Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
  • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
  • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
  • H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
  • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
  • H01M8/1233—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with one of the reactants being liquid, solid or liquid-charged
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
  • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
  • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
  • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
  • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
  • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
  • H01M8/126—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing cerium oxide
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
  • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
  • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
  • H01M8/1266—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing bismuth oxide
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
  • H01M8/182—Regeneration by thermal means
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/245—Stationary reactors without moving elements inside placed in series
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
  • H01M2008/1293—Fuel cells with solid oxide electrolytes
• • 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
  • 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
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to an electricity production installation comprising a non-galvanic fuel cell.
• Hydrogen fuel cells are known to operate at high temperatures, ranging in particular from 450°C to 1000°C. In these cells, the hydrogen is oxidized, either at the cathode, if the hydrogen crosses the electrolyte in ionic form towards it, or at the anode if the oxygen crosses the electrolyte towards the anode as in the case of SOFC solid oxide batteries. The energy efficiency of all these fuel cells, however, rarely exceeds 60% of the energy.
• the document JP 2005 306624 A describes the use of the heat produced by the combustion in a burner of the residual gases of the pile, to provide thermal energy to the reactors where the stages of separation and concentrations of products intended for the production of hydrogen but does not recycle all the heat given off by the electrolyte nor the electrodes of the cell in which the dihydrogen reacts with the dioxygen, possibly using only the part of the said heat transferred to the dioxygens and dihydrogens which do not have not reacted, and further requiring a combustion chamber in which the dioxygen burns the dihydrogen outside the electrochemical cell while the dihydrogen can be separated from the water with which it can be mixed at the outlet of the anode by simple cooling under a pressure lower than the critical pressure of water, to be reintroduced at the inlet of said cell, or to be separated by a membrane.
• the document JP H09 320627 A describes an installation which makes it possible to use, when starting up the installation, the heat produced by a fuel cell using phosphoric acid as electrolyte.
• the fuel cell is completely fueled by the chemical reactions taking place in the hydrogen and oxygen production unit which operates with the contribution of the heat given off by the fuel cell.
• This installation does not allow recycling of the products of the electrochemical reaction of the cell, for the production of dihydrogen and dioxygen.
• the installation creates toxic co-products, the phosphorus reacting with the hydrogen.
• the present invention relates to a method for producing electricity implementing a non-galvanic fuel cell, said method making it possible to valorize the heat given off by said cell to generate fuel for said fuel cell by a thermal dissociation process, applied to the product of the same chemical composition as that produced by said cell, at least part of the heat given off by said cell being supplied to at least one of the endothermic reactions of said dissociation process, and the oxidizers and fuels of the fuel cell react directly with each other outside of said stack.
• the fuel enters the installation and mixes with the fuel possibly resulting from the reactors of the chemical cycle to be introduced into a fuel cell, said fuel cell producing electricity which is one of the products of the installation, as well that a product which is partly extracted from the installation in and partly recycled towards the chemical cycle reactors, the heat released by the fuel cell being transferred to the chemical cycle which produces fuel.
• the fuel cell is for example a solid oxide hydrogen cell whose combustion product is water, formed at the electrode in contact with the hydrogen.
• a dihydrogen concentrator (150) is advantageously arranged to extract the water from the water-dihydrogen mixture, for example consisting of a metallic membrane, of vanadium covered with silicon oxide on each face, themselves covered with a fine 20 micron layer of platinum as described in the article: 'Hydrogen-permeable metal membranes for high-temperature gas separations' published by David Edlund, Dwayne Friesen, Bruce Johnson and William Pledge in 1994 in the journal 'Gas Separation and Purification' Volume 8.
• thermal dissociation of water is for example the iodine sulfur cycle or any other similar cycle from hydrogen halide using for example bromine or chlorine instead of iodine, during which the reactions following used are respectively 2 H 2 S0 4 ® 2 SO2 + 2 H2O + O2; 2 HBr Br2 + Fh;
• each of the products of the thermal dissociation of water can then be used in part by the hydrogen fuel cell.
• the products dissociated by the thermal dissociation process all come from the overall chemical reaction taking place in the cell, and all the products resulting from the thermal dissociation are consumed by said cell.
• the sulfur iodine cycle allows in a first reaction at for example 120°C between di-iodine, sulfur dioxide and water to produce hydrogen iodide and sulfuric acid (I2 + SO2 + 2 H2O ® 2 Hl +H2SO4), the hydrogen iodide being recycled in a first endothermic reaction at for example 650°C in di-iodine and dihydrogen (2 Hl ® I2 + H2) and the sulfuric acid in dioxide of sulphur, water and dioxygen (2 H 2 S0 ® 2 SO2 + 2 H2O + O2) in a second endothermic reaction, for example at 830° C.; the heat necessary for the first and/or the second endothermic reaction coming from the hydrogen fuel cell, either by means of a thermal connection between the said fuel cell and the reactor(s) of the first and/or of the second endothermic reaction, or transported to said reactors by the water released from the hydrogen fuel cell during its operation.
• the thermal water dissociation process can use an alkali metal hydride in which water mixed with the alkali metal reacts to form a hydride of the alkali metal and oxygen (H2O + 2 Me -> 2MeH + 1 ⁇ 2 O2) while the alkali metal hydride is transformed in another reactor into metal and dihydrogen (2MeH -> 2Me + H2).
• an alkali metal hydride in which water mixed with the alkali metal reacts to form a hydride of the alkali metal and oxygen (H2O + 2 Me -> 2MeH + 1 ⁇ 2 O2) while the alkali metal hydride is transformed in another reactor into metal and dihydrogen (2MeH -> 2Me + H2).
• the dissociation of water can be made using Iron III chloride and Iron II chloride (6FeCl2 + 8 FI2O -> 2Fe 3 0 4 + 12HCI + 2H 2 ; 2Fe 3 0 4 + 12HCI + 3CI 2 -> 6FeCI 3 + 6H2O + 0 2 and 6FeCI 3 -> 6FeCI 2 +3CI 2 ).
• the dissociation of water can be done using vanadium chloride and vanadium tetrachloride (CI2 + H2 -> 2HCI + 1 ⁇ 2 O2; 2HCI + VCI2 -> 2VCI 3 + H 2 ; 2VCI 3 -> VCI 2 + VCI 4 ; 2VCU -> 2VCI 3 + Cl 2 )
• the process for the thermal dissociation of water can use hydrocarbons, methane reacting for example in a first reactor with water to form dihydrogen and carbon monoxide (CFU+FhO -> CO + 3H2), carbon monoxide and dihydrogen reacting in a second reactor to form methanol (CO+2FI2 -> CH 3 OH), methanol reacting in a third reactor with arsenate to form arsenious anhydride and dioxygen (CFI 3 OFI + As2 ⁇ 4 -> 1 ⁇ 2 As 2 0 3 + 1 ⁇ 2 O2), a fourth and a fifth reactor allowing the formation of arsenate and dioxygen from arsenious anhydride (1/2 AS2O5 -> 1 ⁇ 2 As 2 0 3 + 1 ⁇ 2 O2 and 1 ⁇ 2 AS2O5 + 1 ⁇ 2 As 2 0 3 -> As 2 0 4 ).
• the present invention also relates to an installation for the production of electricity making it possible to implement the method for producing electricity described above.
• the installation
• At least one fuel cell generating electricity and using a fuel, such as dihydrogen, as reducing fuel and operating at a given operating temperature, said cell being connected to a main source of dihydrogen;
• a fuel such as dihydrogen
• a chemical reactor/chemical production unit thermally connected to said cell and allowing the chemical production of fuel from the product of the reaction taking place in the cell, or from a chemical compound of the same composition, via at least an endothermic chemical reaction that takes place at a temperature less than or equal to said operating temperature of said cell, and
• said chemical reactor/said chemical production unit comprises at least one main compartment/main reactor allowing the chemical production of dihydrogen and di-iodine from hydrogen iodide (Hl ), a first secondary compartment/first secondary reactor allowing the chemical production of dioxygen from sulfuric acid (H 2 SO 4 ), and/or at least a second secondary compartment which allows the reaction between the di-iodine, the sulfur and water, which produces hydrogen iodide and sulfuric acid.
• This second secondary compartment therefore contains diatomic iodine, water and sulfur dioxide and possibly the products of this reaction, that is to say hydrogen iodide and sulfuric acid.
• Said first compartment/secondary reactor and/or said reactor/main compartment are thermally connected to said stack.
• the production unit further comprises means for introducing di-iodine produced in said main compartment/reactor to the second compartment/secondary reactor, means for introducing sulfuric acid produced in said second compartment/secondary reactor in said first compartment/secondary reactor and means for introducing the dioxygen produced in said first compartment/secondary reactor to said cell so that the latter serves there as oxidizer.
• the cycles of the hydrogen/dioxygen production reactions are not limited according to the invention. This may be, for example, one of the water splitting processes described above.
• the fuel cell of the installation of the invention is connected to a main source of fuel and to a main source of oxidizer.
• the supply of fuel and oxidizer provided by the operation of the chemical unit or the chemical reactor is an additional contribution.
• the chemical reactor/said chemical production unit comprises at least one main compartment/main reactor allowing the production of dihydrogen from hydrogen iodide, a first secondary compartment/first secondary reactor allowing the reaction between two molecules of sulfuric acid to produce in particular dioxygen and at least one second secondary compartment/second secondary reactor which allows the reaction between di-iodine, sulfur oxide and water to produce sulfuric acid and hydrogen iodide.
• the cycle used is then that described in figure 1.
• the installation according to the invention therefore makes it possible to produce, at the same time, electricity, dihydrogen and dioxygen, which are used as fuel in the cell within said installation itself.
• the heat generated continuously by the hydrogen fuel cell during its operation is used for the production of dihydrogen and/or dioxygen during endothermic reactions and the remaining heat, if any, can still be used for the production electricity by a turbine or for heating, for example.
• the cell is thermally connected only to said first reactor/secondary compartment, the main reactor being thermally connected to the first secondary reactor and the second secondary reactor to the main reactor.
• the cell is thermally connected to the three reactors.
• the chemical production unit includes reactors thermally connected to each other, either directly by contact or by a heat transfer fluid circuit.
• the use of a heat exchanger operating with a heat transfer fluid makes it possible to regulate the flow of heat transmitted by regulating the flow of heat transfer fluid.
• a heat transfer fluid can circulate in the walls of the main reactor to lower the temperature and transfer the calories which have passed through said walls, which are themselves preferably surrounded by thermal insulation, to the second secondary reactor.
• the chemical reactor or the chemical production unit can be configured to receive directly by convection or conduction the heat given off by the cell.
• the installation may also comprise thermal connection means between said stack and said main reactor/compartment and/or between said stack and said first reactor/secondary compartment which make it possible in particular to continuously supply the heat given off by said fuel cell and regulate the amount of heat supplied.
• thermal connection means can be or include, for example, a heat transfer fluid circuit circulating between the cell, close to the anode and the cathode, and the reactor.
• the endothermic chemical reaction 2HI® I2 + H2 can take place in the gas phase at 830°C.
• the main compartment therefore contains hydrogen iodide and possibly the reaction products (namely dihydrogen and di-iodine).
• the first compartment/secondary reactor allowing the reaction between two molecules of sulfuric acid to produce dioxygen (this compartment/reactor therefore contains at least sulfuric acid and possibly the products of the reaction, i.e. carbon dioxide sulfur, water and oxygen).
• the second compartment/secondary reactor allows the reaction between di-iodine, sulfur oxide and water, which produces hydrogen iodide and sulfuric acid.
• This second compartment/secondary reactor therefore contains diatomic iodine, water and sulfur dioxide and possibly the products of this reaction, that is to say hydrogen iodide and sulfuric acid.
• Said secondary compartments/reactors may be thermally connected to said main compartment and/or to said stack. Indeed, the publication entitled “Sulfur-lodineThermochemical Cycle”, by P.
• the aforementioned Sulfur-Iodine cycle makes it possible, using high heat, to produce hydrogen.
• the I2 + SO 2 + 2 H 2 O 2 Hl + H 2 SO 4 reaction operates at 120°C.
• the two endothermic reactions: 2 H 2 S0 4 ® 2 SO2 + 2 H2O + O2 and 2 Hl I2 + H2 are preferably carried out, respectively at 830° C. and 650° C., the SOFC cell preferably operating at 860° C. or more.
• reactor allowing the reaction between A and B encompasses a reactor containing the reactants A and B and optionally the products and by-products of this reaction.
• said operating temperature of said cell is greater than or equal to 850°C or 860°C. It is advantageously less than or equal to 1000°C or 1100°C.
• the battery is not limited according to the invention. It can be a proton exchange membrane hydrogen fuel cell or a solid oxide hydrogen fuel cell (SOFC). It may also for example also be a direct methanol cell, for example with a solid oxide electrolyte whose fuel is methanol; the reactions then being at the anode: CH3OH + 3 O 2 CO2 + 2 H2 O + 6 e and at the cathode: O2 + 4 e 2 O 2 ; then the carbon dioxide separated from the water, for example cooling and pressurizing, for example at 30° C.
• SOFC solid oxide hydrogen fuel cell
• the cell is advantageously chosen from solid oxide fuel cells, which have a high operating temperature, that is to say, greater than 850°C.
• the solid electrolyte of the SOFC battery (“solid oxide fuel cells”) is not limited.
• this is a solid electrolyte of metal oxide(s) type, it can, for example, be chosen from yttrium oxides stabilized with zirconium (YSZ), scandium oxides stabilized with zirconium , (ScSZ), gadolinium doped with/with cerium oxides (GDC), bismuth stabilized with erbium oxide(s) (ERB), cerium oxides doped with one or more samarium oxides and mixtures of at least two of these oxides.
• YSZ yttrium oxides stabilized with zirconium
• ScSZ scandium oxides stabilized with zirconium ,
• GDC gadolinium doped with/with cerium oxides
• ERB bismuth stabilized with erbium oxide(s)
• solid electrolyte containing or consisting of ceramics it can, for example, be chosen from ceramics and in particular composite ceramics containing salts of cerium oxide(s), (CSCs).
• CSCs cerium oxide(s),
• the means of introduction into chemical reactors can be simple pipes possibly equipped with nozzles preceded by compressors.
• the phase of di-iodine and sulfuric acid during their reintroduction is not limiting according to the invention. They can be liquid or gaseous, independently of each other, depending on the temperature and pressure conditions in the separators that equip the outlets of the reactor compartments.
• the installation of the invention thus makes it possible to produce both dihydrogen and dioxygen which are used in the electrochemical reaction of the cell.
• the installation of the invention can therefore operate with a reduced supply of dihydrogen and/or external oxygen. It is therefore particularly ecological and proves to be economically advantageous.
• the installation of the invention can be used to produce electric current, for example for industrial or domestic use, added to one or more electric motors for moving vehicles.
• the present invention also relates to a method for producing electricity by means of a fuel cell using dihydrogen as reducing fuel according to which the heat produced during the operation of said fuel cell is continuously used to chemically generate dihydrogen via the endothermic chemical reaction 2 H1 I2 + H2, said hydrogen then possibly being introduced into said cell to serve there as fuel.
• thermally connected indicate that two or more elements are in a thermal relationship either directly, by contact allowing the phenomenon of conduction, or by means of a suitable liquid or gaseous heat transfer fluid.
• solid oxide designates, within the meaning of the invention, a metal oxide allowing the transport of O 2 ions .
• solid oxide fuel cell designate any electrochemical device making it possible to produce electricity by oxidation of a fuel and comprising a solid electrolyte which may be a solid metal oxide, a mixture of metal oxides or a ceramic.
• Fig. 1 represents a schematic view of a particular embodiment of the present invention.
• Fig. 2 represents a diagram of the various flows of matter and energy necessary for the invention, entering, leaving and internal to the installation.
• Fig. 3 represents a diagram of the various flows of material and energy necessary for the invention, entering, leaving and internal to the installation, the fuel being methanol.
• Fig. 4 represents a diagram of the various flows of material and energy necessary for the invention, using a dihydrogen-water separator making it possible to maintain the proportion of dihydrogen in the gaseous mixture supplied to the anode of the cell stable. Examples
• the installation comprises a cell 1, which is a solid metal oxide fuel cell. Despite its operation at high temperature (from 850° C. to 1000° C.), battery 1 gives off heat.
• Cell 1 is thermally connected to a chemical reactor 3, which has three compartments. A thermal gradient is present in the chemical reactor 3 in order to ensure the appropriate reaction temperatures.
• the two upper compartments of the reactor are thermally connected to each other.
• the chemical reactor 3 comprises a main compartment 310 which is central in FIG. 1.
• a first secondary compartment 311 is located above the main compartment 310. This first secondary compartment 311 is arranged so as to first recover the heat produced by the battery 1 so that the temperature within it is higher than in the main compartment 310.
• a second secondary compartment 312 is arranged under the main compartment 310; the di-iodine from the separator 14 is advantageously brought into the tank 312 at a temperature of 120° C. in liquid form; a mixture of water and sulfur dioxide is supplied from the separator 65 and from a supply of water introduced via line 164, preferably also at a temperature of 120° C., and preferably under a pressure allowing that the two components of this gaseous mixture are liquid, the partial pressure of the sulfur dioxide being for example 50 bars.
• the temperature of the second secondary compartment 312 is lower than that of the main compartment 310.
• the two upper compartments are thermally connected so that the heat is transmitted from the first secondary compartment to the main compartment.
• the arrangement of the compartments is not limited to that shown in Fig. 1.
• the compartments may not have a common wall through which the heat is transmitted.
• a heat transfer liquid whose speed is regulated circulates between the 3 compartments to heat said compartments and maintain them at the temperature necessary for the chemical reactions they house, if these are the site of endothermic reactions.
• the residual heat resulting from the operation of the installation is evacuated at the level of the second secondary compartment 312, for example by means of a circuit cooling (not shown) in which circulates a heat transfer liquid. A portion of this circuit crosses said compartment or is in contact with the wall of the latter.
• This heat can be used, for example, to produce electricity by means of a turbine.
• the installation may also comprise an electricity production turbine.
• the installation comprises a gas separator 14 whose inlet is located at the outlet of the main compartment 310.
• the outlet of this separator 14 is connected by a pipe 141 to the battery and by a pipe 142 to the second secondary compartment 312
• the separator 14 can operate for example by concomitant expansion and cooling of the gas coming from the compartment 310, the di-iodine becoming liquid, between 184°C and its critical temperature being 545.8°C.
• the liquid di-iodine is then optionally recompressed to reach the operating pressure of reactor 312.
• the installation also comprises a separator 16 arranged at the entrance to the main compartment 310.
• the entrance to the separator 16 is connected via a pipe 161 to the second secondary compartment 312.
• the exit from the separator 16 is connected on the one hand to the main compartment 310 via a pipe 162 and on the other hand to the first compartment 311 via another pipe 163.
• liquid bars The reaction product mixture from reactor 312 is therefore preferably withdrawn from said reactor 312 after the reaction is complete.
• the pressure of the hydrogen iodide is advantageously lowered to the operating pressure of the reactor 310, for example 10 bars.
• a third separator 65 has its inlet connected to the first secondary compartment 311 (pipe not referenced and indicated by an arrow in FIG. 1) and its outlet connected by a first pipe (not shown) to the battery 1 and by a second pipe (not shown), to the second secondary compartment 312.
• the separator 65 operates for example by one or a series of compressions followed by cooling of the gas resulting from the decomposition of the sulfuric acid.
• Battery 1 produces electricity supplying a network not shown in Fig. 1, by consuming dihydrogen.
• the heat given off by cell 1 is used to heat the first secondary compartment 311 of chemical reactor 3. In the particular embodiment represented here, only this compartment is thermally connected to cell 1.
• the acid sulfur reacts on itself to produce water, oxygen and sulfur dioxide.
• the reaction products are separated in the separator 65; the sulfur dioxide and the water are brought into the second secondary compartment 312; the oxygen is brought to cell 1 to serve, in addition to the oxygen brought elsewhere, for example from the outside air, to the oxidation-reduction reaction which takes place in the latter.
• the reaction which takes place in the main compartment 310 produces gaseous di-iodine and gaseous dihydrogen. These produced gases are separated in the separator 14; the dihydrogen is routed (via line 141) to cell 1 to react there. The gaseous iodine leaving the separator 14 is routed via line 142 to the second secondary compartment 312.
• iodine reacts with sulfur dioxide and water from the first secondary compartment to produce hydrogen iodide (HI) and sulfuric acid.
• HI hydrogen iodide
• sulfuric acid is brought into the first secondary compartment by line 163 connected to separator 16.
• the fuel 201 enters the installation 200 and mixes with the fuel 203 from the chemical cycle reactors 212 to be introduced at 205 into the fuel cell 207.
• the oxidant is introduced into the installation (202) to be mixed there with the oxidant 204 from the chemical cycle reactors 212, to be introduced at 206 into the fuel cell 207.
• the fuel cell produces electricity 209 which is one of the products of the installation, as well as a product, for example water which is partly extracted from the installation at 211 and partly recycled at 210 to the reactors of the chemical cycle .
• the heat 208 given off by the battery 207 is transferred to the chemical cycle 212.
• the chemical cycle produces fuel 203; oxidant 204 and, optionally, residual heat 213 extracted from the installation.
• the methanol 501 enters the installation 500 and mixes with the methanol 503 from the chemical cycle reactors 512 to be introduced at 505 into the direct methanol fuel cell 507.
• the oxygen is introduced into the installation 502 to be mixed with the dioxygen 504 from the reactors of the chemical cycle 512, to be introduced at 506 into the fuel cell 507.
• the fuel cell produces electricity 509 which is one of the products of the installation, as well as water and carbon dioxide 511 which are partly extracted from the installation at 511 and partly recycled at 510 to the reactors of the chemical cycle.
• the heat 508 released by the battery 507 is transferred to the chemical cycle 512.
• the chemical cycle produces methanol 503; oxygen 504 and possibly residual heat 513 extracted from the installation.
• the gaseous mixture brought to the anode of cell 1 is put into circulation, that is to say brought and withdrawn by the pipe or pipes 153 to be in thermal and gaseous communication with the device 150 which is in thermal contact by the connection 152 with the reactor 310 at a temperature of approximately 650° C. to which said gas mixture is therefore cooled.
• the gaseous mixture is enriched in dihydrogen in the device 150 using one or more metal membrane(s) which makes it possible to extract the dihydrogen and/or the water which is rejected by the pipe 154.
• This water is advantageously used in part (not shown), to supply the dihydrogen production cycle, being then introduced into the pipe 164.
• the heat from this water is advantageously brought to the reactor 312 (not shown) or else to heat the dihydrogen and /or dioxygen introduced into the installation.

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• 2021
  • 2021-07-21 FR FR2107884A patent/FR3125648B1/fr active Active
• 2022
  • 2022-07-18 KR KR1020247005613A patent/KR20240035586A/ko active Pending
  • 2022-07-18 AU AU2022315507A patent/AU2022315507A1/en active Pending
  • 2022-07-18 EP EP22751368.6A patent/EP4374440A1/de active Pending
  • 2022-07-18 WO PCT/EP2022/070100 patent/WO2023001779A1/fr not_active Ceased
  • 2022-07-18 CN CN202280061719.9A patent/CN117981127A/zh active Pending
  • 2022-07-20 US US17/869,459 patent/US20230022610A1/en not_active Abandoned

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