US20140284220A1 - Method for generating hydrogen and oxygen by steam electrolysis - Google Patents

Method for generating hydrogen and oxygen by steam electrolysis Download PDF

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US20140284220A1
US20140284220A1 US14/350,844 US201214350844A US2014284220A1 US 20140284220 A1 US20140284220 A1 US 20140284220A1 US 201214350844 A US201214350844 A US 201214350844A US 2014284220 A1 US2014284220 A1 US 2014284220A1
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cathode
anode
steam
current
proton
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Béatrice Sala
Frédéric Grasset
Olivier Lacroix
Abdelkader Sirat
Kamal Rahmouni
Michel Keddam
Hisasi Takenouti
Dominique Goeuriot
Baroudi Bendjeriou
Philippe Colomban
Arie Van Der Lee
José Grégorio Sanchez
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Areva SA
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/22—Non-catalytic cracking in the presence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a method for generating highly reactive hydrogen and oxygen by steam electrolysis by means of a proton-conducting membrane.
  • Conductive ceramic membranes are today the subject of widespread research to increase their performances; in particular, said membranes find particularly interesting applications in fields such as the electrolysis of water at high temperature for the production of hydrogen or the treatment of carbon gases (CO 2 , CO) by electrochemical hydrogenation.
  • Patent applications WO2008152317 and WO2009150352 describe examples of such methods.
  • Hydrogen (H 2 ) appears today as a very interesting energy vector, which is likely to take more and more importance for treating among others petroleum products, and which could, in the longer term, advantageously act as a substitute for oil and fossil fuels, the reserves of which are going to decrease considerably over coming decades. In this perspective, it is nevertheless necessary to develop efficient methods of producing hydrogen.
  • a promising way forward for the industrial production of hydrogen is the technique known as steam electrolysis, for example at high temperature (HTE), at moderate temperature, typically above 200° C., or instead at intermediate temperature comprised between 200° C. and 1000° C.
  • HTE high temperature
  • moderate temperature typically above 200° C.
  • intermediate temperature typically comprised between 200° C. and 1000° C.
  • an electrolyte is used that is capable of conducting O 2 ⁇ ions and operating at temperatures generally comprised between 750° C. and 1000° C.
  • FIG. 1 schematically represents an electrolyser 1 comprising a ceramic membrane 2 , conducting O 2 ⁇ ions, assuring the function of electrolyte separating an anode 3 and a cathode 4 .
  • the O 2 ⁇ ions more specifically the oxygen vacancies (V ⁇ ), migrate through the electrolyte 2 to form oxygen O 2 at the surface of the anode 3 , electrons e′ being released according to the oxidation reaction:
  • this first method makes it possible to generate at the outlet of the electrolyser 1 oxygen—anodic compartment—and hydrogen mixed with steam—cathodic compartment.
  • an electrolyte is used that is capable of conducting protons and operating at lower temperatures than those required by the first method described above, generally comprised between 200° C. and 800° C.
  • FIG. 2 schematically represents an electrolyser 10 comprising a proton-conducting ceramic membrane 11 assuring the function of electrolyte separating an anode 12 and a cathode 13 .
  • H + ions or OH. O in the Kröger-Vink notation migrate through the electrolyte 11 , to form hydrogen H 2 at the surface of the cathode 13 according to the equation:
  • this method provides at the outlet of the electrolyser 10 pure hydrogen—cathodic compartment—and oxygen mixed with steam—anodic compartment.
  • H 2 goes through the formation of intermediate compounds, which are atoms of hydrogen adsorbed at the surface of the cathode with variable energies and degrees of interaction and/or radical hydrogen atoms H. (or H Electrode X the Kröger-Vink notation). These species being highly reactive, they usually recombine to form hydrogen H 2 according to the equation:
  • the charge carriers are not intrinsic to the structure of the membrane and are thus consequently more limited in the structure than the charge carriers of an anionic conduction, which are formed by the vacancies of the structure.
  • the present invention aims to propose a method for generating highly reactive hydrogen and oxygen adsorbates by steam electrolysis using an electrolysis cell comprising a solid proton-conducting electrolyte, said method being able to be industrialised while limiting the risks of delamination of the electrodes.
  • the invention proposes a method for generating hydrogen and oxygen adsorbates by steam electrolysis at 200° C. to 800° C. using an electrolysis cell comprising a solid electrolyte, which is made of a proton-conducting ceramic, said electrolyte being arranged between an anode and a cathode, said anode and cathode each comprising a proton-conducting ceramic and the ratio of the electroactive surface to the geometric surface of each of which is equal to at least 10, said method comprising the following steps:
  • the current may be continuous or pulsed; in the case of a pulsed current, current density is taken to mean the current density corresponding to the maximum value of the current intensity reached during the pulse.
  • the generation of the current may be obtained by different means:
  • reactive hydrogen atoms are taken to mean hydrogen atoms adsorbed at the surface of the cathode and/or radical hydrogen atoms H. (or H Electrode X in the Kröger-Vink notation).
  • Geometric surface of an electrode is taken to mean its flat external surface and electroactive surface is taken to mean the surface constituted of the internal surface of the pores of the electrode wherein takes place the electrochemical reaction; in other words, it is the internal surface on which the reaction takes place: 2e′+2OH. O ⁇ 2O O X +H 2 .
  • the electrodes according to the invention thus have a large number of triple points, namely points or contact surfaces between an ionic conductor, an electron conductor and a gas phase.
  • electrodes comprising a proton-conducting ceramic (typically electrodes formed of a cermet including a mixture of said ceramic of perovskite type and a metal alloy and/or a perovskite doped with a lanthanide with one or more degrees of oxidation) surrounding a proton-conducting electrolyte and having a sufficiently high electroactive surface/geometric surface ratio makes it possible to work at much higher current densities than those provided in the prior art without risk of delamination of said electrodes.
  • a proton-conducting ceramic typically electrodes formed of a cermet including a mixture of said ceramic of perovskite type and a metal alloy and/or a perovskite doped with a lanthanide with one or more degrees of oxidation
  • the method according to the invention generates highly reactive hydrogen at the cathode of the electrolyser (particularly hydrogen atoms adsorbed on the surface of the electrode and/or radical hydrogen atoms).
  • Electrode X are formed at the surface of the cathode according to the reaction:
  • the method according to the invention may also have one or more of the characteristics below, considered individually or according to any technically possible combinations thereof:
  • the subject matter of the present invention is also an electrolysis cell for the implementation of the method according to the invention comprising:
  • Said means for inducing a current circulating between the anode and the cathode may be a voltage, current generator or a potentiostat (in this case, the cell will also comprise at least one cathodic or anodic reference electrode).
  • the cell may also comprise means of introducing and evacuating pressurised gas in the cathodic compartment and/or means of introducing and evacuating pressurised gas in the anodic compartment.
  • FIGS. 1 and 2 are simplified schematic representations of steam electrolysers
  • FIG. 3 is a general simplified schematic representation of an electrolysis cell for the implementation of the method according to the invention.
  • FIGS. 4 to 6 are illustrations of applications using the cell of FIG. 3 .
  • FIG. 3 represents in a general, schematic and simplified manner an electrolysis cell 30 , also known as elementary assembly, implementing the electrolysis method according to the invention.
  • This electrolysis cell 30 has a structure similar to that of the device 20 of FIG. 2 .
  • the cell 30 comprises:
  • partial and relative pressure designates the insertion pressure compared to atmospheric pressure.
  • partial pressure will designate either the total pressure of the gaseous current in the case where the latter is uniquely constituted of steam or the partial pressure of steam in the case where the gaseous current comprises gases other than steam.
  • the anode 32 and the cathode 33 are preferentially formed of a cermet constituted of a mixture of a proton-conducting ceramic and an electron-conducting passivable alloy that is able to form a passive protection layer so as to protect it in an oxidising environment (i.e. at the anode of an electrolyser).
  • This passivable alloy is preferentially a metal alloy.
  • the passivable alloy comprises for example chromium (and preferentially at least 40% of chromium) so as to have a cermet having the particularity of not oxidising at temperature.
  • the chromium content of the alloy is determined so that the melting point of the alloy is above the sintering temperature of the ceramic.
  • Sintering temperature is taken to mean the sintering temperature required to sinter the electrolyte membrane so as to make it leak tight to gas.
  • the chromium alloy may also comprise a transition metal so as to retain an electron-conducting character of the passive layer.
  • the chromium alloy is an alloy of chromium and one of the following transition metals: cobalt, nickel, iron, titanium, niobium, molybdenum, tantalum, tungsten, etc.
  • the ceramic of the anodic and cathodic electrodes 32 and 33 is advantageously the same ceramic as that used by the formation of the electrolytic membrane of the electrolyte 31 .
  • the proton-conducting ceramic used by the formation of the cermet of the electrodes 32 and 33 and of the electrolyte 31 is a perovskite of zirconate type of generic formula AZrO 3 being able to be doped advantageously by an element A selected from lanthanides.
  • the use of this type of ceramic for the formation of the membrane thus requires the use of a high sintering temperature in order to obtain a sufficient densification to be leak tight to gas.
  • the sintering temperature of the electrolyte 31 is more specifically defined as a function of the nature of the ceramic but also as a function of the desired porosity level. Conventionally, it is estimated that to be leak tight to gas, the electrolyte 31 must have a porosity level below 6% (or a density above 94%).
  • the sintering of the ceramic is carried out under a reducing atmosphere so as to avoid oxidation of the metal at high temperature, i.e. under atmosphere of hydrogen (H 2 ) and argon (Ar), or even carbon monoxide (CO) if there is no risk of carburation.
  • a reducing atmosphere so as to avoid oxidation of the metal at high temperature, i.e. under atmosphere of hydrogen (H 2 ) and argon (Ar), or even carbon monoxide (CO) if there is no risk of carburation.
  • the electrodes 32 and 33 of the cell 30 are also sintered at a temperature above 1500° C. (according to the example of sintering of a zirconate type ceramic).
  • the anode 32 and the cathode 33 may also be formed of a ceramic material that is a perovskite doped with a lanthanide.
  • the perovskite may be a zirconate of formula AZrO 3 .
  • the zirconate is doped with a lanthanide that is for example erbium.
  • the perovskite doped with a lanthanide is doped with a doping element taken from the following group: niobium, tantalum, vanadium, phosphorous, arsenic, antimony, bismuth.
  • doping elements are chosen to dope the ceramic because they can pass from a degree of oxidation equal to 5 to a degree of oxidation of 3, which makes it possible to release oxygen during sintering.
  • the doping element is preferably niobium or tantalum.
  • Each electrode may also comprise a metal mixed with the ceramic so as to form a cermet.
  • the ceramic comprises for example between 0.1% and 0.5% by weight of niobium, between 4 and 4.5% by weight of erbium and the remainder zirconate.
  • the fact of doping the ceramic with niobium, tantalum, vanadium, phosphorous, arsenic, antimony or bismuth makes it possible to render the ceramic electron-conducting.
  • the ceramic is then a ceramic with mixed conduction; in other words, it is conducting both to electrons and to protons whereas in the absence of these doping elements, perovskite doped with a lanthanide with a single degree of oxidation is not conducting to electrons.
  • perovskite doped with a lanthanide with a single degree of oxidation is not conducting to electrons.
  • the electrodes 32 and 33 of the cell 30 are designed to have a ratio of their electroactive surface to their geometric surface that is equal to at least 10 and preferentially no less than 100.
  • Geometric surface is taken to mean the flat external surface of the electrode, i.e. the surface receiving the flux of electrons.
  • Specific (or developed) surface is taken to mean the surface accessible to a gas within the electrode: it is thus essentially constituted of the internal surface of the pores.
  • Electroactive surface is taken to mean the part of the specific surface on which the electrochemical reaction takes place; in other words, it is the internal surface on which the reaction takes place:
  • the means 34 making it possible to inject a current circulating between the anode 32 and the cathode 33 , wherein the density of the current is no less than 500 mA/cm 2 and preferentially no less than 2 A/cm 2 without risk of drop of current or delamination of the electrodes.
  • the applicant has advantageously noted that the fact of using electrodes made of a proton-conducting material and having a sufficient electroactive surface (advantageously no less than 100) makes it possible to increase notably the current density that can be used without risk of delamination of the electrodes.
  • the determination of the ratio between the electroactive surface and the geometric surface is carried out for example by means of a method of characterising the porous surface of a cermet electrode detailed in the publication “Characterization of porous texture of cermet electrode for steam electrolysis at intermediate temperature”, C. Deslouis, M. Keddam, K. Rahmouni, H. Takenouti, F. Grasset, O. Lacroix, B. Sala, Electrochimica Acta 56 (2011) 7890-7898.
  • H + ions (or OH. O in the Kröger-Vink notation) migrate through the electrolyte 31 , to form hydrogen H 2 at the surface of the cathode 33 according to the equation:
  • this method provides at the outlet of the cell 30 pure hydrogen—cathodic compartment—and oxygen mixed with steam—anodic compartment.
  • H 2 goes through the formation of intermediate compounds, which are hydrogen atoms adsorbed at the surface of the cathode 33 and/or radical hydrogen atoms H. (or H Electrode X in the Kröger-Vink notation). These species being highly reactive,
  • oxygen atoms adsorbed at the surface of the anode 32 may advantageously be used to carry out the production of oxygen adsorbate O Electrode X being able to be used in an oxygenation reaction at the anode, for example by injecting sulphur dioxide SO 2 or SO X at the anode, which reacts with oxygen to form sulphuric acid H 2 SO 4 or to form oxygen for the oxycombustion.
  • sulphur dioxide SO 2 or SO X at the anode, which reacts with oxygen to form sulphuric acid H 2 SO 4 or to form oxygen for the oxycombustion.
  • T1 of the device 30 depends on the type of material used for the membrane 31 ; whatever the case, said temperature is above 200° C. and generally below 800° C., or even below 600° C. Said operating temperature corresponds to a conduction assured by H + protons.
  • FIG. 4 and following each illustrate a particular use of the cell 30 of FIG. 3 , in which highly reactive hydrogen is used to recombine with other compounds at the cathode 33 .
  • FIG. 4 illustrates a first example in which the electrolysis cell 30 is used to form compounds of C X H y O Z type, (where x ⁇ 1, 0 ⁇ y ⁇ (2x+2) and 0 ⁇ z ⁇ 2x) after the reduction of the CO 2 and/or CO.
  • the cell 30 of FIG. 3 further comprises means 36 making it possible to insert under pressure gas (pCO 2 or/and CO) in the cathodic compartment 33 .
  • pCO 2 or/and CO under pressure gas
  • the water is oxidised while releasing electrons while H + ions (in OH. O form) are generated.
  • H + ions migrate through the electrolyte 31 and are thus capable of reacting with different compounds, which could be injected at the cathode 33 , CO 2 and/or CO type carbon compounds reacting at the cathode 33 with said H + ions to form C x H y O z type compounds (where x ⁇ 1, 0 ⁇ y ⁇ (2x+2) and 0 ⁇ z ⁇ 2x) and water at the cathode.
  • C X H y O z compounds synthesised at the cathode depends on numerous operating parameters such as, for example, the pressure of the cathodic compartment, the partial pressure of the gases, the operating temperature T1, the potential/current couple applied at the cathode, the dwell time of the gas and the nature of the electrodes.
  • the relative pressure of CO 2 and/or CO of the current is no less than 1 bar and no more than the rupture pressure of the assembly.
  • the total pressure imposed in a compartment may be compensated in the other compartment so as to have a pressure difference between the two compartments to avoid the rupture of the membrane assembly, electrode support if this has a too low rupture strength.
  • the operating temperature T1 of the device 30 also depends, in the range between 200 and 800° C., on the nature of the C X H y O Z carbon compounds that it is wished to generate.
  • FIG. 5 illustrates a second example in which the electrolysis cell 30 is used to reduce NO x type compounds (x ⁇ 2) to form N t O y H Z type compounds (where t ⁇ 1, y ⁇ 0 and z ⁇ 0).
  • the cell 30 of FIG. 3 further comprises means 36 making it possible to insert under pressure NO x type compounds (x ⁇ 2) into the cathodic compartment 33 .
  • the problem consists in enabling the reduction by electro-catalytic hydrogenation of the NO x content of effluents produced for example during the combustion of hydrocarbons or gas.
  • the production of these molecules is 60% due to urban transport and 40% due to boilers and thermal power plants. These molecules easily penetrate the bronchioles and affect respiration, causing hyper reactivity of the bronchial tubes in asthmatics, as well as increased vulnerability of the bronchial tubes to microbes, at least in children. Consequently, the regulations in force require industries to limit their NO X discharges.
  • the method of using the cell 30 according to FIG. 5 is based on the following principle: pressurised steam is introduced at the anodic compartment 32 and the NO x is fed under pressure at the cathodic compartment 33 .
  • the incorporation under pressure of steam is going to lead to oxidation of this water in the form of steam at the surface of the anode so as to generate protonated species in the membrane which, after migration within the membrane, are reduced at the surface of the cathode into very reactive hydrogen capable of reducing by hydrogenation the NO x introduced into the cathodic compartment, such that the NO x are reduced into less oxidised NO y (where y ⁇ x), then into nitrogen then into ammonia.
  • the monoatomic hydrogen adsorbates are formed at the surface of the cathode 33 according to the reaction: e′+OH. O ⁇ O O X +H Electrode X .
  • these compounds are either NO y less oxidised than the NO x compounds fed in under pressure, nitrogen N 2 , or ammonia NH 3 .
  • the solution according to the invention makes it possible to reduce the number of reactors required for the reduction of NOx to a single and unique reactor accommodating the electro-hydrogenation.
  • FIG. 6 illustrates a third example in which the electrolysis cell 30 is used to produce ammonia by electro-catalytic hydrogenation of N 2 . It should be noted that, according to this embodiment, it is also possible to produce other N x H y type compounds where x ⁇ 1 and y ⁇ 0 before resulting in the formation of NH 3 .
  • the cell 30 of FIG. 3 further comprises means 36 making it possible to insert nitrogen N 2 under pressure into the cathodic compartment 33 .
  • the problem is here to produce in massive quantity, at low cost and without emission of CO 2 , ammonia, by electro-catalytic hydrogenation of N 2 .
  • ammonia is produced by catalytic hydrogenation reaction of N 2 during steam reforming of hydrocarbons.
  • the synthesis of this product thus indirectly emits CO 2 .
  • the synthesis method induces a very great volatility of the production price of NH 3 .
  • 80% of the price of NH 3 is directly dependent on the price of the gas from which is produced the hydrogen required for the synthesis.
  • the volatility of the price of ammonia is very high and dependent on that of the gas.
  • the solution implemented in the cell 30 of FIG. 6 aims to produce ammonia using a single reactor.
  • the hydrogenated monoatomic compounds are formed at the surface of the cathode according to the reaction: e′+OH. O ⁇ O O X +H Electrode X .
  • the hydrogen required for the reduction of the nitrogen is no longer produced from fossil energy; the method according to the invention is “cleaner” in so far as it does not generate CO 2 .
  • the highly reactive hydrogen produced by the cell 30 of FIG. 3 may be used industrially for very different applications.
  • the invention is not limited to the embodiments that have been described.
  • the hydrogenation by the highly reactive hydrogen atoms may also be used in the petrochemical industry, for example to convert aromatic compounds into saturated alkanes (paraffins) and into cycloalkanes (naphthenes).
  • the method according to the invention may also be used to carry out hydrocracking making it possible to convert, under hydrogen pressure and at sufficiently high temperature, heavy petroleum products into light products: typically, hydrocracking makes it possible to obtain products such as diesel oil or kerosene from heavy residues.

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US14/350,844 2011-10-12 2012-10-11 Method for generating hydrogen and oxygen by steam electrolysis Abandoned US20140284220A1 (en)

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FR1159221A FR2981368B1 (fr) 2011-10-12 2011-10-12 Procede de generation d'hydrogene et d'oxygene par electrolyse de vapeur d'eau
FR1159221 2011-10-12
PCT/EP2012/070214 WO2013053858A1 (fr) 2011-10-12 2012-10-11 Procédé de génération d'hydrogène et d'oxygène par électrolyse de vapeur d'eau

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US10081872B2 (en) * 2014-08-08 2018-09-25 Kabushiki Kaisha Toshiba Hydrogen production system and method for producing hydrogen
US20190006695A1 (en) * 2015-12-14 2019-01-03 Aquahydrex Pty Ltd Method and system for efficiently operating electrochemical cells
US11421330B2 (en) * 2017-03-16 2022-08-23 Battelle Energy Alliance, Llc Methods for carbon dioxide hydrogenation
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EP2766512A1 (fr) 2014-08-20
JP2014532119A (ja) 2014-12-04
CN103987878A (zh) 2014-08-13
IN2014DN03034A (OSRAM) 2015-05-08
FR2981368A1 (fr) 2013-04-19

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