolysiertechnik may correspond in their off ⁇ design of the battery described in WO 2011/070006 Al. This publication is hereby expressly incorporated by reference into the present application.
  • the battery described therein which corresponds to the present electrolysis unit in its structure in Wesentli ⁇ Chen, has numerous gas channels, is fed to a cathode means wel ⁇ cher oxygen-containing process gas.
  • the oxygen-containing process gas is, in order to reduce the risk ⁇ potential as well as to increase the efficiency, atmospheric oxygen.
  • the oxygen contained in the process gas is reduced during the discharge state and passes through the ion-conductive Cathode through. Due to the prevailing oxidation potentials, the reduced oxygen continues to migrate through a solid-state electrolyte and to an anode where the ionic oxygen releases its charge and combines with molecular hydrogen to form water.
  • the solid electrolyte is in this case advantageously suitable for anionic conductivity, but prevents electrical conduction of charge carriers.
  • the solid electrolyte comprises, for example, a metal oxide, such as zirconium oxide and / or cerium oxide, which in turn is doped with a metal, for example scandium. Owing to the doping, oxygen vacancies are produced in the metal oxide, which permit the anionic transport of reduced oxygen (ie doubly negatively charged oxygen atoms) or increase the stability of the electrolyte.
  • the anionic oxygen is converted to H 2 O according to the following equation:
  • the electrons released in this case can be tapped off at the anode and fed to an electrical consumption circuit.
  • gaseous What ⁇ ser is sticiansrefractress to provide a starting material for this Methani- introduced into a support body, the oxidizable Materi- al, preferably in the form of an elemental metal.
  • the material may be present as a powder or as a porous compact.
  • elemental hydrogen is generated, for example, according to the following equation:
  • Me an oxidizable material, in particular a metal, and represents the chemical energy storage of the electrolysis unit. This can during the Ladezu ⁇ stands by suitable reduction of the oxidized Material he testifies ⁇ or be regenerated. Due to suitably chosen electronegativities of the oxidizable material, the tendency of the gaseous water to react more strongly with the material in the support body than with a metal of the anode material. As a result, the anode material is advantageously protected against corrosion. Further details regarding the specific construction of the battery or of the electrolysis unit can be found in the above-cited publication.
  • the electrolysis unit comprises a metal and / or a metal oxide as a chemical energy store, which can be oxidized during the discharge state.
  • the metal and / or Me ⁇ talloxid therefore allow the information stored in them chemical energy during the discharge state again by appropriate means of releasing se.
  • the metal and / or metal oxide may preferably be selected from the group of lithium, manganese, iron, titanium or tungsten.
  • the metal and / or Me ⁇ talloxid is present as a powder or porous compact.
  • such a metal and / or metal oxide enables a suitable reaction with gaseous water, as indicated above in Equation 2. As a result, molecular hydrogen is liberated, which can serve as the starting material for the methanization reaction.
  • the electrolysis unit comprises a metal oxide which can be reduced during the charge state.
  • the metal oxide is present in a relatively lower oxidation state, or in pure metallic form, and can thus provide a chemical energy store, which provides the chemical energy for the chemical conversion in the electrolysis on discharge.
  • a chemical energy store which provides the chemical energy for the chemical conversion in the electrolysis on discharge.
  • the molecular oxygen is delivered in a sense as Maupro ⁇ domestic product during the charging state.
  • the Elektrolysierech a supply line, which is adapted to the Elektrolysie ⁇ purity with water, especially with steam to versor ⁇ gene.
  • the water or water vapor are provided as process fuel or process gas, which allow to operate the electrolysis unit in a charging or discharging state.
  • Be ⁇ vorzugt water vapor can also be provided during the discharge state as a transport material for elemental oxygen.
  • the oxygen is chemically bound and consequently ensures the chemical storage of electrical energy.
  • the water or the water vapor can serve to provide elemental oxygen during the state of charge, whereby the release of oxygen for the methane nticiansrepress required hydrogen can be provided.
  • Water or water vapor are cost-effective and relatively unge ⁇ dangerous in terms of their handling.
  • the Elektrolysierech comprises a solid electrolyte, which in particular separates two electrical electrodes electrically iso ⁇ lating each other, but a predetermined conductivity ion, in particular an anion conductivity in ⁇ has.
  • the solid electrolyte ensured in vorteilhaf ⁇ ter way an electric insulation which the Vorausset ⁇ wetting of a controlled electrical
  • the electrolysis unit is suitable for operation for at least 500.degree. C., in particular of at least 600.degree. C. and preferably between 600.degree. C. and 800.degree.
  • the high operating temperatures ensure an efficient charge or discharge operation, and hence an efficient tion Be ⁇ woman on top of starting materials for the Methanmaschinesreak-.
  • advantageous sier bain serve the waste heat of electrolytically as waste heat to preheat some of the réellestof ⁇ fe before they are introduced into the methanation reactor.
  • the power plant has a CO 2 separator, which is designed to separate CO 2 from an exhaust gas stream of the power plant and gas ⁇ shaped CO 2 as the starting material for the Methanleitersreakti- on in the methanation reactor and / or for the electrolysis of the electrolysis provide.
  • the CO2 separation device thus ensures the particularly selective treatment of the exhaust stream of the power plant to provide the starting material, which is converted to synthetic methane during the methanation reaction.
  • Other pollutants are not specifically separated for use in the C02 separation device, and thus do not or not significantly contribute to impurities in the methanation reactor.
  • the selective separation of CO2 from ⁇ increases the efficiency with which synthe ⁇ schematic of methane can be produced.
  • the targeted separa- allows voltage of CO2 from the exhaust gas stream of the power plant in a quantitative controlled We ⁇ sentlichen supply of CO2 in the Me ⁇ than Deutschensreaktor.
  • a thermal bridge is further provided s michssystems which is adapted to conduct thermal energy from the Methani ⁇ sticiansreaktor to Elektrolysierü.
  • the thermal bridge is particularly intended to conduct positive and ne gative ⁇ thermal energy, that is, the heat conduction can be effected in both directions. Since the methanization reaction is typically highly exothermic, the heat released can be used to preheat the electrolysis unit. This heat is supplied to the electrolysis unit by means of the thermal bridge. Likewise, the heat released during the methanation reaction is suitable for conditioning the water introduced into the electrolysis unit in order to evaporate it, for example.
  • the heat arising during the methanation reaction can be used partly or mostly for the operation of the electrolysis unit. It is likewise conceivable for the heat to be used for preheating process gas streams which are fed to the electrolysis unit. This heat utilization consequently increases the overall efficiency of the embodiment Methanation system. It also simplifies the heat Manage ⁇ ment during operation of Methanmaschinessystems.
  • a water return is provided, which is designed to water, which is incurred after the methanation reaction, again to the electroly- sieratti or to the supply line, which is at least abandonedbil ⁇ det to supply the electrolysis with water , due.
  • the water return thus reduces on the one hand excessive water consumption, and on the other hand, an undesirable energy consumption for the thermal conditioning of the electrolysis unit supplied water. Since the water produced after the methanation reaction typically still has a high heat content, it requires relatively little energy to re-evaporate this water for use in the electrolysis unit. Thus a water re ⁇ management enables efficient material and réellema ⁇ management.
  • the electrolysis unit in particular continuously, in either a charging or in a discharging state.
  • the continuous operation of che Elektrolysierussi ensures the continu ⁇ ous supply of raw materials for the methanation. Consequently, it is not necessary to stock these source materials prior to delivery to the methanation reactor.
  • the continuous operation of the electrolysis unit also enables high economic efficiency of operation.
  • the charging and discharging states alternate.
  • efficient continuous operation can be achieved.
  • the electrolysis unit is in particular then transferred from the discharge state into a state of charge, if can not be provided from ⁇ reaching amounts of starting materials for the methanation reaction during the energy self-sufficient discharge status. Consequently, an advantageously high efficiency can be achieved in the execution of Ge ⁇ yakvons through targeted alternation of discharge and charging status.
  • the starting materials are fed in substantially stoichiometric amounts as a mixture to the methanization reactor.
  • the deviations from the required stoichiometric amounts are less than 20%, more preferably less than 10%, and be ⁇ Sonders preferably less than 5%.
  • the methanation reactor thus essentially only those amounts of starting materials are supplied, which can be fully implemented during the Methanmaschinesreak- tion. Consequently, the synthetic methane produced in the methanation reactor is contaminated to a relatively lower degree of foreign matter, so that expensive gas separation after preparation of the synthetic methane is not required.
  • the synthetic methane removed from the methanization reactor will be contaminated by water only.
  • the water which is typically vaporous at the temperatures prevailing in the methanation reactor, can easily be condensed out of ⁇ and then, for example, be redirected to the electrolysis unit via suitable water recycling.
  • the products which are removed from the methanization ⁇ tion reactor not fed to a process for reconverting. It is also possible to supply the products directly to an infrastructure for handling natural gas as a synthetic gas. Reverse conversion, which would result in thermal and electrical power losses, can thus be avoided.
  • the methanation reactor is operated continuously.
  • the continuous operation assures insbeson ⁇ particular a high process efficiency as well as a desired con tinuous ⁇ provision of synthetic methane.
  • FIG. 1 shows a schematic representation of the methanation system according to the invention according to a first embodiment
  • FIG. 2 shows a schematic representation of the methanation system according to the invention in accordance with a second embodiment
  • FIG. 3 shows a schematic representation of individual chemical reactions and processes during operation of the electrolysis unit in a state of charge
  • Fig. 5 is a schematic flow diagram for monitoring Veranschauli ⁇ a first embodiment of the inventive method.
  • FIG. 6 is a schematic flow diagram for Veranschauli ⁇ monitoring a process according to a second embodiment.
  • Fig. 1 shows a first embodiment of the Methanmaschinessystems 1 of the invention which still has a Elektrolysierussi 3 in addition to a fossil be85 ⁇ th power plant 2.
  • Both the power plant 2 and the electrolysis unit 3 are designed to provide starting materials 10 (not shown in the present case) and to feed them to a methanization reactor 4, in which the starting materials 10 are suitably chemically converted into synthetic methane.
  • the fossil-fueled power plant 2 provides 12 gaseous CO 2 in a supply line.
  • the supplied CO 2 was separated in the power plant 2 by means of a not shown C0 2 -Abtrennvoriques from an exhaust stream of the power plant 2.
  • a power supply line 15 is further provided, which allows the
  • electric power can also be supplied via a network extraction line 14 are taken from the public power supply networks, and the electrolysis unit 3 are supplied.
  • the electrolysis unit 3 For the operation of the electrolysis unit 3 in a discharge / charge state, it may be necessary to supply this air via an air supply line 16.
  • the supplied gas is discharged again from the air outlet 17 after proper use of the electrolysis unit 3 or during the intended use of the electrolysis unit 3. After removal of this gas, for example, the ambient air can be supplied again. It serves on the one hand a suitable heat dissipation and on the other hand to dissipate the oxygen formed during the Ladezu ⁇ conditions .
  • the operation of the electrolysis unit 3 requires the supply of a suitable process substance, which can be supplied via the supply line 11 of the electrolysis unit 3.
  • this process substance is water or water vapor, which is at least partly converted into hydrogen in the electrolysis unit 3 during the discharge state and the state of charge.
  • the starting material 10 produced by electrolysis or chemical reaction for the methanation reaction is fed to the methanation reactor 4 by means of the transfer line 18. Is in the 3 Elektrolysierillon no complete reaction of water he ⁇ ranges, so the unreacted quantities are conveyed at least partially also in the methanation reactor 4 together with the electrolytically produced hydrogen.
  • the supply line 12 discharges into the transmission line 18 to provide CO 2 , so that the hydrogen therein can mix together with the CO 2 .
  • This mixture is then fed to the methanization reactor 4, in which the starting materials 10 are converted to synthetic methane.
  • the synthetic methane thus produced is derived from the methanation reactor using a Pro ⁇ dukt 19th
  • the product taken from the product discharge 19, ideally a mixture of synthetic methane and water, requires suitable separation of water from the product stream. This can be achieved, for example, by advantageous condensation of the water contained in the product stream, with the water being able to be fed back to the supply line 11 for supply to the electrolysis unit 3 via a water return 25.
  • Fig. 2 shows another embodiment of the invention shown SEN Methanmaschinessystems 1. It differs from that shown in Fig. 1 Methanmaschinessystem 1 only in that the utilizatge- through the supply line 12 set CO 2 is not in the transmission line 18 for supply to the methanation reactor 4 is provided, but for introduction into the supply line 11 to be supplied to the electrolysis unit 3. Consequently, a mixture of CO 2 and water is fed as process materials through the lead 11 of the Elektrolysiertechnik 3, wherein the two substances in the electric ⁇ lysiertechnik 3 according implemented by electrolysis who can ⁇ . CO 2 is set in the Elektrolysiertechnik 3 to ⁇ to CO, so is water, according to the above, in Hydrogen reacted.
  • both substances are used as starting materials in synthetic reacted ⁇ methane accordingly. If complete conversion of water and CO 2 is not achieved in the electrolysis unit 3, the unreacted amounts are also conveyed into the methanation reactor 4 together with the hydrogen and the CO.
  • FIG. 1 and according to FIG. 2 illustrates that no intermediate storages are provided in which the starting materials 10 would have to be intermediately stored before being fed into the methanation reactor. Rather, both the fossil-fired power plant 2 and the electrolysis unit 3 as well as the methanation ⁇ reactor 4 are in substantially continuous operation, so that from the product discharge 19 continuously synthetically produced methane can be removed.
  • the electrolyte ⁇ sieratti 3 comprises an arrangement of a first electrical electrode 6 and a second electrical electrode 7, which are both electrically isolated from each other by a solid electrolyte 5.
  • the first electrical electrode 6 is in this case with air as the process gas in direct Contact.
  • the first electrical electrode may comprise a substance having a perovskite structure. It may have a layer thickness between 10 and 200 ym, where they be ⁇ vorzugt comprises about 50 ym.
  • the solid-state electrolyte 5 is typically embodied as a metal-doped metal oxide and has a layer thickness of typically between 20 and 100 ⁇ m, preferably 50 ⁇ m.
  • the second electrode 7 may be designed as a metal-ceramic composite material, a so-called cermet of ⁇ , being able to be advantageous metals lithium, manganese, iron, titanium, tungsten or nickel.
  • the second electrode 7 is in contact with gaseous water.
  • a metal oxide Mo
  • Mo metal oxide
  • the metal serves as a chemical energy ⁇ memory 8 during the discharge state shown in Fig. 4.
  • metal oxide is again reduced to the form suitable for chemical storage, namely the metal.
  • Hydrogen at the second electrode 7 is not further reacted, it can be fed as the starting material 10 of the methanization reaction the methanization reactor 4.
  • the metal over- thus takes on the role of the chemical energy storage 8, wel ⁇ cher provides the energy for the ongoing electrolysis of water to hydrogen available.
  • the running reactions which are shown for the state of charge in Fig. 3 and for the discharge state in Fig. 4 within the Elektrolysierussi, a proportion of water is always converted into a proportion of hydrogen.
  • This can serve as the starting material 10 for the methanization reaction in the methanization reactor 4.
  • hydrogen can be provided as starting material both during the state of charge and during the state of discharge, independently of the operating state.
  • the reactions taking place in the energy store 8 are shown here by way of example for a divalent metal. However, this is not intended to be limiting. Rather, can contribute in some other appropriate substances over ⁇ the principle. The reaction equations change accordingly.
  • a mixture of CO 2 and water can also be supplied, with CO 2 being converted into CO and water into hydrogen.
  • CO 2 is converted by the emission of an oxygen atom at the second electrode 7 in CO.
  • FIG. 5 shows a schematic sequence of method steps for illustrating a first embodiment of the method according to the invention in a flow chart.
  • a first step water to a first step
  • Fig. 6 another embodiment of the erfindungsge ⁇ MAESSEN method is illustrated as a flow chart.
  • un ⁇ the procedure of the method shown in Fig. 5 shown in Fig. 6 differs merely in that the Elektrolysiertechnik in a second step, a mixture of water and CO2 is fed.
  • the electrolysis unit 3 converts electrolytically or chemically water into hydrogen and CO2 into CO.
  • the thus get ⁇ ne mixture is approximately reactor in a fourth step a methanized 4 supplied, so that the raw materials contained therein can be implemented in a 10 methanation reaction to synthetic methane.

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  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un système de méthanisation (1) basé sur une centrale électrique, lequel système comporte, en plus d'une centrale électrique (2) à combustible fossile, une unité d'électrolyse (3) et un réacteur de méthanisation (4). La centrale électrique (2) et l'unité d'électrolyse (3) sont réalisées de manière à alimenter le réacteur de méthanisation (4) en matières premières (10) pour une réaction de méthanisation. L'unité d'électrolyse (3) peut fonctionner à la fois dans un état de charge et dans un état de décharge, état de charge dans lequel l'unité d'électrolyse (3) est alimentée en courant électrique et un accumulateur d'énergie chimique (8) est chargé simultanément, et état de décharge dans lequel l'accumulateur d'énergie chimique (8) est déchargé.
EP13714880.5A 2012-04-10 2013-03-22 Système de méthanisation basé sur une centrale électrique Withdrawn EP2823088A1 (fr)

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EP12163588.2A EP2650401A1 (fr) 2012-04-10 2012-04-10 Système de méthanation basée sur une centrale électrique
EP13714880.5A EP2823088A1 (fr) 2012-04-10 2013-03-22 Système de méthanisation basé sur une centrale électrique
PCT/EP2013/056065 WO2013152942A1 (fr) 2012-04-10 2013-03-22 Système de méthanisation basé sur une centrale électrique

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US9537189B2 (en) 2012-06-11 2017-01-03 Siemens Aktiengesellschaft Temperature control system for a high-temperature battery or a high-temperature electrolyzer
DE102014105067A1 (de) * 2014-04-09 2015-10-15 Mitsubishi Hitachi Power Systems Europe Gmbh Verfahren und Vorrichtung zur Flexibilisierung von mit kohlenstoffhaltigen Brennstoffen befeuerten Kraftwerken mittels der Produktion kohlenstoffhaltiger Energieträger
WO2015055349A1 (fr) * 2013-10-16 2015-04-23 Paul Scherrer Institut Procédé/unité intégrée de stockage du co2 par conversion en un gaz naturel de synthèse
WO2016182567A1 (fr) * 2015-05-13 2016-11-17 GM Global Technology Operations LLC Structure entre un radar et un carénage
US9859703B2 (en) * 2015-11-19 2018-01-02 Shepherd Hydricity, Inc. Method for using chemical thermodynamics to buffer the voltage of electric circuits and power systems
CN111315378A (zh) 2017-11-16 2020-06-19 诺华股份有限公司 包含lsz102和瑞博西尼的药物组合
EP3716969A1 (fr) 2017-12-01 2020-10-07 Novartis AG Combinaison pharmaceutique comprenant du lsz102 et de l'alpésilib
CA3164837A1 (fr) * 2020-03-31 2021-10-07 Osaka Gas Co., Ltd. Systeme de production d'hydrocarbures
WO2024013968A1 (fr) * 2022-07-15 2024-01-18 三菱電機株式会社 Système de synthèse de méthane
JP2024054767A (ja) * 2022-10-05 2024-04-17 株式会社デンソー 炭化水素生成システム及び二酸化炭素循環システム

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