WO2017167605A1 - Dispositif et procédé pour produire un gaz, en particulier un gaz de synthèse - Google Patents

Dispositif et procédé pour produire un gaz, en particulier un gaz de synthèse Download PDF

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Publication number
WO2017167605A1
WO2017167605A1 PCT/EP2017/056671 EP2017056671W WO2017167605A1 WO 2017167605 A1 WO2017167605 A1 WO 2017167605A1 EP 2017056671 W EP2017056671 W EP 2017056671W WO 2017167605 A1 WO2017167605 A1 WO 2017167605A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
product gas
electrolyzer
product
line
Prior art date
Application number
PCT/EP2017/056671
Other languages
German (de)
English (en)
Inventor
Manfred Baldauf
Marc Hanebuth
Katharina Stark
Original Assignee
Siemens Aktiengesellschaft
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
Priority claimed from DE102016207420.2A external-priority patent/DE102016207420A1/de
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO2017167605A1 publication Critical patent/WO2017167605A1/fr

Links

Classifications

    • 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
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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

  • Electrolysers convert carbon dioxide CO 2 into carbon monoxide CO and oxygen O 2 .
  • Electrolyzers in particular CO 2 _ electrolysers, have so far only been the subject of basic research in the field of the materials used in each case.
  • a first Labormus ⁇ ter is set up currently, during its operation, first excess is worked with high CO2 and obtained the product gas with CO2 ver ⁇ thinned. This gas would have to be treated before further use by means of gas purification process to remove interfering CO2.
  • Concepts for the targeted production ei ⁇ nes defined synthesis gas with a low C02 content by a suitable operating concept of an electrolysis stack are not known.
  • Electrolyzer with aqueous electrolyte in which the educt gas (CO2) is added by means of a gas diffusion electrode (GDE).
  • GDE gas diffusion electrode
  • the reactant gas flows through the electrolyzer only once, so that, depending on the CO 2 excess, a fixed CO: H 2: CO 2 ratio results, but in a large number of cases too much CO 2 and too little H 2 for contains use in downstream syntheses.
  • CO2 reactant gas
  • Electrolysers are variable parameters that primarily determine the product gas composition, the current density or voltage that corresponds to the applied load, and the CO2
  • variable conditions include the choice of egg ⁇ umpumprate the electrolyte, and pressure and temperature.
  • Feedstock gas is in particular supplied gas.
  • Product gas is especially gas discharged.
  • Product product gas is in particular a desired product gas for a preferred further use.
  • the object is achieved by a device according to the main claim and a method according to the independent claim.
  • an apparatus for the manufacture ⁇ development of a product gas, particularly a synthesis gas proposed, comprising a supply line for supplying a reactant gas in an electrochemical cell of an electrolyzer, wherein a
  • Electrode space is executable
  • a method for producing a product gas, in particular a synthesis gas is proposed with the following steps:
  • GDE gas diffusion electrode
  • the electrolyzer can be a low-temperature electrolyzer, which is to be understood here as an electrolyzer operated at less than 100 ° C., the first electrode space being a cathode space, the second electrode space being an anode space, the membrane being ion space.
  • the electrolyzer can be conductive, in particular cation-conducting, and a plurality of electrochemical cells may be fluidly connected in parallel to each other, wherein the cells are electrically connected in series with each other.
  • the electrolyzer may be an aqueous electrolyte using CO 2 - electrolyzer for converting carbon dioxide CO 2 as educt gas in carbon monoxide CO as desired product gas and Sau ⁇ oxygen O 2 as an additional product gas, the product gas in particular in addition to the carbon monoxide CO as value ⁇ product gas, hydrogen H 2 as the second electrolysis gas and unconverted educt gas carbon dioxide CO 2 may have.
  • the electrolyzer may have a regulating device for adjusting the recirculated volume flow and thus a recycling rate, wherein the regulating device comprises a flow device arranged in the return line, in particular blower and / or a valve and / or a throttle flap, and / or a static or dynamic flow divider controls.
  • the regulating device comprises a flow device arranged in the return line, in particular blower and / or a valve and / or a throttle flap, and / or a static or dynamic flow divider controls.
  • the electrolyzer may have the regulating device for setting an electrical current density, wherein the regulating device regulates the current.
  • the control device for adjusting the Have metered addition of Edukgases per period of time controls the Zudosierrate.
  • control device can regulate such that in the product gas a ratio of desired product gas to second electrolysis gas to unconverted feed gas, in particular of CO to H 2 to CO 2 , is selectively adjustable in the first discharge line after the branching of the return line ,
  • Ratios of 1: 1.5 to 1: 3 be adjustable.
  • Figure 1 is a representation of the prior art
  • Figure 2 shows an embodiment of an inventive
  • Figure 3 shows an embodiment of an inventive
  • FIG. 1 shows a representation of the prior art.
  • CO: H2: CO2 9: 1: 15 to 20 arise.
  • FIG. 2 shows an arrangement according to the invention of a CO 2 electrolyzer.
  • a CO 2 electrolyzer By way of example, only one electrochemical cell is shown, wherein in reality a plurality of cells are arranged in the form of a cell stack. Not shown are the anode and the aqueous electrolyte ⁇ lyt with the corresponding circuits or
  • Reference numeral 1 denotes the inventive arrangement of a C02 _ electrolyzer for the production of a synthesis ⁇ gas.
  • 2a and 2b indicate a reactant feed, wherein 2a represents the access of CO2 and 2b additionally recycled
  • Reference numeral 10 denotes an electrochemical cell of the C02 _ electrolyzer, which is exemplified for ei ⁇ NEN entire cell stack.
  • Reference numeral 11 denotes a gas diffusion electrode (GDE).
  • Reference numeral 12 denotes a cathode compartment.
  • Reference numeral 13 denotes a membrane which may be provided, for example, cation-conductive to separate gas spaces.
  • strainszei ⁇ chen 14 represents an anode chamber, wherein in Figure 2, the anode is not shown.
  • Reference numeral 20 denotes the anode gas produced, which is oxygen here.
  • Reference symbols 21a and 21b denote the produced cathode gas as a product of value.
  • reference numeral 30 denotes a ⁇ he invention proper recirculation, in an inventive Ge ⁇ blower is arranged 31st It can also be inventively a re ⁇ gelbares valve and / or a throttle and / or a static or dynamic flow divider can be installed as control devices in the return line.
  • a control device 40 regulates such that in the product gas, a ratio of desired product gas to second electrolysis gas to unconverted educt gas, in particular of CO to H 2 to CO 2 , 30 is selectively adjustable in the first discharge line 21b after the diversion of the return line.
  • the synthesis gas is partially recirculated , so that a further portion of the CO.sub.2 still present in the synthesis gas is present in the second and optionally further
  • the aim of the proposed concept is to remove just enough product gas and introduce the right amount of additional CO2 so that a desired ratio of CO: H2: CO2 is achieved in the product gas by having exactly the composition required for the use of the synthesis gas ,
  • Both the injection of CO2 and the discharge of product gas can take place continuously or batchwise. Likewise, a dynamic operation is executable.
  • An aqueous electrolyte C02 electrolyzer is operated to produce a mixture of H2 and CO.
  • the produced gas should have the lowest possible amount of CO2 and a certain ratio of H2: CO, for example, at least 1.5: 1, more preferably more than 2: 1, but not more than 3: 1.
  • a recycle through which a significant portion of the product gas is directed into the reactant gas is provided.
  • the return contains a controllable blower and / or a valve or a throttle valve and / or a static or dynamic flow divider, with which the volume flow of this return or the recycling rate can be varied.
  • a new operating and Steuerungskon ⁇ concept for a C02 _ electrolyzer in which a required synthesis gas ⁇ composition can be adjusted by means of gas return, by the fraction of the discharged product gas and the amount of the newly supplied CO2 depending on the use of the synthesis gas.
  • control parameters that can be used to set variable product gas compositions that are conventionally unachievable and that are distinguished by meeting the specification for a synthesis gas for delivery to chemical syntheses. These are in particular CO: CO 2 _ ratios above 1.5 with simultaneous H2: CO ratio of 2 or more.
  • a control concept in which by means of selection of the control parameters mass or volume menpound in the recycle stream, recycle rate as a proportion of the out ⁇ infiltrated fraction, and mass or volumetric flow of the re-dosed CO2 as a function of the current density which corresponds to the electrical ⁇ rule load product concentration on, a defined CO: H2: C02 Ratio can be adjusted.
  • a defined CO: H2: C02 Ratio can be adjusted.
  • Fig. 3 shows an embodiment of a method according to the invention.
  • the method is used for producing a Pro ⁇ duktgases, particularly a synthesis gas, comprising the following steps.
  • (S1) supplying a starting gas into an electrochemical cell (10) of an electrolyzer (1) by means of a supply line (2), wherein a metered addition of the educt gas into a spatially separated from a second electrode space (14) by means of a membrane (13) first electrode space (12) is executable.
  • S2 removing the product gas from the first electrode space (12) by means of a first discharge line (21);

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un dispositif et un procédé pour produire un gaz, en particulier un gaz de synthèse, une conduite d'alimentation (2a, 2b) pour acheminer un gaz d'alimentation dans une cellule électrochimique (10) d'un électrolyseur (1). Il est possible d'ajouter du gaz d'alimentation dans une première chambre d'électrode (12) séparée d'une seconde chambre d'électrode (14) au moyen d'une membrane (13) et une première conduite d'évacuation (21a, 21b) pour évacuer le gaz de la première chambre d'électrode (12) ; une seconde conduite d'évacuation (20) pour évacuer un gaz additionnel de la seconde chambre d'électrode (14) ainsi qu'une conduite de retour (30) sortant de la première conduite d'évacuation (21a, 21b) pour renvoyer une partie du gaz dans la conduite d'alimentation (2a, 2b) sont fournies.
PCT/EP2017/056671 2016-03-31 2017-03-21 Dispositif et procédé pour produire un gaz, en particulier un gaz de synthèse WO2017167605A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102016205380.9 2016-03-31
DE102016205380 2016-03-31
DE102016207420.2 2016-04-29
DE102016207420.2A DE102016207420A1 (de) 2016-03-31 2016-04-29 Vorrichtung und Verfahren zur Herstellung eines Produktgases, insbesondere Synthesegases

Publications (1)

Publication Number Publication Date
WO2017167605A1 true WO2017167605A1 (fr) 2017-10-05

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Application Number Title Priority Date Filing Date
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WO (1) WO2017167605A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020001851A1 (fr) * 2018-06-25 2020-01-02 Siemens Aktiengesellschaft Rétroréaction électrochimique de conversion de gaz à l'eau à basse température
CN117779123A (zh) * 2024-02-27 2024-03-29 成都中核高通同位素股份有限公司 一种电化学法分离提纯放射性核素的流控系统

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077199A1 (fr) * 2010-12-08 2012-06-14 トヨタ自動車株式会社 Dispositif et système de production de gaz mixte
WO2014210484A1 (fr) * 2013-06-27 2014-12-31 The Board Of Trustees Of The University Of Illinois Catalyseurs pour la conversion de dioxyde de carbone
WO2015082130A1 (fr) * 2013-12-05 2015-06-11 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de production de gaz de synthese par coelectrolyse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077199A1 (fr) * 2010-12-08 2012-06-14 トヨタ自動車株式会社 Dispositif et système de production de gaz mixte
WO2014210484A1 (fr) * 2013-06-27 2014-12-31 The Board Of Trustees Of The University Of Illinois Catalyseurs pour la conversion de dioxyde de carbone
WO2015082130A1 (fr) * 2013-12-05 2015-06-11 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procede de production de gaz de synthese par coelectrolyse

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020001851A1 (fr) * 2018-06-25 2020-01-02 Siemens Aktiengesellschaft Rétroréaction électrochimique de conversion de gaz à l'eau à basse température
CN117779123A (zh) * 2024-02-27 2024-03-29 成都中核高通同位素股份有限公司 一种电化学法分离提纯放射性核素的流控系统
CN117779123B (zh) * 2024-02-27 2024-04-30 成都中核高通同位素股份有限公司 一种电化学法分离提纯放射性核素的流控系统

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