EP2819768A1 - Method and device for separating the carbon dioxide from a gaseous mixture - Google Patents
Method and device for separating the carbon dioxide from a gaseous mixtureInfo
- Publication number
- EP2819768A1 EP2819768A1 EP13713469.8A EP13713469A EP2819768A1 EP 2819768 A1 EP2819768 A1 EP 2819768A1 EP 13713469 A EP13713469 A EP 13713469A EP 2819768 A1 EP2819768 A1 EP 2819768A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cell
- intermediate plate
- porous intermediate
- sub
- gaseous mixture
- 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- Withdrawn
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000008246 gaseous mixture Substances 0.000 title claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 26
- 239000012528 membrane Substances 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000002347 injection Methods 0.000 claims abstract description 5
- 239000007924 injection Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 230000005611 electricity Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- 238000002485 combustion reaction Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010248 power generation Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 16
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 26
- 238000009434 installation Methods 0.000 description 10
- 238000004891 communication Methods 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- 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
- B01D53/22—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 diffusion
-
- 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
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
- B01D63/082—Flat membrane modules comprising a stack of flat membranes
- B01D63/0822—Plate-and-frame devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0236—Glass; Ceramics; Cermets
-
- 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
- H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
-
- 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
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0668—Removal of carbon monoxide or carbon dioxide
-
- 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
-
- 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
-
- 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
- H01M8/14—Fuel cells with fused electrolytes
- H01M2008/147—Fuel cells with molten carbonates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/40—Combination of fuel cells with other energy production systems
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to a method and a device for separating carbon dioxide from a gaseous mixture.
- the invention is applicable at the head of any sector aimed at capturing carbon dioxide (CO 2) in a gaseous mixture, especially in combustion products.
- CO 2 carbon dioxide
- the capture process that is the subject of the invention is essentially a so-called "post-combustion" process, which method is adaptable to any installation, including an existing one, producing such discharges or combustion products.
- the invention is particularly suitable for applications aimed at capturing carbon dioxide from so-called diffuse sources, such as internal combustion engines or domestic boilers.
- PSA pressure swing absorption
- the invention aims to solve the drawbacks of the prior art and in particular to provide a device and a method for separating carbon dioxide from a gaseous mixture whose volume is sufficiently small to be installed in a vehicle or in a room for cleaning. dwelling of an individual.
- the invention relates to a device for separating the carbon dioxide contained in a gaseous mixture, which device comprises an elementary cell comprising:
- a first set of membrane electrodes constituting an electrochemical subcell in the form of a solid oxide fuel cell operating in power generation mode b. a second set of membrane electrodes constituting an electrochemical sub-cell in the form of a molten carbonate fuel cell operating in the electrolyser mode;
- a first electrically conductive porous intermediate plate interposed between the first and the second set of membrane electrodes and in electrical and hydraulic connection therewith;
- injection means for injecting the gaseous mixture into said first porous intermediate plate
- the invention advantageously uses an electrochemical sub-cell in the form of a molten carbonate fuel cell or MCFC, acronym for "Molten Cabonate Fuel Cell” operating in electrolyser mode and performing the electrolysis of the water contained in the gaseous mixture.
- the electrical energy required for this electrolysis is partly provided by the solid oxide electrochemical sub-cell, or SOFC, an acronym for “Solid Oxide Fuel Cell", which electrochemical cell operates in fuel cell mode.
- SOFC solid oxide electrochemical sub-cell
- the device that is the subject of the invention is also very compact.
- the device that is the subject of the invention is particularly suitable for separating the CO 2 from the exhaust gases of the internal combustion engine of a vehicle, or for an installation on a domestic boiler and more generally for any application where the compactness separation device is an essential factor.
- the invention also relates to a process for separating carbon dioxide from a gaseous mixture comprising steam which process is implemented by means of the device of the invention comprising a plurality of juxtaposed elementary cells, which method comprises the steps of:
- the operation of the MCFC sub-cells in the electrolyser mode requires the transfer of the CO 3 2 - ions through the membrane, from the anode to the cathode of these electrochemical sub-cells so as to effect the separation of the CO 2 from the mixture.
- the oxygen and hydrogen produced during the electrolysis in the MCFC sub-cell are used for the operation of the SOFC cells connected on either side of said MCFC sub-cell, SOFC cells where the oxygen reacts with the hydrogen resulting from the electrolysis in the MCFC stack, in a redox reaction, so as to form water
- the process makes it possible to recover the purified CO 2 on the second porous intermediate plate the i th cell and the other components of the gas mixture on the first porous intermediate plate of the i th cell.
- the device according to the invention comprises a plurality of juxtaposed elementary cells, each elementary cell being mechanically, hydraulically and electrically connected to the next via its second porous intermediate plate.
- the device that is the subject of the invention is easily adapted to the quantity and flow rate of gaseous mixture to be treated, by multiplying the number of elementary cells.
- the porous intermediate plates of the device which is the subject of the invention consist of a ceramic material.
- the differential thermal expansion between said porous plates and the electrochemical cells is reduced and the device is more resistant to thermal cycles of high amplitude as encountered for mobile applications.
- the porous plates consist of silicon carbide (SiC).
- the porous plates consist of silicon carbide titanate (Ti 3 SiC 2 ).
- These ceramics exhibit characteristic properties of ceramics and metallic materials such as electrical and thermal conductivity, high modulus of elasticity and high temperature and corrosion resistance.
- the device which is the subject of the invention furthermore comprises:
- the device that is the subject of the invention is capable of treating a gaseous mixture that does not include, or not enough, water vapor to initiate the reactions.
- step i) using a device comprising a water reservoir, the gas mixture not comprising water vapor, said process comprises, before step i), a step consisting in:
- the method which is the subject of the invention comprises the steps of:
- the device that is the subject of the invention makes it possible to compress the carbon dioxide in liquid form so as to reduce the storage volume.
- the invention also relates to a vehicle comprising a combustion engine internal and comprising:
- a tank adapted to store carbon dioxide in liquefied form
- an electric generator adapted to derive a portion of the engine power to generate an electric current capable of supplementing the electric power generated by the SOFC cells
- t. means for electrically connecting the electric generator with the first porous plates of the elementary cells.
- FIGS. 1 to 8 The invention is described below according to its preferred embodiments, in no way limiting, and with reference to FIGS. 1 to 8, in which:
- FIG. 1 schematically represents an installation for separating carbon dioxide from a gaseous mixture comprising a device according to the invention
- FIG. 2 shows in a schematic sectional view an embodiment of the device object of the invention
- FIG. 3 shows in perspective an elementary cell according to an embodiment of the device of the invention, Figure 3A, assembled, and Figure 3B in an exploded view;
- FIG. 4 is a perspective view of the porous intermediate plates of the device that is the subject of the invention, according to an exemplary embodiment thereof;
- FIG. 5 is a perspective view of an exemplary embodiment of the device according to the invention comprising a plurality of assembled elementary cells
- FIG. 6 is a perspective and exploded view of the device of FIG. 5;
- - Figure 7 is a perspective view and exploded of an embodiment of the end corresponding to the negative terminal of the device shown in Figure 5;
- FIG. 8 is a perspective and exploded view of the end corresponding to the positive terminal of the device of FIG. 5.
- a carbon dioxide separation plant of a gaseous mixture comprises an emission source of said mixture (100).
- a mixture comprises CO 2 and other gases, called diluents, such as N 2 .
- a source is, according to an exemplary embodiment, a thermal machine consuming a fossil fuel such as an internal combustion engine or a boiler.
- This gaseous mixture (100) is initially stored in a tank (181) provided with a safety vent (182). Said reservoir (181) cooperates with a regulated valve (183) to control the flow of gas in the installation.
- the gas mixture of the buffer tank (181) is heated in a means (184) adapted to bring it to a temperature suitable for subsequent reactions.
- This heating means (184) is for example electric or uses any other form of available energy, depending on the application.
- water vapor (101) is mixed with the gas in appropriate mixing means (185).
- the gas mixture (102) comprising steam is sent to the device (1 10) object of the invention to separate the constituents, and more particularly the CO 2 .
- the CO 2 (103) separated from the gaseous mixture is sent to storage means (191) from which it is then sent to a subsequent treatment.
- these storage means (191) are combined with compression means (not shown) to store said C0 2 in a liquid form.
- the mixture (104) comprising the diluents and water vapor is sent to a condenser (192), which allows to recover the water (101 ' ) contained in said mixture (104), the diluents (105) being evacuated, for example, in the open air.
- Means (193) control the level of water (101 ') recovered by condensation in the condenser (192) and control a valve (194) to send the water to a reservoir (195) buffer.
- the volume of this tank (195) that is to say the volume of buffer water, is calculated according to the characteristics of the installation and the nature of the gaseous mixture (100) to be treated.
- the water (101 ') contained in this buffer tank is sent to heating means (196) to form steam (101) and mix with the initial gas mixture (100).
- this water is also used as heat transfer fluid in the condenser (192).
- the water is treated in closed circuit in the installation and the volume of the buffer water tank (195) is calculated according to the target flow rate and the amount of water initially required to start the operation of the installation implementing the device (1 10) object of the invention.
- FIG. 2 according to a schematic representation, the device that is the subject of the invention
- (110) comprises a plurality (i-1), i, (i + 1) of stacked elementary cells.
- Each elementary cell consists of sub-cells:
- a first porous plate (212) intermediate for conveying, in the elementary cell, the gas to be treated
- a second porous intermediate plate (214) for collecting the separated CO 2 and collecting the electrons necessary for ionizing the oxygen used for the operation of the next SOFC electrochemical sub-cell in the stack.
- the first porous intermediate plates (212) of each elementary cell also make it possible to convey electrons provided externally thereto into the device. These plates (212) are connected to the negative terminal of the device object of the invention, the second intermediate plates (214) porous being connected to the positive terminal of said device.
- the gas mixture (102) comprising carbon dioxide and water vapor is injected into the first porous intermediate plate (212).
- CO 2 and H 2 O form H 2 and CO 3 2 - ions by electrolysis of water on the catalytic sites of the MCFC sub-cell.
- the CO 3 2 - ions diffuse through the membrane of the sub-cell MCFC (213).
- the CO 3 2 - ions release an electron generating CO 2 and 1 / 2.0 2.
- the hydrogen formed at the anode of the MCFC sub-cell (213) diffuses through the pores of the first intermediate plate (212) to the SOFC sub-cell (21 1) Similarly, the oxygen formed at the cathode of the MCFC sub-cell (213) diffuses through the pores of the second porous plate (214), just like the electrons released at this cathode, to the anode of the SOFC sub-cell (21 1) of the next elementary cell (i + 1) in the stack.
- the device On the catalytic sites of the anode of the SOFC sub-cell (211) of the elementary cell (i + 1), O 2 forms ions O 2 " with the electrons released at the second porous plate (214) of the ith elementary cell, preceding in the stack
- the O 2 ions thus generated diffuse through the (i + 1) th SOFC sub-cell (211) to react with the cathode of this sub-cell with the H 2 molecules produced at the cathode of the MCFC sub-cell (213) of this same (i + 1) th elementary cell
- H 2 and O 2 " react on the catalytic sites of said SOFC cell (21 1) to form H 2 O in the same fluid vein in which H 2 O is" consumed "by the MCFC cell (213).
- the device is able to treat a gaseous mixture (101) containing no water, provided to initiate the reaction by injecting water into said gas. Then, the water circulates
- the SOFC sub-cell (21 1) operates in generator mode and generates a portion of the electrons necessary for the operation of the MCFC sub-cell (213) operating in electrolyser mode. Since this SOFC sub-cell (21 1) is the seat of an exothermic reaction, it also produces part of the heat necessary to compensate for the endothermic nature of the electrolysis reaction in the MCFC sub-cell (213), which sub-cell MCFC cell (213) thus dissipates the thermal energy released by the exothermic reaction whose sub-cell SOFC (21 1) is the seat.
- the endothermic nature of the electrolysis reaction in the MCFC sub-cell (213) is a function of the temperature of the gaseous mixture to be treated and also conditions the amount of electrical energy necessary for the operation of this sub-cell.
- the operating point of the device according to the invention is selected as a function of the temperature of the gaseous mixture to be treated so that it operates autonomously without external energy input or by minimizing this external supply of energy, electrical or thermal, depending on the sources available according to the intended application.
- the operating temperature of the device is limited to 650 ° C, which corresponds to a current operating temperature for MCFC sub-cells (213).
- the external power consumption is 1 .KW. hour for 0.86 Kg to 2.21 Kg of separated C0 2 .
- FIG. 3 according to an exemplary embodiment, an elementary cell (300) constituted by a stack of sub-cells (211, 212, 213, 214) of substantially quadrangular shape, said sub-cells being inserted between two types of joints ( 31 1, 312) perforated in a substantially rectangular centered opening corresponding to the exchange surface between the sub-cell and whose periphery provides the sealing function.
- the type 1 joints (31 1) are placed on either side of each SOFC (21 1) and MCFC (213) cell and seal with the non-porous part of the intermediate plates (212, 213).
- the type 2 seals (312) provide sealing between the intermediate plates, and include oblong slots (321, 322) extending in substantially perpendicular directions, on the outer edge of the seal, and which, once the stacked and assembled elementary cells (300) draw distribution circuits for the incoming gas mixture and separate gas collection.
- the intermediate plates (212, 214) of the two types are essentially the same, the second intermediate plate (214) being identical in structure to the first (212) but rotated 90 ° clockwise.
- the type 2 seals (312) corresponding to these intermediate plates comprise for this purpose two types of notches (421, 422) on two perpendicular sides of said seals, which notches act as keyed during assembly of the device object of the invention.
- Said porous plates (212, 214) consist of an electrically conductive material such as a metallic material. They are advantageously constituted by an electrically conductive ceramic, whose lower coefficient of thermal expansion is more suitable for mounting in stack and at the operating temperature of the device object of the invention.
- the low density of these ceramics makes it possible to reduce the weight of the device.
- the porosity of the plates is defined so as to minimize the pressure drop across the porous parallelepiped said plates while maximizing the effective contact area with the other sub-cells, so as to reduce the electrical contact resistance.
- the current density at the interfaces is of the order of 200 mA.cm -2 .
- the device (1 10) object of the invention consists of the assembly of such elementary cells.
- the mass of such a device is of the order of 500 kg for a treatment capacity of approximately 103 kg of CO 2 per hour.
- the device of the invention is particularly well suited to the treatment of vehicle exhaust gases such as locomotives, heavy goods vehicles, recreational or tourism boats, construction or farm machinery, as well as than domestic boilers.
- the device (1 10) which is the subject of the invention comprises a plurality of elementary cells stacked and held together by clamping by means of tie rods (550) which clamp said elementary cells between two plates (512, 514 ) say end.
- the two ends (522, 524) of the device according to the invention comprise, according to this embodiment, means for injecting the gaseous mixture to be treated and collecting the products resulting from this treatment.
- the first end (522) corresponding to the positive terminal of the device comprises means for injecting the gaseous mixture to be treated and means for collecting a portion of C0 2 separated from this mixture.
- the second end (524) corresponding to the negative terminal of the device comprises means for collecting the mixture consisting of water vapor and diluents and a portion of CO 2 separated from the initial gas mixture.
- FIG. 6, according to an exploded view of an exemplary embodiment of the device that is the subject of the invention, the gaseous mixture to be treated is injected at the first end by connection means (602) at the top of the device according to this seen and circulates in said device through the duct drawn in the upper part of this device by the upper oblong slots (321) substantially horizontal type 2 joints of said device.
- the mixture comprising water vapor and diluents is collected at the second end by means (604) in communication with the duct drawn by the oblong grooves (321) located at the bottom of the type 2 seals.
- Means (603) ) C0 2 collection are placed substantially in the center of each of the end plates (512, 514) in communication with the ducts drawn by the substantially vertical oblong grooves (322) of the type 2 seals.
- the end (524) corresponding to the negative terminal of this device comprises a connector (704) adapted to collect in its lower part the mixture of diluents and water vapor, by an oblong slot (721) in communication with the adjacent oblong slots (321) of the type 2 seals.
- This oblong slot (721) of the connector (704) is in hydraulic connection with the means (604). ) of collecting this mixture.
- This connector (704) further comprises substantially vertical oblong slots (722) in communication with the adjacent oblong slots (322) of the type 2 seals.
- the end (522) corresponding to the positive terminal of said device comprises a connector (802) able to collect in its upper part the gas mixture to be treated, by an oblong slot (821) in communication with the adjacent oblong slots (321) of the type 2 seals.
- This oblong slot (821) of the connector (802) is in hydraulic connection with the injection means (602) of this mixture .
- This connector (802) further comprises substantially vertical oblong slots (822) in communication with the adjacent oblong slots (322) of the type 2 joints.
- a cover (803) including corresponding oblong slots obstructs the oblong slot (821).
- the invention Achieved objectives, in particular it allows for a C0 2 separation device ungaz combustion product, which device is particularly compact and low energy consumption.
- the device that is the subject of the invention is suitable for use in collecting the carbon dioxide produced by a vehicle comprising an internal combustion engine.
- the C0 2 separated from the exhaust gas is advantageously stored in liquefied form so as to reduce the storage volume.
- a portion of the power of the heat engine is advantageously used to compress the gas and to produce, by a generator, the electrical energy in addition to the production of the SOFC sub-cells for the functioning of the operating MCFC sub-cells. in endothermic mode.
- the CO 2 thus harvested at the source is recovered, thanks to specific equipment, when said vehicle is refueling.
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Abstract
The invention relates to a device (110) for separating the carbon dioxide contained in a gaseous mixture (100), said device comprising: a) a membrane electrode assembly forming an electrochemical sub-cell (211) in the form of a solid oxide fuel cell (SOFC) operating in electricity production mode; b) a second membrane electrode assembly forming an electrochemical sub-cell (213) in the form of a molten carbonate fuel cell (MCFC) operating in electrolyser mode; c) a first porous intermediate plate (212) interposed between the first (211) and the second (213) membrane electrode assemblies; d) injection means (602, 321) for injecting the gaseous mixture into said first porous intermediate plate; e) a second porous intermediate plate (214) linked with the second membrane electrode assembly; f) collection means (603, 322) for collecting the carbon dioxide separated from the gaseous mixture on said second porous intermediate plate (212).
Description
PROCÉDÉ ET DISPOSITIF DE SÉPARATION DU DIOXYDE DE CARBONE METHOD AND DEVICE FOR SEPARATING CARBON DIOXIDE
D'UN MÉLANGE GAZEUX OF A GASEOUS MIXTURE
L'invention concerne un procédé et un dispositif de séparation du dioxyde de carbone d'un mélange gazeux. L'invention est applicable en tête de toute filière visant la captation du dioxyde de carbone (C02), dans un mélange gazeux notamment dans des produits de combustion. Pour cette raison le procédé de captation objet de l'invention est essentiellement un procédé dit « postérieur à la combustion » lequel procédé est adaptable à toute installation, y compris existante, produisant de tels rejets ou produits de combustion. L'invention est particulièrement adaptée à des applications visant la captation du dioxyde de carbone issu de sources dites diffuses, telles que des moteurs à combustion interne ou des chaudières domestiques. The invention relates to a method and a device for separating carbon dioxide from a gaseous mixture. The invention is applicable at the head of any sector aimed at capturing carbon dioxide (CO 2) in a gaseous mixture, especially in combustion products. For this reason, the capture process that is the subject of the invention is essentially a so-called "post-combustion" process, which method is adaptable to any installation, including an existing one, producing such discharges or combustion products. The invention is particularly suitable for applications aimed at capturing carbon dioxide from so-called diffuse sources, such as internal combustion engines or domestic boilers.
La production d'énergie par combustion, notamment à partir de combustibles fossiles, rejette dans l'atmosphère du dioxyde de carbone lequel contribue à l'effet de serre et au réchauffement climatique. La captation de ce dioxyde de carbone est une solution pour limiter ces rejets atmosphériques. Néanmoins, les produits de combustion mettant en oeuvre ces combustibles se présentent sous la forme de mélanges gazeux où ledit dioxyde de carbone est combiné avec d'autres gaz tels que de l'azote, du méthane, des oxydes d'azote (NOx), de la vapeur d'eau des résidus hydrocarbures, du dioxyde de soufre, etc. Aussi, pour capter le dioxyde de carbone il est nécessaire de le séparer de ces autres composés. The production of energy from combustion, especially from fossil fuels, releases into the atmosphere carbon dioxide, which contributes to the greenhouse effect and to global warming. The capture of this carbon dioxide is a solution to limit these atmospheric discharges. Nevertheless, the products of combustion using these fuels are in the form of gaseous mixtures in which the said carbon dioxide is combined with other gases such as nitrogen, methane, nitrogen oxides (NOx), water vapor from hydrocarbon residues, sulfur dioxide, etc. Also, to capture the carbon dioxide it is necessary to separate it from these other compounds.
Selon l'art antérieur, la séparation du C02 d'un tel mélange gazeux est réalisée par différents procédés, parmi lesquels : According to the prior art, the separation of CO 2 from such a gaseous mixture is carried out by various methods, among which:
- la séparation par voie chimique : - chemical separation:
lavage du gaz par des solvants, notamment des aminés ; washing the gas with solvents, especially amines;
la séparation par carbonatation minérale ; separation by mineral carbonation;
- la séparation par voie mécanique : - mechanical separation:
séparation membranaire sur membrane polymère membrane separation on polymer membrane
séparation sur tamis moléculaire de type zéolite couramment désignée PSA acronyme de « pressure swing absorption » zeolite-type molecular sieve separation commonly referred to as "pressure swing absorption" PSA
- la séparation par voie thermique : - thermal separation:
- par voie cryogénique ;
la condensation après oxy-combustion à l'oxygène pur. - cryogenically; the condensation after oxy-combustion with pure oxygen.
La voie chimique nécessite des surfaces d'échange suffisantes entre le gaz et les produits absorbant le dioxyde de carbone. La voie mécanique nécessite une différence de pression au passage du tamis moléculaire ou de la membrane et la voie thermique nécessite des moyens de refroidissement ou d'injection d'oxygène pur au moment de la combustion. Ainsi, les installations pour la mise en oeuvre de ces procédés occupent des volumes importants. Le procédé dit « PSA », acronyme de « Pressure Swing Absorption » utilise une absorption sélective des gaz ayant une affinité avec certains zéolites. Ce procédé de l'art antérieur, fonctionnant à température ambiante, conduit aux installations de séparation gazeuses les plus compactes connues de l'art antérieur. Il nécessite cependant pour sa mise en oeuvre des installations occupant un volume de l'ordre de la dizaine de m3 au minimum. Or, une grande partie du CO2 rejeté dans l'atmosphère est produite par le transport ou par des installations domestiques, c'est-à-dire dans des véhicules ou dans des bâtiments qui ne peuvent pas intégrer des installations d'un tel volume. Ainsi, la captation de CO2 par les procédés de l'art antérieur est limitée aux applications mettant en oeuvre des installations de production fixes, telles que des centrales thermiques, des cimenteries ou, pour les plus compactes, des chaudières industrielles. The chemical route requires sufficient heat exchange surfaces between the gas and the carbon dioxide absorbing products. The mechanical path requires a difference in pressure at the passage of the molecular sieve or the membrane and the thermal path requires means for cooling or injecting pure oxygen at the moment of combustion. Thus, the installations for carrying out these processes occupy large volumes. The process known as "PSA", an acronym for "Pressure Swing Absorption" uses a selective absorption of gases having an affinity with certain zeolites. This method of the prior art, operating at ambient temperature, leads to the most compact gas separation plants known from the prior art. However, it requires for its implementation facilities occupying a volume of the order of ten or more m 3 minimum. However, a large part of the CO 2 released into the atmosphere is produced by transport or by domestic installations, that is to say in vehicles or buildings that can not integrate installations of such a volume. . Thus, the capture of CO 2 by the processes of the prior art is limited to applications using fixed production facilities, such as thermal power plants, cement plants or, for the more compact, industrial boilers.
L'invention vise à résoudre les inconvénients de l'art antérieur et notamment à proposer un dispositif et un procédé de séparation du dioxyde de carbone d'un mélange gazeux dont le volume soit suffisamment réduit pour être installé dans un véhicule ou dans un local d'habitation d'un particulier. The invention aims to solve the drawbacks of the prior art and in particular to provide a device and a method for separating carbon dioxide from a gaseous mixture whose volume is sufficiently small to be installed in a vehicle or in a room for cleaning. dwelling of an individual.
À cette fin, l'invention concerne un dispositif pour la séparation du dioxyde de carbone contenu dans un mélange gazeux, lequel dispositif comprend une cellule élémentaire comportant : To this end, the invention relates to a device for separating the carbon dioxide contained in a gaseous mixture, which device comprises an elementary cell comprising:
a. un premier ensemble d'électrodes à membrane constituant une souscellule électrochimique sous la forme d'une pile à combustible à oxyde solide fonctionnant en mode production d'électricité ; b. un deuxième ensemble d'électrodes à membrane constituant une sous-cellule électrochimique sous la forme d'une pile à combustible à carbonate fondu fonctionnant en mode électrolyseur ; at. a first set of membrane electrodes constituting an electrochemical subcell in the form of a solid oxide fuel cell operating in power generation mode; b. a second set of membrane electrodes constituting an electrochemical sub-cell in the form of a molten carbonate fuel cell operating in the electrolyser mode;
c. une première plaque intermédiaire poreuse électriquement conductrice
intercalée entre le premier et le deuxième ensemble d'électrodes à membrane et en liaison électrique et hydraulique avec ceux-ci ; vs. a first electrically conductive porous intermediate plate interposed between the first and the second set of membrane electrodes and in electrical and hydraulic connection therewith;
d. des moyens d'injection pour injecter le mélange gazeux dans ladite première plaque intermédiaire poreuse ; d. injection means for injecting the gaseous mixture into said first porous intermediate plate;
e. une deuxième plaque intermédiaire poreuse électriquement conductrice en liaison électrique et hydraulique avec le deuxième ensemble d'électrodes à membrane ; e. a second electrically conductive porous intermediate plate in electrical and hydraulic connection with the second set of membrane electrodes;
f. des moyens de collecte, pour collecter le dioxyde de carbone séparé dumélange gazeux sur ladite deuxième plaque intermédiaire poreuse. Ainsi, l'invention utilise avantageusement une sous-cellule électrochimique sous la forme d'une pile à combustible à carbonate fondu ou MCFC, acronyme de « Molten Cabonate Fuel Cell » fonctionnant en mode électrolyseur et effectuant l'électrolyse de l'eau contenu dans le mélange gazeux. L'énergie électrique nécessaire à cette électrolyse est en partie fournie par la sous-cellule électrochimique à oxyde solide, ou SOFC, acronyme de « Solid Oxyde Fuel Cell », laquelle cellule électrochimique fonctionne en mode pile à combustible. Ainsi, le dispositif objet de l'invention produit une bonne part de l'énergie nécessaire à son fonctionnement. Basé sur une juxtaposition de sous-cellules électrochimiques constituées d'ensemble d'électrodes à membrane, le dispositif objet de l'invention est également très compact. Ainsi, le dispositif objet de l'invention est particulièrement adapté pour la séparation du C02 des gaz d'échappement du moteur à combustion interne d'un véhicule, ou pour une installation sur une chaudière domestique et plus généralement pour toute application où la compacité du dispositif de séparation est un facteur essentiel. f. collection means for collecting the carbon dioxide separated from the gaseous mixture on said second porous intermediate plate. Thus, the invention advantageously uses an electrochemical sub-cell in the form of a molten carbonate fuel cell or MCFC, acronym for "Molten Cabonate Fuel Cell" operating in electrolyser mode and performing the electrolysis of the water contained in the gaseous mixture. The electrical energy required for this electrolysis is partly provided by the solid oxide electrochemical sub-cell, or SOFC, an acronym for "Solid Oxide Fuel Cell", which electrochemical cell operates in fuel cell mode. Thus, the device object of the invention produces a good part of the energy necessary for its operation. Based on a juxtaposition of electrochemical sub-cells consisting of a set of membrane electrodes, the device that is the subject of the invention is also very compact. Thus, the device that is the subject of the invention is particularly suitable for separating the CO 2 from the exhaust gases of the internal combustion engine of a vehicle, or for an installation on a domestic boiler and more generally for any application where the compactness separation device is an essential factor.
L'invention concerne également un procédé de séparation du dioxyde carbone d'un mélange gazeux comprenant de la vapeur d'eau lequel procédé est mis en oeuvre au moyen du dispositif objet de l'invention comportant une pluralité de cellules élémentaires juxtaposées, lequel procédé comprend les étapes consistant à : The invention also relates to a process for separating carbon dioxide from a gaseous mixture comprising steam which process is implemented by means of the device of the invention comprising a plurality of juxtaposed elementary cells, which method comprises the steps of:
i. injecter le mélange gazeux dans la première plaque intermédiaire poreuse de la ième cellule élémentaire; i. injecting the gaseous mixture into the first porous intermediate plate of the ith elementary cell;
ii. réaliser l'électrolyse de l'eau contenue dans ledit mélange dans la ième sous-cellule électrochimique MCFC de sorte à former, à la cathode de ladite sous-cellule, du dioxyde de carbone (C02) et du dioxygène (02), et
du dihydrogène (H2) à l'anode de ladite sous-cellule ; ii. performing the electrolysis of the water contained in said mixture in the i th MCFC electrochemical sub-cell so as to form, at the cathode of said sub-cell, carbon dioxide (CO 2 ) and dioxygen (O 2 ) , and dihydrogen (H 2 ) at the anode of said sub-cell;
iii. diffuser H2 vers la cathode de la sous-cellule électrochimique SOFC de la ième cellule élémentaire à travers la première plaque intermédiaire poreuse de ladite ième cellule iii. diffusing H 2 to the cathode of the SOFC electrochemical sub-cell of the i th elementary cell through the first porous intermediate plate of said i th cell
iv. diffuser C02 et 02 à travers la deuxième plaque intermédiaire poreuse de la ième cellule élémentaire vers l'anode de la sous-cellule électrochimique SOFC de la (i+1 )ème cellule élémentaire ; iv. diffusing C0 2 and O 2 through the second porous intermediate plate of the i th elementary cell to the anode of the SOFC electrochemical sub-cell of the (i + 1) th elementary cell;
v. consommer O2 dans la (i+1 )ème sous-cellule SOFC pour la production d'électricité et récolter le CO2 sur la deuxième plaque intermédiaire poreuse de la ième cellule élémentaire. v. consume O 2 in the (i + 1) th SOFC sub-cell for the production of electricity and collect the CO 2 on the second porous intermediate plate of the ith elementary cell.
Ainsi, le fonctionnement des sous-cellules MCFC en mode électrolyseur impose le transfert à travers la membrane, de l'anode à la cathode de ces sous-cellules électrochimiques, des ions CO3 2" pour ainsi opérer la séparation du CO2 du mélange gazeux. L'oxygène et l'hydrogène produits lors de l'électrolyse dans la sous-cellule MCFC, sont utilisés pour le fonctionnement des piles SOFC connectées de part et d'autre de ladite sous-cellule MCFC, piles SOFC où l'oxygène réagit avec l'hydrogène issue de l'électrolyse dans la pile MCFC, dans une réaction d'oxydo-réduction, de sorte à former de l'eau. Ainsi, le procédé permet de récupérer le CO2 purifié sur la deuxième plaque intermédiaire poreuse de la ième cellule et les autres composants du mélange gazeux sur la première plaque intermédiaire poreuse de la ième cellule. Thus, the operation of the MCFC sub-cells in the electrolyser mode requires the transfer of the CO 3 2 - ions through the membrane, from the anode to the cathode of these electrochemical sub-cells so as to effect the separation of the CO 2 from the mixture. The oxygen and hydrogen produced during the electrolysis in the MCFC sub-cell are used for the operation of the SOFC cells connected on either side of said MCFC sub-cell, SOFC cells where the oxygen reacts with the hydrogen resulting from the electrolysis in the MCFC stack, in a redox reaction, so as to form water Thus, the process makes it possible to recover the purified CO 2 on the second porous intermediate plate the i th cell and the other components of the gas mixture on the first porous intermediate plate of the i th cell.
L'invention est avantageusement mise en oeuvre selon les modes de réalisation exposés ci-après, lesquels sont à considérer individuellement ou selon toute combinaison techniquement opérante. The invention is advantageously implemented according to the embodiments described below, which are to be considered individually or in any technically operative combination.
Avantageusement, le dispositif objet de l'invention comprend une pluralité de cellules élémentaires juxtaposées, chaque cellule élémentaire étant connectée mécaniquement, hydrauliquement et électriquement à la suivante par l'intermédiaire de sa deuxième plaque intermédiaire poreuse. Ainsi, le dispositif objet de l'invention est aisément adapté à la quantité et au débit de mélange gazeux à traiter, en multipliant le nombre de cellules élémentaires. Advantageously, the device according to the invention comprises a plurality of juxtaposed elementary cells, each elementary cell being mechanically, hydraulically and electrically connected to the next via its second porous intermediate plate. Thus, the device that is the subject of the invention is easily adapted to the quantity and flow rate of gaseous mixture to be treated, by multiplying the number of elementary cells.
Avantageusement, les plaques intermédiaires poreuses du dispositif objet de l'invention sont constituées d'un matériau céramique. Ainsi, la dilatation thermique différentielle entre lesdites plaques poreuses et les cellule électrochimiques est réduite
et le dispositif est plus résistant à des cycles thermiques d'amplitude importante tels que rencontrés pour des applications mobiles. Advantageously, the porous intermediate plates of the device which is the subject of the invention consist of a ceramic material. Thus, the differential thermal expansion between said porous plates and the electrochemical cells is reduced and the device is more resistant to thermal cycles of high amplitude as encountered for mobile applications.
Selon un exemple de réalisation les plaques poreuses sont constituées de carbure de silicium (SiC). According to an exemplary embodiment, the porous plates consist of silicon carbide (SiC).
Selon un autre mode de réalisation les plaques poreuses sont constituées de titanate de carbure de silicium (Ti3SiC2). According to another embodiment, the porous plates consist of silicon carbide titanate (Ti 3 SiC 2 ).
Ces céramiques présentent des propriétés caractéristiques des céramiques et des matériaux métalliques telles que la conductivité électrique et thermique, un module d'élasticité élevé et une résistance mécanique et à la corrosion à haute température. These ceramics exhibit characteristic properties of ceramics and metallic materials such as electrical and thermal conductivity, high modulus of elasticity and high temperature and corrosion resistance.
Avantageusement le dispositif objet de l'invention comprend en outre : Advantageously, the device which is the subject of the invention furthermore comprises:
g. un réservoir d'eau et des moyens pour collecter l'eau produite par les sous-cellules électrochimiques SOFC et l'envoyer dans ce réservoir ; h. des moyens pour injecter de l'eau de ce réservoir conjointement à l'injection du mélange gazeux dans les premières plaques intermédiaires poreuses des cellules élémentaires. boy Wut. a water tank and means for collecting the water produced by the SOFC electrochemical sub-cells and sending it into this tank; h. means for injecting water from this reservoir together with injecting the gaseous mixture into the first porous intermediate plates of the elementary cells.
Ainsi, le dispositif objet de l'invention est apte à traiter un mélange gazeux ne comprenant pas, ou pas suffisamment, de vapeur d'eau pour initier les réactions. Thus, the device that is the subject of the invention is capable of treating a gaseous mixture that does not include, or not enough, water vapor to initiate the reactions.
Selon un mode de réalisation du procédé objet de l'invention, utilisant un dispositif comprenant un réservoir d'eau, le mélange gazeux ne comprenant pas de vapeur d'eau, ledit procédé comprend avant l'étape i) une étape consistante à : According to one embodiment of the method which is the subject of the invention, using a device comprising a water reservoir, the gas mixture not comprising water vapor, said process comprises, before step i), a step consisting in:
vi. injecter de la vapeur d'eau avec le mélange gazeux pour initier la réaction. vi. injecting steam with the gaseous mixture to initiate the reaction.
L'injection d'un supplément d'eau n'est nécessaire que pour l'initiation de la réaction, ensuite, l'eau est recyclée depuis les sous-cellules SOFC. The injection of a supplement of water is only necessary for the initiation of the reaction, then the water is recycled from SOFC sub-cells.
Avantageusement, le procédé objet de l'invention comprend les étapes consistant à : Advantageously, the method which is the subject of the invention comprises the steps of:
vii comprimer le CO2 au sortir de la deuxième plaque intermédiaire poreuse pour le liquéfier ; vii compress the CO 2 out of the second porous intermediate plate to liquefy it;
viii. traiter à basse pression les autres composés du gaz séparé du CO2 et récoltés au sortir de la première plaque intermédiaire poreuse. viii. to treat at low pressure the other compounds of the gas separated from CO2 and harvested at the end of the first porous intermediate plate.
Ainsi, le dispositif objet de l'invention permet de comprimer le dioxyde de carbone sous forme liquide de sorte à réduire le volume de stockage. Thus, the device that is the subject of the invention makes it possible to compress the carbon dioxide in liquid form so as to reduce the storage volume.
L'invention concerne également un véhicule comprenant un moteur à combustion
interne et comportant : The invention also relates to a vehicle comprising a combustion engine internal and comprising:
x. un dispositif selon l'un des modes de réalisation précédents connecté à la sortie de l'échappement dudit moteur pour la mise en oeuvre d'un procédé selon le mode de réalisation précédent ; x. a device according to one of the preceding embodiments connected to the output of the exhaust of said engine for the implementation of a method according to the previous embodiment;
y. un réservoir apte à stocker du dioxyde de carbone sous forme liquéfiée, z. un générateur électrique apte à dériver une partie de la puissance du moteur pour générer un courant électrique apte à compléter la puissance électrique générée par les cellules SOFC ; there. a tank adapted to store carbon dioxide in liquefied form, z. an electric generator adapted to derive a portion of the engine power to generate an electric current capable of supplementing the electric power generated by the SOFC cells;
t. des moyens pour connecter électriquement le générateur électrique avec les premières plaques poreuses des cellules élémentaires. Un tel véhicule capte toutes ses émissions de CO2 lesquelles sont récupérées dudit véhicule en vue de leur fixation, par exemple, lors de chaque plein de carburant dudit véhicule. La majeure partie de l'énergie nécessaire au fonctionnement du dispositif de captation étant fournie par les cellules SOFC fonctionnant en mode pile à combustible, le fonctionnement du dispositif reste compatible avec l'utilisation du véhicule sans conséquence inacceptable sur les performances dudit véhicule. t. means for electrically connecting the electric generator with the first porous plates of the elementary cells. Such a vehicle captures all its CO 2 emissions which are recovered from said vehicle for attachment, for example, each time the vehicle is refueled. Most of the energy required for the operation of the capture device being provided by the SOFC cells operating in fuel cell mode, the operation of the device remains compatible with the use of the vehicle without unacceptable consequences on the performance of said vehicle.
L'invention est exposée ci-après selon ses modes de réalisation préférés, nullement limitatifs, et en référence aux figures 1 à 8, dans lesquelles : The invention is described below according to its preferred embodiments, in no way limiting, and with reference to FIGS. 1 to 8, in which:
- la figure 1 représente schématiquement une installation de séparation du dioxyde de carbone d'un mélange gazeux comprenant un dispositif selon l'invention ; FIG. 1 schematically represents an installation for separating carbon dioxide from a gaseous mixture comprising a device according to the invention;
- la figure 2 montre selon une vue schématique en coupe un exemple de réalisation du dispositif objet de l'invention ; - Figure 2 shows in a schematic sectional view an embodiment of the device object of the invention;
- la figure 3 représente en perspective une cellule élémentaire selon un exemple de réalisation du dispositif objet de l'invention, figure 3A, assemblée, et figure 3B selon une vue en éclaté ; - Figure 3 shows in perspective an elementary cell according to an embodiment of the device of the invention, Figure 3A, assembled, and Figure 3B in an exploded view;
- la figure 4 est une vue en perspective des plaques intermédiaires poreuses du dispositif objet de l'invention, selon un exemple de réalisation de celui-ci ; FIG. 4 is a perspective view of the porous intermediate plates of the device that is the subject of the invention, according to an exemplary embodiment thereof;
- la figure 5 est une vue en perspective d'un exemple de réalisation du dispositif objet de l'invention comprenant une pluralité de cellules élémentaires assemblées ; FIG. 5 is a perspective view of an exemplary embodiment of the device according to the invention comprising a plurality of assembled elementary cells;
- la figure 6 est une vue en perspective et en éclaté du dispositif de la figure 5 ;
- la figure 7 est une vue en perspective et en éclaté d'un exemple de réalisation de l'extrémité correspondant à la borne négative du dispositif représenté figure 5 ; FIG. 6 is a perspective and exploded view of the device of FIG. 5; - Figure 7 is a perspective view and exploded of an embodiment of the end corresponding to the negative terminal of the device shown in Figure 5;
- et la figure 8 est une vue en perspective et en éclaté de l'extrémité correspondant à la borne positive du dispositif de la figure 5. and FIG. 8 is a perspective and exploded view of the end corresponding to the positive terminal of the device of FIG. 5.
Figure 1 , selon un exemple de réalisation, une installation de séparation du dioxyde de carbone d'un mélange gazeux comprend une source d'émission dudit mélange (100). Un tel mélange comprend du C02 et d'autres gaz, dits diluants, tels que N2. Une telle source est, selon un exemple de réalisation, une machine thermique consommant un combustible fossile telle qu'un moteur à combustion interne ou une chaudière. Ce mélange gazeux (100) est initialement stocké dans un réservoir (181 ) muni d'un évent (182) de sécurité. Ledit réservoir (181 ) coopère avec une vanne (183) régulée pour contrôler le débit de gaz dans l'installation. Selon cet exemple de réalisation, le mélange gazeux du réservoir tampon (181 ) est réchauffé dans un moyen (184) adapté, pour le porter à une température adéquate pour les réactions ultérieures. Ce moyen de chauffage (184) est par exemple électrique ou utilise toute autre forme d'énergie disponible, en fonction de l'application. Dans le cas où le mélange gazeux initial (100) ne contient pas ou pas suffisamment d'eau, de la vapeur d'eau (101 ) est mélangée au gaz dans des moyens de mélange (185) appropriés. Le mélange gazeux (102) comprenant de la vapeur d'eau est envoyé vers le dispositif (1 10) objet de l'invention pour en séparer les constituants, et plus particulièrement le C02. En sortie du dispositif (1 10) objet de l'invention le C02 (103) séparé du mélange gazeux est envoyé vers des moyens de stockage (191 ) depuis lesquels il est ensuite envoyé vers un traitement ultérieur. Selon un mode de réalisation particulier, ces moyens de stockage (191 ) sont combinés avec des moyens de compression (non représentés) afin de stocker ledit C02 sous une forme liquide. Figure 1, according to an exemplary embodiment, a carbon dioxide separation plant of a gaseous mixture comprises an emission source of said mixture (100). Such a mixture comprises CO 2 and other gases, called diluents, such as N 2 . Such a source is, according to an exemplary embodiment, a thermal machine consuming a fossil fuel such as an internal combustion engine or a boiler. This gaseous mixture (100) is initially stored in a tank (181) provided with a safety vent (182). Said reservoir (181) cooperates with a regulated valve (183) to control the flow of gas in the installation. According to this embodiment, the gas mixture of the buffer tank (181) is heated in a means (184) adapted to bring it to a temperature suitable for subsequent reactions. This heating means (184) is for example electric or uses any other form of available energy, depending on the application. In the case where the initial gas mixture (100) contains no or not enough water, water vapor (101) is mixed with the gas in appropriate mixing means (185). The gas mixture (102) comprising steam is sent to the device (1 10) object of the invention to separate the constituents, and more particularly the CO 2 . At the output of the device (1 10) which is the subject of the invention, the CO 2 (103) separated from the gaseous mixture is sent to storage means (191) from which it is then sent to a subsequent treatment. According to a particular embodiment, these storage means (191) are combined with compression means (not shown) to store said C0 2 in a liquid form.
Selon une autre sortie du dispositif (1 10) objet de l'invention, le mélange (104) comprenant les diluants et de la vapeur d'eau est envoyé vers un condenseur (192), qui permet de récupérer l'eau (101 ') contenue dans ledit mélange (104), les diluants (105) étant évacués, par exemple, à l'air libre. Des moyens (193) permettent de contrôler le niveau de l'eau (101 ') récupérée par condensation dans le condenseur (192) et de piloter une vanne (194) pour envoyer cette eau vers un réservoir (195) tampon. Le
volume de ce réservoir (195), c'est-à-dire le volume d'eau tampon, est calculé en fonction des caractéristiques de l'installation et de la nature du mélange gazeux (100) à traiter. L'eau (101 ') contenue dans ce réservoir tampon est envoyée vers des moyens de chauffage (196) pour former de la vapeur (101 ) et la mélanger au mélange gazeux (100) initial. Selon un exemple de réalisation, cette eau est également utilisée comme fluide caloporteur dans le condenseur (192). Ainsi, l'eau est traitée en circuit fermé dans l'installation et le volume du réservoir d'eau tampon (195) est calculé en fonction du débit visé et de la quantité d'eau initialement nécessaire pour amorcer le fonctionnement de l'installation mettant en oeuvre le dispositif(1 10) objet de l'invention. According to another output of the device (1 10) object of the invention, the mixture (104) comprising the diluents and water vapor is sent to a condenser (192), which allows to recover the water (101 ' ) contained in said mixture (104), the diluents (105) being evacuated, for example, in the open air. Means (193) control the level of water (101 ') recovered by condensation in the condenser (192) and control a valve (194) to send the water to a reservoir (195) buffer. The volume of this tank (195), that is to say the volume of buffer water, is calculated according to the characteristics of the installation and the nature of the gaseous mixture (100) to be treated. The water (101 ') contained in this buffer tank is sent to heating means (196) to form steam (101) and mix with the initial gas mixture (100). According to an exemplary embodiment, this water is also used as heat transfer fluid in the condenser (192). Thus, the water is treated in closed circuit in the installation and the volume of the buffer water tank (195) is calculated according to the target flow rate and the amount of water initially required to start the operation of the installation implementing the device (1 10) object of the invention.
Figure 2, selon une représentation schématique, le dispositif objet de l'invention FIG. 2, according to a schematic representation, the device that is the subject of the invention
(110) comprend une pluralité (i-1 ), i, (i+1 ) de cellules élémentaires empilées. Chaque cellule élémentaire est constituée de sous-cellules : (110) comprises a plurality (i-1), i, (i + 1) of stacked elementary cells. Each elementary cell consists of sub-cells:
- une sous-cellule électrochimique (21 1 ) de type SOFC fonctionnant en mode production d'électricité ; an electrochemical sub-cell (21 1) of the SOFC type operating in power generation mode;
- une première plaque poreuse (212) intermédiaire pour l'acheminement, dans la cellule élémentaire, du gaz à traiter ; a first porous plate (212) intermediate for conveying, in the elementary cell, the gas to be treated;
- une sous-cellule (213) électrochimique de type MCFC fonctionnant en mode électrolyse ; an electrochemical sub-cell (213) of the MCFC type operating in electrolysis mode;
- une seconde plaque poreuse (214) intermédiaire pour la collecte du C02 séparé et la collecte des électrons nécessaires pour ioniser l'oxygène utilisée pour le fonctionnement de la sous-cellule électrochimique SOFC suivante dans l'empilement. a second porous intermediate plate (214) for collecting the separated CO 2 and collecting the electrons necessary for ionizing the oxygen used for the operation of the next SOFC electrochemical sub-cell in the stack.
Les premières plaques intermédiaires poreuses (212) de chaque cellule élémentaire permettent également d'acheminer dans le dispositif des électrons apportés extérieurement à celui-ci. Ces plaques (212) sont reliées à la borne négative du dispositif objet de l'invention, les secondes plaques intermédiaires (214) poreuses étant reliées à la borne positive dudit dispositif. The first porous intermediate plates (212) of each elementary cell also make it possible to convey electrons provided externally thereto into the device. These plates (212) are connected to the negative terminal of the device object of the invention, the second intermediate plates (214) porous being connected to the positive terminal of said device.
Le mélange de gaz (102) comprenant du dioxyde de carbone et de la vapeur d'eau est injecté dans la première plaque intermédiaire poreuse (212). En suivant les échanges entre les sous-cellules d'une cellule élémentaire (i), CO2 et H2O forment H2 et des ions CO3 2" par électrolyse de l'eau sur les sites catalytiques de la sous-cellule MCFC (213). Les ions CO3 2" diffusent à travers la membrane de la sous-cellule
MCFC (213). À la cathode de ladite sous-cellule (213), les ions CO3 2" libèrent un électron générant CO2 et 1/2.02. L'hydrogène formée à l'anode de la sous-cellule MCFC (213) diffuse à travers les pores de la première plaque intermédiaire (212) jusqu'à la sous-cellule SOFC (21 1 ). De même, l'oxygène formé à la cathode de la sous-cellule MCFC (213) diffuse à travers les pores de la deuxième plaque poreuse (214), tout comme les électrons libérés à cette cathode, jusqu'à l'anode de la sous-cellule SOFC (21 1 ) de la cellule élémentaire (i+1 ) suivante dans l'empilement. The gas mixture (102) comprising carbon dioxide and water vapor is injected into the first porous intermediate plate (212). By following the exchanges between the sub-cells of an elementary cell (i), CO 2 and H 2 O form H 2 and CO 3 2 - ions by electrolysis of water on the catalytic sites of the MCFC sub-cell. (213) The CO 3 2 - ions diffuse through the membrane of the sub-cell MCFC (213). At the cathode of said sub-cell (213), the CO 3 2 - ions release an electron generating CO 2 and 1 / 2.0 2. The hydrogen formed at the anode of the MCFC sub-cell (213) diffuses through the pores of the first intermediate plate (212) to the SOFC sub-cell (21 1) Similarly, the oxygen formed at the cathode of the MCFC sub-cell (213) diffuses through the pores of the second porous plate (214), just like the electrons released at this cathode, to the anode of the SOFC sub-cell (21 1) of the next elementary cell (i + 1) in the stack.
Sur les sites catalytiques de l'anode de la sous-cellule SOFC (211 ) de la cellule élémentaire (i+1 ), O2 forme des ions O2 " avec les électrons libérés à la seconde plaque poreuse (214) de la ième cellule élémentaire, précédente dans l'empilement. Les ions O2 ainsi générés, diffusent à travers la (i+1 )ème sous-cellule SOFC (211 ) pour réagir à la cathode de cette sous-cellule avec les molécules H2 produites à la cathode de la sous-cellule MCFC (213) de cette même (i+1 )ème cellule élémentaire. Ainsi, à la cathode de la sous-cellule SOFC (211 ) de la (i+1 )ème cellule élémentaire, H2 et O2 " réagissent sur les sites catalytiques de ladite cellule SOFC (21 1 ) pourformer H2O dans la même veine fluide dans laquelle H2O est « consommée » par la cellule MCFC (213). Ainsi, le dispositif est apte à traiter un mélange gazeux (101 ) ne contenant pas d'eau, à condition d'initier la réaction en injectant de l'eau dans ledit gaz. Ensuite, l'eau circule en circuit fermé. On the catalytic sites of the anode of the SOFC sub-cell (211) of the elementary cell (i + 1), O 2 forms ions O 2 " with the electrons released at the second porous plate (214) of the ith elementary cell, preceding in the stack The O 2 ions thus generated diffuse through the (i + 1) th SOFC sub-cell (211) to react with the cathode of this sub-cell with the H 2 molecules produced at the cathode of the MCFC sub-cell (213) of this same (i + 1) th elementary cell Thus, at the cathode of the SOFC sub-cell (211) of the (i + 1) th elementary cell, H 2 and O 2 " react on the catalytic sites of said SOFC cell (21 1) to form H 2 O in the same fluid vein in which H 2 O is" consumed "by the MCFC cell (213). Thus, the device is able to treat a gaseous mixture (101) containing no water, provided to initiate the reaction by injecting water into said gas. Then, the water circulates in closed circuit.
La sous-cellule SOFC (21 1 ) fonctionne en mode générateur et génère une partie des électrons nécessaires au fonctionnement de la sous-cellule MCFC (213) fonctionnant en mode électrolyseur. Cette sous cellule SOFC (21 1 ) étant le siège d'une réaction exothermique, elle produit également une partie de la chaleur nécessaire pour compenser le caractère endothermique de la réaction d'électrolyse dans la sous-cellule MCFC (213), laquelle sous-cellule MCFC (213) permet ainsi de dissiper l'énergie thermique libérée par la réaction exothermique dont la sous-cellule SOFC (21 1 ) est le siège. Le caractère endothermique de la réaction d'électrolyse, dans la sous-cellule MCFC (213), est fonction de la température du mélange gazeux à traiter et conditionne également la quantité d'énergie électrique nécessaire au fonctionnement de cette sous-cellule. Ainsi, hormis la phase de démarrage où un apport externe d'énergie est nécessaire, le point de fonctionnement du dispositif objet de l'invention est sélectionné en fonction de la température du mélange gazeux à traiter de sorte que celui-ci
fonctionne de manière autonome sans apport d'énergie externe ou en minimisant cet apport externe d'énergie, électrique ou thermique, en fonction des sources disponibles selon l'application visée. La température de fonctionnement du dispositif est limitée à 650° C, qui correspond à une température de fonctionnement courante pour les sous-cellules de type MCFC (213). Typiquement la consommation électrique en apport externe est de 1 .KW. heure pour 0,86 Kg à 2,21 Kg de C02 séparé. The SOFC sub-cell (21 1) operates in generator mode and generates a portion of the electrons necessary for the operation of the MCFC sub-cell (213) operating in electrolyser mode. Since this SOFC sub-cell (21 1) is the seat of an exothermic reaction, it also produces part of the heat necessary to compensate for the endothermic nature of the electrolysis reaction in the MCFC sub-cell (213), which sub-cell MCFC cell (213) thus dissipates the thermal energy released by the exothermic reaction whose sub-cell SOFC (21 1) is the seat. The endothermic nature of the electrolysis reaction in the MCFC sub-cell (213) is a function of the temperature of the gaseous mixture to be treated and also conditions the amount of electrical energy necessary for the operation of this sub-cell. Thus, apart from the starting phase where an external supply of energy is necessary, the operating point of the device according to the invention is selected as a function of the temperature of the gaseous mixture to be treated so that it operates autonomously without external energy input or by minimizing this external supply of energy, electrical or thermal, depending on the sources available according to the intended application. The operating temperature of the device is limited to 650 ° C, which corresponds to a current operating temperature for MCFC sub-cells (213). Typically the external power consumption is 1 .KW. hour for 0.86 Kg to 2.21 Kg of separated C0 2 .
Figure 3, selon un exemple de réalisation, une cellule élémentaire (300) constituée d'un empilement de sous-cellules (211 , 212, 213, 214) de forme sensiblement quadrangulaire, lesdites sous-cellules sont insérées entre deux types de joints (31 1 , 312) ajourés selon une ouverture centrée sensiblement rectangulaire correspondant à la surface d'échange entre les sous-cellule et dont le pourtour assure la fonction d'étanchéité. Les joints de type 1 (31 1 ), sont placés de part et d'autre de chaque cellule SOFC (21 1 ) et MCFC (213) et réalisent l'étanchéité avec la partie non poreuse des plaques intermédiaires (212, 213). Les joints de type 2 (312) permettent de réaliser l'étanchéité entre les plaques intermédiaires, et comprennent des lumières (321 , 322) oblongues s'étendant dans des directions sensiblement perpendiculaires, sur la bordure externe du joint, et qui, une fois les cellules élémentaires (300) empilées et assemblées, dessinent des circuits de distribution du mélange gazeux entrant, et de collecte des gaz séparés. FIG. 3, according to an exemplary embodiment, an elementary cell (300) constituted by a stack of sub-cells (211, 212, 213, 214) of substantially quadrangular shape, said sub-cells being inserted between two types of joints ( 31 1, 312) perforated in a substantially rectangular centered opening corresponding to the exchange surface between the sub-cell and whose periphery provides the sealing function. The type 1 joints (31 1) are placed on either side of each SOFC (21 1) and MCFC (213) cell and seal with the non-porous part of the intermediate plates (212, 213). The type 2 seals (312) provide sealing between the intermediate plates, and include oblong slots (321, 322) extending in substantially perpendicular directions, on the outer edge of the seal, and which, once the stacked and assembled elementary cells (300) draw distribution circuits for the incoming gas mixture and separate gas collection.
Figure 4, les plaques intermédiaires (212, 214) des deux types sont essentiellement les mêmes, la deuxième plaque intermédiaire (214) étant de structure identique à la première (212) mais tournée de 90° dans le sens horaire. Les joints de type 2 (312) correspondant à ces plaques intermédiaires comprennent à cette fin deux types d'encoches (421 , 422) sur deux côtés perpendiculaires desdits joints, lesquelles encoches agissent comme des détrompeurs lors du montage du dispositif objet de l'invention. Lesdites plaques poreuses (212, 214) sont constituées d'un matériau électriquement conducteur tel qu'un matériau métallique. Elles sont avantageusement constituées d'une céramique électriquement conductrice, dont le plus faible coefficient de dilatation thermique est plus adapté au montage en empilement et à la température de fonctionnement du dispositif objet de l'invention. Parallèlement, la faible densité de ces céramiques permet de réduire le poids du dispositif. La porosité des plaques est définie de sorte à minimiser la perte de charge à travers le parallélépipède poreux
desdites plaques tout en maximisant la surface effective de contact avec les autres sous-cellules, de sorte à réduire la résistance électrique de contact. Typiquement la densité de courant aux interfaces est de l'ordre de 200 mA.cm"2. La surface de contact mécanique étant ainsi optimisée, le dispositif objet de l'invention est apte à fonctionner sous pression. Figure 4, the intermediate plates (212, 214) of the two types are essentially the same, the second intermediate plate (214) being identical in structure to the first (212) but rotated 90 ° clockwise. The type 2 seals (312) corresponding to these intermediate plates comprise for this purpose two types of notches (421, 422) on two perpendicular sides of said seals, which notches act as keyed during assembly of the device object of the invention. . Said porous plates (212, 214) consist of an electrically conductive material such as a metallic material. They are advantageously constituted by an electrically conductive ceramic, whose lower coefficient of thermal expansion is more suitable for mounting in stack and at the operating temperature of the device object of the invention. At the same time, the low density of these ceramics makes it possible to reduce the weight of the device. The porosity of the plates is defined so as to minimize the pressure drop across the porous parallelepiped said plates while maximizing the effective contact area with the other sub-cells, so as to reduce the electrical contact resistance. Typically the current density at the interfaces is of the order of 200 mA.cm -2 .The mechanical contact surface thus being optimized, the device which is the subject of the invention is able to operate under pressure.
Figure 5, le dispositif (1 10) objet de l'invention est constitué de l'assemblage de telles cellules élémentaires. À titre d'exemple, la masse d'un tel dispositif est de l'ordre de 500 Kg pour une capacité de traitement d'environ 103 Kg de C02 par heure. Ainsi, le dispositif objet de l'invention est particulièrement bien adapté au traitement des gaz d'échappement de véhicules tels que des locotracteurs, des poids lourds, des bateaux de plaisance ou de tourisme, des engins de chantier ou d'exploitation agricole, ainsi que des chaudières domestiques. Selon cet exemple de réalisation, le dispositif (1 10) objet de l'invention comprend une pluralité de cellules élémentaires empilées et maintenues entre elles par serrage au moyens de tirants (550) prenant en étau lesdites cellules élémentaires entre deux plaques (512, 514) dites d'extrémité. Les deux extrémités (522, 524) du dispositif objet de l'invention, comprennent, selon ce mode de réalisation, des moyens pour injecter le mélange gazeux à traiter et collecter les produits issus de ce traitement. Ainsi, la première extrémité (522) correspondant à borne positive du dispositif comprend des moyens pour injecter le mélange gazeux à traiter et des moyens pour collecter une partie du C02 séparé de ce mélange. La seconde extrémité (524) qui correspond à la borne négative du dispositif comprend des moyens pour collecter le mélange constitué par la vapeur d'eau et les diluants ainsi qu'une partie du C02 séparé du mélange gazeux initial. Figure 5, the device (1 10) object of the invention consists of the assembly of such elementary cells. By way of example, the mass of such a device is of the order of 500 kg for a treatment capacity of approximately 103 kg of CO 2 per hour. Thus, the device of the invention is particularly well suited to the treatment of vehicle exhaust gases such as locomotives, heavy goods vehicles, recreational or tourism boats, construction or farm machinery, as well as than domestic boilers. According to this exemplary embodiment, the device (1 10) which is the subject of the invention comprises a plurality of elementary cells stacked and held together by clamping by means of tie rods (550) which clamp said elementary cells between two plates (512, 514 ) say end. The two ends (522, 524) of the device according to the invention comprise, according to this embodiment, means for injecting the gaseous mixture to be treated and collecting the products resulting from this treatment. Thus, the first end (522) corresponding to the positive terminal of the device comprises means for injecting the gaseous mixture to be treated and means for collecting a portion of C0 2 separated from this mixture. The second end (524) corresponding to the negative terminal of the device comprises means for collecting the mixture consisting of water vapor and diluents and a portion of CO 2 separated from the initial gas mixture.
Figure 6, selon une vue en éclaté d'un exemple de réalisation du dispositif objet de l'invention, le mélange gazeux à traiter est injecté, à la première extrémité, par des moyens de connexion (602) en partie supérieure du dispositif selon cette vue et circule dans ledit dispositif par l'intermédiaire du conduit dessiné en partie supérieure de ce dispositif par les lumières oblongues supérieures (321 ) sensiblement horizontales des joints de type 2 dudit dispositif. Le mélange comprenant la vapeur d'eau et les diluants est collecté à la seconde extrémité par des moyens (604) en communication avec le conduit dessiné par les rainures oblongues (321 ) situés en partie inférieure des joints de type 2. Des moyens (603) de collecte du C02 sont placés sensiblement au centre de
chacune des plaques (512, 514) d'extrémité en communication avec les conduits dessinés par les rainures oblongues (322) sensiblement verticales des joints de type 2. FIG. 6, according to an exploded view of an exemplary embodiment of the device that is the subject of the invention, the gaseous mixture to be treated is injected at the first end by connection means (602) at the top of the device according to this seen and circulates in said device through the duct drawn in the upper part of this device by the upper oblong slots (321) substantially horizontal type 2 joints of said device. The mixture comprising water vapor and diluents is collected at the second end by means (604) in communication with the duct drawn by the oblong grooves (321) located at the bottom of the type 2 seals. Means (603) ) C0 2 collection are placed substantially in the center of each of the end plates (512, 514) in communication with the ducts drawn by the substantially vertical oblong grooves (322) of the type 2 seals.
Figure 7, selon un exemple de réalisation du dispositif objet de l'invention, l'extrémité (524) correspondant à la borne négative de ce dispositif, comprend un connecteur (704) apte à collecter dans sa partie basse le mélange constitué des diluants et de la vapeur d'eau, par une lumière oblongue (721 ) en communication avec les lumières oblongues (321 ) adjacentes des joints de type 2. Cette lumière oblongue (721 ) du connecteur (704) est en connexion hydraulique avec les moyens (604) de collecte de ce mélange. Ce connecteur (704) comprend en outre des lumières oblongues (722) sensiblement verticales en communication avec les lumières oblongues (322) adjacentes des joints de type 2. Un cache (703), comprenant des lumières oblongues correspondantes, obstruela lumière oblongue (721 ) inférieure dudit connecteur (704) en conservantla communicationhydraulique des lumières oblongues verticales avec la plaque d'extrémité (514), laquelle plaque d'extrémité comprend sur sa face interne un usinage (714) pour collecter le C02 circulant dans ces lumières verticales et le convoyer vers les moyens de collecte (603) du C02 au centre de cette plaque (514). 7, according to an exemplary embodiment of the device according to the invention, the end (524) corresponding to the negative terminal of this device, comprises a connector (704) adapted to collect in its lower part the mixture of diluents and water vapor, by an oblong slot (721) in communication with the adjacent oblong slots (321) of the type 2 seals. This oblong slot (721) of the connector (704) is in hydraulic connection with the means (604). ) of collecting this mixture. This connector (704) further comprises substantially vertical oblong slots (722) in communication with the adjacent oblong slots (322) of the type 2 seals. A cover (703), including corresponding oblong slots, oblong light (721) lower part of said connector (704) by keeping the hydraulic communication of the vertical oblong slots with the end plate (514), which end plate comprises on its inner face a machining (714) for collecting the C0 2 flowing in these vertical lights and the conveying to the collection means (603) of C0 2 in the center of this plate (514).
Figure 8, selon un exemple de réalisation du dispositif objet de l'invention, l'extrémité (522) correspondant à la borne positive dudit dispositif, comprend un connecteur (802) apte à collecter dans sa partie haute le mélange de gaz à traiter, par une lumière oblongue (821 ) en communication avec les lumières oblongues (321 ) adjacentes des joints de type 2. Cette lumière oblongue (821 ) du connecteur (802) est en connexion hydraulique avec les moyens (602) d'injection de ce mélange. Ce connecteur (802) comprend en outre des lumières oblongues (822) sensiblement verticales en communication avec les lumières oblongues (322) adjacentes des joints de type 2. Un cache (803) comprenant des lumières oblongues correspondantes, obstrue la lumière oblongue (821 ) supérieure dudit connecteur (802) en conservant la communication hydraulique des lumières oblongues verticales avec la plaque d'extrémité(512), laquelle plaque d'extrémité comprend, sur sa face interne, un usinage (812) pour collecter le C02 circulant dans ces lumières verticales et le convoyer vers les moyens de collecte (603) du C02 au centre de cette plaque (512). FIG. 8, according to an exemplary embodiment of the device that is the subject of the invention, the end (522) corresponding to the positive terminal of said device, comprises a connector (802) able to collect in its upper part the gas mixture to be treated, by an oblong slot (821) in communication with the adjacent oblong slots (321) of the type 2 seals. This oblong slot (821) of the connector (802) is in hydraulic connection with the injection means (602) of this mixture . This connector (802) further comprises substantially vertical oblong slots (822) in communication with the adjacent oblong slots (322) of the type 2 joints. A cover (803) including corresponding oblong slots obstructs the oblong slot (821). upper of said connector (802) while maintaining the hydraulic communication of the vertical oblong slots with the end plate (512), which end plate comprises, on its inner face, a machining (812) for collecting the C0 2 flowing in these vertical lights and convey it to the collection means (603) of C0 2 in the center of this plate (512).
La description ci-avant et les exemples de réalisation montrent que l'invention
atteint les objectifs visés, en particulier elle permet de réaliser un dispositif de séparation du C02 d'ungaz produit de combustion, lequel dispositif est particulièrement compact et peu consommateur d'énergie. En particulier, le dispositif objet de l'invention est adapté à une utilisation visant à collecter le dioxyde de carbone produit par un véhicule comportant un moteur à combustion interne. Selon cet exemple de réalisation, le C02 séparé du gaz d'échappement est avantageusement stocké sous forme liquéfiée de sorte à réduire le volume de stockage. À cette fin, une partie de la puissance du moteur thermique est avantageusement utilisée pour comprimer le gaz et pour produire, par un générateur, l'énergie électrique en supplément de la production des sous-cellules SOFC pour le fonctionnement des sous-cellules MCFC fonctionnant en mode endothermique. Avantageusement, le CO2 ainsi récolté à la source, est récupéré, grâce à des équipements spécifiques, lorsque ledit véhicule fait le plein de carburant.
The description above and the exemplary embodiments show that the invention Achieved objectives, in particular it allows for a C0 2 separation device ungaz combustion product, which device is particularly compact and low energy consumption. In particular, the device that is the subject of the invention is suitable for use in collecting the carbon dioxide produced by a vehicle comprising an internal combustion engine. According to this embodiment, the C0 2 separated from the exhaust gas is advantageously stored in liquefied form so as to reduce the storage volume. To this end, a portion of the power of the heat engine is advantageously used to compress the gas and to produce, by a generator, the electrical energy in addition to the production of the SOFC sub-cells for the functioning of the operating MCFC sub-cells. in endothermic mode. Advantageously, the CO 2 thus harvested at the source, is recovered, thanks to specific equipment, when said vehicle is refueling.
Claims
REVENDICATIONS
Dispositif (110) pour la séparation du dioxyde de carbone contenu dans un mélange gazeux (100) lequel dispositif est caractérisé en ce qu'il comprend une cellule élémentaire comportant : Device (110) for the separation of the carbon dioxide contained in a gaseous mixture (100) which device is characterized in that it comprises an elementary cell comprising:
a. un premier ensemble d'électrodes à membrane constituant une sous-cellule électrochimique (211 ) sous la forme d'une pile à combustible à oxyde solide (SOFC) fonctionnant en mode production d'électricité ; at. a first set of membrane electrodes constituting an electrochemical sub-cell (211) in the form of a solid oxide fuel cell (SOFC) operating in power generation mode;
b. un deuxième ensemble d'électrodes à membrane constituant une sous-cellule électrochimique (213) sous la forme d'une pile à combustible à carbonate fondu (MCFC) fonctionnant en mode électrolyseur ; b. a second set of membrane electrodes constituting an electrochemical sub-cell (213) in the form of a molten carbonate fuel cell (MCFC) operating in electrolyser mode;
c. une première plaque intermédiaire poreuse (212) électriquement conductrice intercalée entre le premier (211 ) et le deuxième (213) ensemble d'électrodes à membrane et en liaison électrique et hydraulique avec ceux-ci ; vs. a first electrically conductive porous intermediate plate (212) interposed between the first (211) and the second (213) membrane electrode assembly and in electrical and hydraulic connection therewith;
d. des moyens (602, 321 ) d'injection pour injecter le mélange gazeux dans ladite première plaque intermédiaire poreuse ; d. injection means (602, 321) for injecting the gaseous mixture into said first porous intermediate plate;
e. une deuxième plaque intermédiaire poreuse (214) électriquement conductrice en liaison électrique et hydraulique avec le deuxième ensemble d'électrodes à membrane ; e. a second porous intermediate plate (214) electrically conductive in electrical and hydraulic connection with the second set of membrane electrodes;
f. des moyens (603, 322) de collecte pour collecter le dioxyde de carbone séparé du mélange gazeux sur ladite deuxième plaque intermédiaire poreuse (212). f. collection means (603, 322) for collecting carbon dioxide separated from the gaseous mixture on said second porous intermediate plate (212).
Dispositif (110) selon la revendication 1 , caractérisé en ce qu'il comprend un empilement d'une pluralité de cellules élémentaires (300) juxtaposées, chaque cellule élémentaire étant connectée mécaniquement, hydrauliquement et électriquement à la suivante par l'intermédiaire de sa deuxième plaque intermédiaire poreuse (214). Device (110) according to claim 1, characterized in that it comprises a stack of a plurality of elementary cells (300) juxtaposed, each elementary cell being connected mechanically, hydraulically and electrically to the next through its second porous intermediate plate (214).
Dispositif selon la revendication 1 , caractérisé en ce que les plaques
intermédiaires poreuses (212, 214) sont constituées d'un matériau céramique. Device according to claim 1, characterized in that the plates Porous intermediates (212, 214) are made of a ceramic material.
Dispositif selon la revendication 3, caractérisé en ce que les plaques intermédiaires poreuses (212, 214) sont constituées de carbure de silicium (SiC). Device according to claim 3, characterized in that the porous intermediate plates (212, 214) consist of silicon carbide (SiC).
Dispositif selon la revendication 3, caractérisé en ce que les plaques intermédiaires poreuses (212, 214) sont constituées de titanate de carbure de silicium (Ti3SiC2). Device according to Claim 3, characterized in that the porous intermediate plates (212, 214) consist of silicon carbide titanate (Ti 3 SiC 2 ).
Dispositif selon la revendication 2, caractérisé en ce qu'il comprend en outre : Device according to claim 2, characterized in that it further comprises:
g. un réservoir d'eau (195) et des moyens (192, 193, 194) pour collecter l'eau produite par les cellules électrochimiques SOFC (21 1 ) et l'envoyer dans ce réservoir (195) ; boy Wut. a water tank (195) and means (192, 193, 194) for collecting the water produced by the SOFC electrochemical cells (21 1) and sending it into that tank (195);
h. des moyens (196, 185) pour injecter de l'eau de ce réservoir (195) conjointement à l'injection du mélange gazeux dans les premières plaques intermédiaires poreuses des cellules élémentaires. h. means (196, 185) for injecting water from said reservoir (195) together with injecting the gaseous mixture into the first porous intermediate plates of the elementary cells.
Procédé pour la séparation du dioxyde carbone d'un mélange gazeux comprenant de la vapeur d'eau lequel procédé est mis en oeuvre au moyen d'un dispositif selon la revendication 2, caractérisé en ce qu'il comprend les étapes consistant à : Process for the separation of carbon dioxide from a gaseous mixture comprising steam which process is carried out by means of a device according to claim 2, characterized in that it comprises the steps of:
i. injecter le mélange gazeux (102) dans la première plaque intermédiaire poreuse (212) de la ième cellule élémentaire; i. injecting the gaseous mixture (102) into the first porous intermediate plate (212) of the i th elementary cell;
ii. réaliser l'électrolyse de l'eau contenue dans ledit mélange dans la ième sous-cellule électrochimique MCFC (213) de sorte à former, à la cathode de ladite sous-cellule, du dioxyde de carbone (C02) et du dioxygène (02), et du dihydrogène (H2) à l'anode de ladite sous-cellule ; ii. performing the electrolysis of the water contained in said mixture in the i th MCFC electrochemical sub-cell (213) so as to form, at the cathode of said sub-cell, carbon dioxide (CO 2 ) and dioxygen ( 0 2 ), and dihydrogen (H 2 ) at the anode of said sub-cell;
iii. diffuser H2 vers la cathode de la sous-cellule électrochimique SOFC (21 1 ) de la ième cellule élémentaire à travers la première (212) plaque poreuse intermédiaire de ladite ième cellule
iv. diffuser C02 et 02 à travers la deuxième plaque intermédiaire poreuse (214) de la ième cellule élémentaire vers l'anode de la sous-cellule électrochimique SOFC (21 1 ) de la (i+1 )ème cellule élémentaire ; iii. diffusing H 2 to the cathode of the SOFC electrochemical sub-cell (21 1) of the ith elementary cell through the first (212) porous intermediate plate of said ith cell iv. diffusing C02 and O2 through the second porous intermediate plate (214) of the ith elementary cell to the anode of the SOFC electrochemical sub-cell (21 1) of the (i + 1) th elementary cell;
v. consommer O2 dans la (i+1 )ème sous-cellule SOFC (21 1 ) pour la production d'électricité et récolter le CO2 sur la deuxième plaque intermédiaire poreuse (214) de la ième cellule élémentaire. v. consume O 2 in the (i + 1) th SOFC sub-cell (21 1) for the production of electricity and collect the CO 2 on the second porous intermediate plate (214) of the ith elementary cell.
Procédé selon la revendication 7, mis en oeuvre au moyen d'un dispositif selon la revendication 6, caractérisé en ce que le mélange gazeux (100) ne comprenant pas de vapeur d'eau, ledit procédé comprend avant l'étape i) une étape consistant à : Process according to Claim 7, implemented by means of a device according to Claim 6, characterized in that the gaseous mixture (100) does not comprise any water vapor, said process comprises, before step i) a step consists in :
vi. injecter de la vapeur d'eau (101 ) avec le mélange gazeux (100) pour initier la réaction. vi. injecting water vapor (101) with the gaseous mixture (100) to initiate the reaction.
Procédé selon la revendication 7, caractérisé en ce qu'il comprend les étapes consistant à : Method according to claim 7, characterized in that it comprises the steps of:
vii. comprimer le CO2 au sortir de la deuxième plaque intermédiaire poreuse (214) pour le liquéfier ; vii. compressing the CO 2 out of the second porous intermediate plate (214) to liquefy it;
viii traiter à basse pression les autres composés du gaz séparé du CO2 et récoltés au sortir de la première plaque intermédiaire poreuse (212). viii treat at low pressure the other compounds of the gas separated from the CO 2 and collected at the outlet of the first porous intermediate plate (212).
Véhicule comprenant un moteur à combustion interne et caractérisé en ce qu'il comprend: Vehicle comprising an internal combustion engine and characterized in that it comprises:
x. un dispositif selon la revendication 2, connecté à la sortie de l'échappement dudit moteur pour la mise en oeuvre d'un procédé selon la revendication 9 ; x. a device according to claim 2 connected to the exhaust outlet of said engine for carrying out a method according to claim 9;
y. un réservoir apte à stocker du dioxyde de carbone sous forme liquéfiée ; there. a tank capable of storing carbon dioxide in liquefied form;
z. un générateur électrique apte à dériver une partie de la puissance du moteur pour générer un courant électrique apte à compléter la puissance électrique générée par les sous-cellules SOFC (21 1 ) ; t. des moyens pour connecter électriquement le générateur
électrique avec les premières plaques poreuses interméd (212) des cellules élémentaires (300).
z. an electric generator adapted to derive a portion of the engine power to generate an electric current capable of supplementing the electric power generated by the SOFC sub-cells (21 1); t. means for electrically connecting the generator with the first intermediate porous plates (212) of the elementary cells (300).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1251965A FR2987562B1 (en) | 2012-03-02 | 2012-03-02 | METHOD AND DEVICE FOR SEPARATING THE CARBON DIOXIDE FROM A GASEOUS MIXTURE |
PCT/FR2013/050447 WO2013128144A1 (en) | 2012-03-02 | 2013-03-01 | Method and device for separating the carbon dioxide from a gaseous mixture |
Publications (1)
Publication Number | Publication Date |
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EP2819768A1 true EP2819768A1 (en) | 2015-01-07 |
Family
ID=48044930
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13713469.8A Withdrawn EP2819768A1 (en) | 2012-03-02 | 2013-03-01 | Method and device for separating the carbon dioxide from a gaseous mixture |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2819768A1 (en) |
FR (1) | FR2987562B1 (en) |
WO (1) | WO2013128144A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10581502B2 (en) | 2017-06-29 | 2020-03-03 | Telefonaktiebolaget Lm Ericsson (Publ) | First radio node and methods therein for adjusting a set of beams for communication in a wireless communications network |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1879685A2 (en) * | 2005-04-18 | 2008-01-23 | The Trustees of Columbia University in the City of New York | Ion conducting membranes for separation of molecules |
US7790332B2 (en) * | 2006-07-03 | 2010-09-07 | Appliedus Corporation | Fuel cells and methods of manufacturing the same |
-
2012
- 2012-03-02 FR FR1251965A patent/FR2987562B1/en active Active
-
2013
- 2013-03-01 WO PCT/FR2013/050447 patent/WO2013128144A1/en active Application Filing
- 2013-03-01 EP EP13713469.8A patent/EP2819768A1/en not_active Withdrawn
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10581502B2 (en) | 2017-06-29 | 2020-03-03 | Telefonaktiebolaget Lm Ericsson (Publ) | First radio node and methods therein for adjusting a set of beams for communication in a wireless communications network |
Also Published As
Publication number | Publication date |
---|---|
FR2987562A1 (en) | 2013-09-06 |
FR2987562B1 (en) | 2014-04-25 |
WO2013128144A1 (en) | 2013-09-06 |
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