CN113793963A - Fluidized bed catalytic electrode ammonia direct fuel cell system - Google Patents
Fluidized bed catalytic electrode ammonia direct fuel cell system Download PDFInfo
- Publication number
- CN113793963A CN113793963A CN202110899804.XA CN202110899804A CN113793963A CN 113793963 A CN113793963 A CN 113793963A CN 202110899804 A CN202110899804 A CN 202110899804A CN 113793963 A CN113793963 A CN 113793963A
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- solid oxide
- gas
- oxide fuel
- fluidized bed
- 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.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—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
Abstract
The invention provides a fluidized bed catalytic electrode ammonia direct fuel cell system. The temperature of the solid oxide fuel cell is maintained in a proper range, the fuel control module stably conveys fuel gas to the anode of the solid oxide fuel cell and conveys air to the cathode of the tubular fluidized bed bin containing cathode particles, the cathode particles are driven by air flow to repeatedly collide with the tubular fluidized bed bin, the surface charge and temperature distribution of the electrode are updated, and then the surface of the cathode particles is used as a reaction site to replace a traditional plane, so that the reaction interface of the electrode is increased, and the power density of a cell unit is improved; the irregular motion of cathode particles in the fluidized bed can lead the surface of the electrode to be continuously updated, improve the heat transfer and mass transfer efficiency of the electrode and greatly reduce the thermal stress generated by the traditional solid electrode structure due to uneven temperature. The invention solves the technical difficulties of anode peroxidation and low power density in the fuel cell, improves the energy conversion efficiency of the device, and has the advantages of modular design, easy amplification and the like.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fluidized bed catalytic electrode ammonia direct fuel cell system.
Background
Since the 21 st century, the traditional fossil fuel is facing the risk of exhaustion, and the environmental pollution problem is becoming more serious, so that it is urgent to find a new energy source capable of replacing fossil energy. Among numerous candidates, hydrogen is favored by people by virtue of the advantages of environmental protection, high combustion heat value and the like, and is expected to become an important energy carrier in the future society. However, the safety and storage and transportation of hydrogen energy become key obstacles in hydrogen energy utilization technology, and therefore, a safe and feasible hydrogen carrier needs to be found. Ammonia has a high volumetric energy density (3.5 kWh.L.) compared to hydrogen-1) The hydrogen content is high (17.7 wt%), the liquefaction is easy, the combustible range is narrow, and the matched storage and transportation technology and infrastructure are mature, so that the hydrogen storage form is extremely safe and effective.
The traditional energy conversion mode mainly adopts thermal power generation and is limited by Carnot cycle, and the power generation efficiency only reaches about 40%. The fuel cell is considered as a fourth power generation technology following hydroelectric power generation, thermal power generation and atomic power generation, has the characteristics of high power generation efficiency, wide fuel range and the like, and the power generation efficiency in practical application can reach 50-70%; zero pollution of products can be realized when clean energy such as ammonia gas and the like is used, and the method has wide application prospect.
At present, the ammonia fuel cell is not yet applied to the field of distributed energy sources with important market prospects in a large scale, and one of the main reasons is that the output characteristic, environmental protection and safety of the fuel cell are difficult to meet the actual application requirements due to the lack of reasonable structural design of the traditional ammonia fuel cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a fluidized bed catalytic electrode ammonia direct fuel cell system, which solves the technical difficulties of anode peroxidation and low power density in a fuel cell through a catalytic electrode and a fluidized bed electrode, improves the energy conversion efficiency of the device, and also has the good advantages of modularization, easy amplification and the like.
The invention specifically adopts the following technical scheme.
To achieve the above object, a fluidized-bed catalytic electrode ammonia direct fuel cell system is provided, which includes:
the heating module comprises a muffle furnace and a heating module, wherein the muffle furnace is used for heating the solid oxide fuel cell structure and maintaining the temperature of the solid oxide fuel cell between 700 ℃ and 800 ℃;
a fuel control module for stabilizing the delivery of fuel gas to the anode of the solid oxide fuel cell;
the cell module comprises a plurality of solid oxide fuel cells which are connected in series to output power, each solid oxide fuel cell comprises an anode arranged in the center and a cathode surrounding the periphery of the anode, the anode of each solid oxide fuel cell is connected with the fuel control module through a fuel gas pipeline to receive fuel gas, the cathode of each solid oxide fuel cell receives air through an air main pipe, a tubular fluidized bed bin containing cathode particles is formed on the cathode of each solid oxide fuel cell, the cathode particles are driven by air flow input by the air main pipe to collide with the tubular fluidized bed bin, and the surface charge and the temperature distribution of the electrodes are updated.
The above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, characterized in that, the heating module includes: the muffle furnace receives power supply of an external power supply to heat the solid oxide fuel cell during the starting process of the solid oxide fuel cell; after the output of the solid oxide fuel cell supplies power, the solid oxide fuel cell directly receives the electric energy generated by the solid oxide fuel cell to maintain the temperature of the solid oxide fuel cell; the temperature sensor assembly is arranged outside the tubular fluidized bed bin of the solid oxide fuel cell, is positioned in the middle of the solid oxide fuel cell in the axial direction and is tightly attached to the wall of the cathode tube; and the temperature controller assembly is connected with the temperature sensor assembly and the muffle furnace and is used for adjusting the power supply current of the muffle furnace according to the temperature detected by the temperature sensor assembly so as to maintain the temperature of the solid oxide fuel cell between 700 ℃ and 800 ℃.
Alternatively, in the above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, the temperature sensor assembly includes but is not limited to: k-index nickel chromium-nickel silicon thermocouples.
The above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, characterized in that, the fuel control module comprises: the fuel gas pipeline (2) comprises a fuel gas mother pipe and fuel gas connecting pipes connected between the fuel gas mother pipe and each solid oxide fuel cell, and the fuel gas mother pipe is communicated with the fuel gas connecting pipes so as to stably output fuel gas to each solid oxide fuel cell; a flow meter connected to the fuel gas pipe (2) and detecting the flow rate of the fuel gas; a safety valve connected in the fuel gas pipeline (2) for adjusting the flow rate of the fuel gas; the fuel gas supply device comprises a gas storage tank, wherein fuel gas is stored in the gas storage tank and is used for outputting the fuel gas to the fuel gas pipeline (2); the air pump is connected to each solid oxide fuel cell through an air main pipe and is used for stably pumping air into each solid oxide fuel cell; and the gas recovery processing device is connected with the gas outlet of the anode of each solid oxide fuel cell and receives and recovers gas products in the operation process of each solid oxide fuel cell.
Optionally, in the above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, the fuel gas includes, but is not limited to, any one of hydrogen, carbon fuel such as methane, and ammonia gas.
The above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, characterized in that, the fuel gas supply device further comprises: the wind energy ammonia production module or the solar energy ammonia production module is used for producing ammonia gas, and the produced ammonia gas is pressurized, liquefied and stored in a gas storage tank to be supplied to each solid oxide fuel cell through a fuel gas pipeline (2).
The above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system is characterized in that, in each of the solid oxide fuel cells: the anode is a hollow anode tube, the bottom of the anode tube is connected with a fuel gas pipeline, and the top of the anode tube is connected with a gas recovery processing device; the cathode includes: the tubular cathode layer surrounds the periphery of the anode tube, and an electrolyte layer is arranged between the inner wall of the tubular cathode layer and the outer wall of the anode tube in an isolated mode; the tubular fluidized bed bin surrounds the periphery of the tubular cathode layer, the top and the bottom of the tubular fluidized bed bin are respectively connected with the outer wall of the tubular cathode layer in a sealing mode, a tubular cavity for containing cathode particles is formed between the inner wall of the tubular fluidized bed bin and the outer wall of the tubular cathode layer, an air side inlet is formed in the bottom of the tubular fluidized bed bin, the tubular fluidized bed bin is connected with an air main pipe through an air flow pipeline of the air side inlet, and the cathode particles are blown by air flow input by the air main pipe from bottom to top to collide with the inner wall of the tubular cavity.
Optionally, in the above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, the inner side surface of the anode tube is coated with silver paste to form an anode current collector layer; the outer side surface of the tubular cathode layer is coated with silver paste to form a cathode collector layer; the electrolyte layer is made of yttrium oxide and/or zirconium oxide materials which are sintered, fixed and integrally connected between the tubular cathode layer and the anode tube.
The fluidized bed catalytic electrode ammonia direct fuel cell system is characterized in that an air side outlet is arranged at the top of the tubular fluidized bed bin and discharges gas in the tubular cavity through an exhaust pipeline; air side inlets of the solid oxide fuel cells are connected in parallel to an air mother pipe through an air flow pipeline, the bottoms of anode pipes of the solid oxide fuel cells are connected in parallel to the fuel gas mother pipe through a fuel gas connecting pipe, the tops of the anode pipes of the solid oxide fuel cells are connected in parallel to a gas recovery processing device through a recovery pipeline, and air side outlets of the solid oxide fuel cells are connected in parallel to the outer side of the muffle furnace through exhaust pipes; and independent valves are optionally arranged on the gas flow pipeline, the fuel gas connecting pipe, the top of the anode pipe or the exhaust pipe to adjust the on-off of each gas pipeline.
In the above-mentioned fluidized bed catalytic electrode ammonia direct fuel cell system, the outer side of the solid oxide fuel cell is further provided with a bottom heat-insulating layer, and the bottom heat-insulating layer completely covers the bottom of the anode tube, the air side inlet and the bottom of the tubular fluidized bed chamber; and the air side outlet of the solid oxide fuel cell and the top of the anode tube are positioned outside the heating range of the muffle furnace.
Advantageous effects
1. The invention utilizes the heating module to maintain the temperature of the solid oxide fuel cell in a proper range, the fuel control module stably conveys fuel gas to the anode of the solid oxide fuel cell and conveys air to the cathode of the tubular fluidized bed bin containing cathode particles, and the cathode particles are driven by the air flow to repeatedly collide with the tubular fluidized bed bin, so that the surface charge and the temperature distribution of the electrode are updated. According to the method, the surfaces of the cathode particles are used as reaction sites instead of the traditional planes, so that the electrode reaction interface is increased, and the power density of the battery unit can be effectively improved; the cathode particles do irregular motion in the tubular fluidized bed bin of the cathode continuously, so that the surface of the electrode is updated continuously, the heat transfer and mass transfer efficiency of the electrode can be effectively improved, the thermal stress generated due to uneven temperature under the traditional solid electrode structure is greatly reduced, and the device is easier to amplify. The invention solves the technical difficulties of anode peroxidation and low power density in the fuel cell, improves the energy conversion efficiency of the device, and has the advantages of modular design, easy amplification and the like.
2. The catalytic electrode technology adopted by the invention enhances the interaction between the active components and the carrier, further improves the dispersing capacity of the active center, and effectively reduces the activation energy required by the reaction, thereby improving the catalytic effect, and having obvious advantages in the aspects of ammonia conversion rate, hydrogen production rate, circulation stability and the like compared with the traditional method.
3. The fluidized bed tubular electrode technology adopted by the invention preferably selects the tubular electrode with better safety, improves the tubular electrode current collecting effect by the fluidized bed electrode technology, greatly improves the cathode reaction rate, effectively prevents the problems of local overheating, concentration polarization and the like in the large-scale application process, ensures that the electrode temperature is uniform, greatly reduces the thermal stress generated by uneven temperature of the traditional solid electrode, accelerates the starting rate of the fuel cell, increases the use safety of the fuel cell, and is convenient for the large scale of the device.
4. The invention designs and builds the ammonia direct solid oxide fuel cell device adopting the fluidized bed catalytic electrode, realizes the reliable and stable operation of the device, fills the technical blank in the field, is convenient for large-scale production, and has wide application prospect in the fuel cell industrialization aspect.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a tubular fluidized bed cartridge housing for a single solid oxide fuel cell in a cell module of the present invention;
FIG. 2 is a schematic view of a corundum tube used to connect solid oxide fuel cells to fuel gas connecting tubes in a cell module of the present invention;
FIG. 3 is a schematic view of the overall structure of a single solid oxide fuel cell in a cell module of the present invention;
FIG. 4 is a cross-sectional view of a single solid oxide fuel cell of the present invention;
FIG. 5 is a schematic view of the connection mounting relationship between the heating module of the present invention and the solid oxide fuel cell unit;
FIG. 6 is a schematic view of the gas channel connections between solid oxide fuel cells of the present invention;
FIG. 7 is a schematic external view of the whole of a fluid catalytic electrode ammonia direct fuel cell system of the present invention;
fig. 8 is a functional block diagram of a fluid catalytic electrode ammonia direct fuel cell system of the present invention.
In the figure, 1 denotes an outlet corundum tube; 2 denotes an anode tube; 21 denotes an anode current collecting layer; 22 denotes an electrolyte layer; 23 denotes a tubular cathode layer; 3 denotes an air side outlet; 4 denotes a tubular fluidized bed chamber; 41 denotes a muffle furnace heating range; 42 denotes a bottom insulating layer; 45 denotes cathode particles; 5 denotes an air-side inlet; and 6 denotes an inlet corundum tube.
Detailed Description
In order to make the purpose and technical solution of the embodiments of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The meaning of "and/or" in the present invention means that the respective single or both of them exist individually or in combination.
The meaning of "inside and outside" in the present invention means that the direction from the tubular fluidized bed bin pipe housing to the internal fuel gas is inside and vice versa, with respect to each solid oxide fuel cell itself; and not as a specific limitation on the mechanism of the device of the present invention.
The term "connected" as used herein may mean either a direct connection between the components or an indirect connection between the components via other components.
Fig. 7 is a fluid catalytic electrode ammonia direct fuel cell system according to the present invention, comprising:
the heating module comprises a muffle furnace, the heating temperature is set through a control panel of the muffle furnace to heat the solid oxide fuel cell structure, and the temperature of the solid oxide fuel cell is maintained between 700 ℃ and 800 ℃;
the fuel control module comprises a gas channel for providing fuel gas and a gas channel for conveying air, and is used for stably conveying the fuel gas to the anode of the solid oxide fuel cell and correspondingly discharging the reacted gas for harmless treatment;
the cell module comprises a plurality of solid oxide fuel cells which are connected in series to output power, each solid oxide fuel cell comprises an anode arranged in the center and a cathode surrounding the periphery of the anode, the anode of each solid oxide fuel cell is connected with a fuel control module through a fuel gas pipeline in a mode shown in figure 6 to receive fuel gas, the cathode of each solid oxide fuel cell receives air through an air main pipe, a tubular fluidized bed bin 4 containing cathode particles 45 is formed in the cathode of each solid oxide fuel cell, the cathode particles 45 are driven by air flow input by the air main pipe to collide with the tubular fluidized bed bin 4, and electrode surface charge and temperature distribution are updated.
Therefore, the fluidized bed catalytic electrode ammonia direct fuel cell system can utilize the heating module to maintain the temperature of the solid oxide fuel cell in a proper range, stably convey fuel gas to the anode of the solid oxide fuel cell through the fuel control module and convey air to the cathode of the tubular fluidized bed bin containing cathode particles, drive the cathode particles in the bin to repeatedly collide with the tubular fluidized bed bin through air flow, update the surface charge and temperature distribution of the electrode, replace the traditional plane with the surface of the cathode particles as a reaction site, increase the reaction interface of the electrode, and effectively improve the power density of a cell unit; the surface of the electrode can be continuously updated in the process that cathode particles do irregular motion ceaselessly in the tubular fluidized bed bin of the cathode, so that the heat transfer and mass transfer efficiency of the electrode is effectively improved, the thermal stress generated by uneven temperature under the traditional solid electrode structure is greatly reduced, and the device is easier to amplify. The invention solves the technical difficulties of anode peroxidation and low power density in the fuel cell, improves the energy conversion efficiency of the device, and has the advantages of modular design, easy amplification and the like.
In a more preferred implementation, the anode of the solid oxide fuel cell may be further provided as a hollow anode tube 2, the bottom of the anode tube is connected to a fuel gas pipeline through an inlet corundum tube 6 shown in fig. 2 or 3, the anode tube receives carbon fuel such as hydrogen, methane or ammonia gas conveyed in the direction of arrow a in fig. 4, and the top of the anode tube 2 is connected to a gas recovery processing device through an outlet corundum tube 1 to perform tail gas processing.
The cathode of the solid oxide fuel cell can be specifically configured as shown in fig. 1, and includes:
a tubular cathode layer 23 surrounding the outer periphery of the anode tube 2, wherein the electrolyte layer 22 is arranged between the inner wall of the tubular cathode layer 23 and the outer wall of the anode tube 2 in an isolated manner;
the tubular fluidized bed bin 4 surrounds the periphery of the tubular cathode layer 23, the top and the bottom of the tubular fluidized bed bin 4 are respectively connected with the outer wall of the tubular cathode layer 23 in a sealing mode, a tubular cavity for containing cathode particles 45 is formed between the inner wall of the tubular fluidized bed bin 4 and the outer wall of the tubular cathode layer 23, an air side inlet 5 is formed in the bottom of the tubular fluidized bed bin 4, the tubular fluidized bed bin 4 is connected with an air main pipe through an air flow pipeline of the air side inlet 5, and the cathode particles 45 are blown by air flow input by the air main pipe from bottom to top and collide with the inner wall of the tubular cavity.
In order to further promote the charge flow between the cathode and the anode, the present application may further coat the inner side surface of the anode tube 2 made of the above-mentioned nickel-based-yttria stabilized zirconia mixture with silver paste to form an anode current collector layer 21, coat the outer side surface of the tubular cathode layer 23 formed of the lanthanum strontium manganese composite material or the lanthanum strontium cobalt iron composite material with silver paste to form a cathode current collector layer, so that the two form catalytic electrodes, and form an electrolyte layer 22 by sintering the yttria and/or zirconia material between the catalytic electrodes, and use the silver paste to dope the transition metal element in the conventional electrode material as an active component, so as to improve the catalytic properties of the electrodes, and improve the catalytic decomposition efficiency of the fuel gas at the anode of the battery, thereby improving the energy conversion efficiency, output power and power density of the fuel battery. Therefore, oxygen ions in the electrolyte layer 22 which is sintered, fixed and integrally connected between the tubular cathode layer 23 and the anode tube 2 can accelerate the movement between the two catalytic electrodes, so that the energy conversion efficiency of the battery is effectively improved.
In order to further accurately control the gas flow in the solid oxide fuel cell, in a manner shown in fig. 6, an air side outlet 3 is further arranged at the top of the tubular fluidized bed chamber 4, and is connected with other cell units in parallel through an exhaust pipeline to exhaust gas in the tubular cavity; similarly, the air side inlets 5 of the solid oxide fuel cells are connected in parallel to an air main pipe through an air flow pipeline, the bottom of the anode pipe 2 of each solid oxide fuel cell can be connected in parallel to the fuel gas main pipe through a fuel gas connecting pipe, the top of the anode pipe 2 of each solid oxide fuel cell can be connected in parallel to a gas recovery processing device through a recovery pipeline, and the air side outlets 3 of the solid oxide fuel cells are connected in parallel to the outer side of the muffle furnace through exhaust pipes. Therefore, the corresponding independent valves can be further arranged at any position on the gas flow pipeline, the fuel gas connecting pipe, the top of the anode pipe 2 or the exhaust pipe to adjust the on-off of each gas pipeline, so that the gas circulation rate in each cell unit is adjusted, and the utilization efficiency of the cell unit to fuel gas is improved.
For example, a fuel gas pipeline (2) for controlling the supply of fuel gas in the fuel control module can be specifically configured to include a fuel gas mother pipe and fuel gas connecting pipes connected between the fuel gas mother pipe and each solid oxide fuel cell, the fuel gas mother pipe is communicated with the fuel gas connecting pipes and stably outputs fuel gas to the corresponding solid oxide fuel cells through inlet corundum pipes; in the fuel gas pipeline (2), the flow rate of the fuel gas can be detected by a flowmeter, and the flow rate of the fuel gas can be adjusted by a safety valve.
The fuel gas supply device in the fuel control module can further prepare ammonia gas through the wind energy ammonia preparation module or the solar energy ammonia preparation module to reduce the cost of obtaining the fuel gas besides the gas storage tank storing the fuel gas. The wind energy ammonia production module or the solar energy ammonia production module can store the obtained ammonia gas in a pressurizing and liquefying mode in a gas storage tank so as to supply the ammonia gas to each solid oxide fuel cell through a fuel gas pipeline (2).
And the air in the pipe B in FIG. 4 can be supplied to each solid oxide fuel cell through an air pump connecting air main pipe to stably pump air into each solid oxide fuel cell.
And the gas recovery processing device can be connected with the gas outlet of the anode of each solid oxide fuel cell through a corresponding pipeline, and receives and recovers the gas product in the operation process of each solid oxide fuel cell.
Therefore, the invention utilizes the cathode bin and the cathode particles to form the fluidized bed cathode, and utilizes the introduced air to ensure that the cathode particles do irregular motion in the cathode bin ceaselessly, so that the surface of the electrode is updated continuously, the heat transfer and mass transfer efficiency of the electrode is improved, and the thermal stress generated by the traditional solid electrode due to uneven temperature is greatly reduced; the particles continuously contact the surface of the electrode, and the surface of the particles replaces the traditional plane as a reaction field, so that the reaction interface of the electrode is enlarged.
When the cell structure is heated by a muffle furnace, in order to protect the gas channel from being damaged by high temperature, a bottom heat-insulating layer 42 is correspondingly arranged on the outer side of the solid oxide fuel cell in a general way shown in fig. 5, and the bottom heat-insulating layer 42 completely covers the bottom of the anode tube 2, the air side inlet 5 and the bottom of the tubular fluidized bed bin 4; the air side outlet 3 of the solid oxide fuel cell and the top of the anode tube 2 are positioned outside the heating range 41 of the muffle furnace; while the middle section of the tubular fluidized bed chamber 4 is exposed to the heating range 41 of the muffle furnace to ensure the reaction temperature. In specific implementation, the fuel cell can be directly placed in the bottom heat insulation layer groove, and the muffle heater is placed on the upper portion of the heat insulation layer, so that the relative position between the electric heating furnace assembly and the solid oxide fuel cell unit is determined. In order to accurately control the reaction temperature, the temperature sensor assembly such as a K-index nickel-chromium-nickel-silicon thermocouple and the like can be further arranged outside the tubular fluidized bed bin 4 of the solid oxide fuel cell, the axial middle position of the solid oxide fuel cell is tightly attached to the wall of the cathode tube so as to accurately collect the reaction temperature of the cell unit, and therefore the temperature controller assembly in the heating module is connected with the temperature sensor assembly and the muffle furnace so as to adjust the power supply current of the muffle furnace according to the temperature detected by the temperature sensor assembly and maintain the temperature of the solid oxide fuel cell at 700-800 ℃.
In order to further reduce the use cost of the fuel cell, the muffle furnace for maintaining the reaction temperature can be set by the control unit in the manner shown in fig. 8: only during the starting process of the solid oxide fuel cell, receiving power supplied by an external power supply to heat the solid oxide fuel cell by raising the temperature; after the output of the solid oxide fuel cell supplies power, the solid oxide fuel cell directly receives the electric energy generated by the solid oxide fuel cell to maintain the temperature of the solid oxide fuel cell;
the operation flow of the embodiment of the present invention is explained in detail below.
Step one, a worker starts a switch of the electric heating furnace to set the heating temperature to 700-. When the specified temperature is reached, the device will prompt the worker.
And step two, opening a valve of the gas storage tank and a valve of the air pump, and adjusting the flow of the two gases through a flowmeter, wherein in the embodiment, the fuel gas is ammonia gas. And (3) introducing ammonia gas into the anode region of the fuel cell through a gas conveying pipeline 6, introducing the ammonia gas into the cathode region of the fuel cell through a gas conveying pipeline 5, and decomposing the ammonia gas into hydrogen and nitrogen under the action of an anode catalyst layer for power generation of the fuel cell. Air in the cathode region of the cell will produce O2-, which is transported into the anode compartment through the electrolyte, reacts with hydrogen to produce water, and releases electrons to the anode current collector. The cathode and anode current collecting layers can adopt silver paste or foamed nickel and other materials. After reaction, the fuel gas is delivered to a gas recovery device through a gas delivery pipeline 1, and the air side is discharged through a gas delivery pipeline 3.
And step three, when the temperature of the heating system reaches a set value and the open-circuit voltage of the fuel cell is stable, opening a fuel cell switch to output electric energy to the outside, and meeting the power consumption requirement of the load. The device enters a self-sustaining operating state.
And step four, after the electric energy is supplied, closing the valve of the ammonia gas storage tank, the air pump and the switch of the fuel cell, and then closing the switch of the electric heating furnace to cool the fuel cell along with the temperature of the furnace. The device assembly can be shut down when the fuel cell module is cooled to room temperature along with the furnace.
Therefore, the fuel gas is led into each solid oxide fuel cell in the cell module to generate electricity by heating the operation temperature of the self-supporting device of the module and ensuring the stability and safety of the fuel gas supply through the fuel control module. The invention adopts the technology of the catalytic electrode and the fluidized bed electrode, the catalytic electrode improves the catalytic characteristic of the electrode, and improves the catalytic decomposition efficiency of fuel gas at the anode of the fuel cell, thereby improving the energy conversion efficiency, the output power and the power density of the fuel cell; the fluidized bed electrode adopts a cathode bin and cathode particles to form a fluidized bed cathode, the particles are continuously contacted with the surface of the electrode, the surface of the particles replaces the traditional plane to be used as a reaction field, the electrode reaction interface is enlarged, and the power density is further improved; the cathode particles do irregular motion in the cathode chamber continuously, so that the surface of the electrode is updated continuously, the heat transfer and mass transfer efficiency of the electrode is improved, the thermal stress generated by uneven temperature of the traditional solid electrode is greatly reduced, and the device is easier to amplify. The invention basically solves the technical difficulties of anode peroxidation and low power density in the fuel cell, improves the energy conversion efficiency of the device, and has the advantages of modular design, easy amplification and the like.
The above are merely embodiments of the present invention, which are described in detail and with particularity, and therefore should not be construed as limiting the scope of the invention. It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the spirit of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (10)
1. A fluid bed catalytic electrode ammonia direct fuel cell system, comprising:
the heating module comprises a muffle furnace and a heating module, wherein the muffle furnace is used for heating the solid oxide fuel cell structure and maintaining the temperature of the solid oxide fuel cell between 700 ℃ and 800 ℃;
a fuel control module for stabilizing the delivery of fuel gas to the anode of the solid oxide fuel cell;
the cell module comprises a plurality of solid oxide fuel cells which are connected in series to output power, each solid oxide fuel cell comprises an anode arranged in the center and a cathode surrounding the periphery of the anode, the anode of each solid oxide fuel cell is connected with the fuel control module through a fuel gas pipeline to receive fuel gas, the cathode of each solid oxide fuel cell receives air through an air main pipe, a tubular fluidized bed bin containing cathode particles is formed on the cathode of each solid oxide fuel cell, the cathode particles are driven by air flow input by the air main pipe to collide with the tubular fluidized bed bin, and the surface charge and the temperature distribution of the electrodes are updated.
2. The fluid catalytic electrode ammonia direct fuel cell system of claim 1, wherein the heating module comprises:
the muffle furnace receives power supply of an external power supply to heat the solid oxide fuel cell during the starting process of the solid oxide fuel cell; after the output of the solid oxide fuel cell supplies power, the solid oxide fuel cell directly receives the electric energy generated by the solid oxide fuel cell to maintain the temperature of the solid oxide fuel cell;
the temperature sensor assembly is arranged outside the tubular fluidized bed bin of the solid oxide fuel cell, is positioned in the middle of the solid oxide fuel cell in the axial direction and is tightly attached to the wall of the cathode tube;
and the temperature controller assembly is connected with the temperature sensor assembly and the muffle furnace and is used for adjusting the power supply current of the muffle furnace according to the temperature detected by the temperature sensor assembly so as to maintain the temperature of the solid oxide fuel cell between 700 ℃ and 800 ℃.
3. The fluid catalytic electrode ammonia direct fuel cell system of claim 2, wherein the temperature sensor assembly includes but is not limited to: k-indexed nickel-chromium-nickel-silicon thermocouples.
4. The fluid catalytic electrode ammonia direct fuel cell system of claim 1, wherein the fuel control module comprises:
the fuel gas pipeline (2) comprises a fuel gas mother pipe and fuel gas connecting pipes connected between the fuel gas mother pipe and each solid oxide fuel cell, and the fuel gas mother pipe is communicated with the fuel gas connecting pipes so as to stably output fuel gas to each solid oxide fuel cell;
a flow meter connected to the fuel gas pipe (2) and detecting the flow rate of the fuel gas;
a safety valve connected in the fuel gas pipeline (2) for adjusting the flow rate of the fuel gas;
the fuel gas supply device comprises a gas storage tank, wherein fuel gas is stored in the gas storage tank and is used for outputting the fuel gas to the fuel gas pipeline (2);
the air pump is connected to each solid oxide fuel cell through an air main pipe and is used for stably pumping air into each solid oxide fuel cell;
and the gas recovery processing device is connected with the gas outlet of the anode of each solid oxide fuel cell and receives and recovers gas products in the operation process of each solid oxide fuel cell.
5. The system as claimed in claim 3, wherein the fuel gas is any one of hydrogen, carbon fuel such as methane, and ammonia gas.
6. The fluid catalytic electrode ammonia direct fuel cell system according to claim 3, wherein the fuel gas supply means further comprises:
the wind energy ammonia production module or the solar energy ammonia production module is used for producing ammonia gas, and the produced ammonia gas is pressurized, liquefied and stored in a gas storage tank to be supplied to each solid oxide fuel cell through a fuel gas pipeline (2).
7. The fluid catalytic electrode ammonia direct fuel cell system of claim 1, wherein in each of the solid oxide fuel cells:
the anode is a hollow anode tube, the bottom of the anode tube is connected with a fuel gas pipeline, and the top of the anode tube is connected with a gas recovery processing device;
the cathode includes:
the tubular cathode layer surrounds the periphery of the anode tube, and an electrolyte layer is arranged between the inner wall of the tubular cathode layer and the outer wall of the anode tube in an isolated mode;
the tubular fluidized bed bin surrounds the periphery of the tubular cathode layer, the top and the bottom of the tubular fluidized bed bin are respectively connected with the outer wall of the tubular cathode layer in a sealing mode, a tubular cavity for containing cathode particles is formed between the inner wall of the tubular fluidized bed bin and the outer wall of the tubular cathode layer, an air side inlet is formed in the bottom of the tubular fluidized bed bin, the tubular fluidized bed bin is connected with an air main pipe through an air flow pipeline of the air side inlet, and the cathode particles are blown by air flow input by the air main pipe from bottom to top to collide with the inner wall of the tubular cavity.
8. The fcc-electrode ammonia direct fuel cell system of claim 7, wherein the inside surface of the anode tube is coated with silver paste to form an anode current collector layer;
the outer side surface of the tubular cathode layer is coated with silver paste to form a cathode collector layer;
the electrolyte layer is made of yttrium oxide and/or zirconium oxide materials which are sintered, fixed and integrally connected between the tubular cathode layer and the anode tube.
9. The fluidized bed catalytic electrode ammonia direct fuel cell system as claimed in claim 7, wherein the top of the tubular fluidized bed chamber is provided with an air side outlet which exhausts the gas in the tubular chamber through an exhaust duct;
air side inlets of the solid oxide fuel cells are connected in parallel to an air mother pipe through an air flow pipeline, the bottoms of anode pipes of the solid oxide fuel cells are connected in parallel to the fuel gas mother pipe through a fuel gas connecting pipe, the tops of the anode pipes of the solid oxide fuel cells are connected in parallel to a gas recovery processing device through a recovery pipeline, and air side outlets of the solid oxide fuel cells are connected in parallel to the outer side of the muffle furnace through exhaust pipes;
and independent valves are optionally arranged on the gas flow pipeline, the fuel gas connecting pipe, the top of the anode pipe or the exhaust pipe to adjust the on-off of each gas pipeline.
10. The fluidized bed catalytic electrode ammonia direct fuel cell system as claimed in any one of claims 1 to 9, wherein the outside of the solid oxide fuel cell is further provided with a bottom thermal insulation layer which completely covers the bottom of the anode tube, the air side inlet and the bottom of the tubular fluidized bed bin;
and the air side outlet of the solid oxide fuel cell and the top of the anode tube are positioned outside the heating range of the muffle furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899804.XA CN113793963B (en) | 2021-08-06 | 2021-08-06 | Fluidized bed catalytic electrode ammonia direct fuel cell system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110899804.XA CN113793963B (en) | 2021-08-06 | 2021-08-06 | Fluidized bed catalytic electrode ammonia direct fuel cell system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113793963A true CN113793963A (en) | 2021-12-14 |
| CN113793963B CN113793963B (en) | 2023-08-01 |
Family
ID=78877215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110899804.XA Active CN113793963B (en) | 2021-08-06 | 2021-08-06 | Fluidized bed catalytic electrode ammonia direct fuel cell system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113793963B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741310A (en) * | 2005-07-15 | 2006-03-01 | 东南大学 | Method for fluid-bed electrode directly carbon converting fuel battery and converting device |
| US20060248800A1 (en) * | 2002-09-05 | 2006-11-09 | Miglin Maria T | Apparatus and process for production of high purity hydrogen |
| US20060257702A1 (en) * | 2005-05-16 | 2006-11-16 | Clean Coal Energy, Llc | High temperature direct coal fuel cell |
| CN1988229A (en) * | 2006-12-22 | 2007-06-27 | 清华大学 | Buried tube type bubbling bed direct carbon fuel cell |
| CN101694883A (en) * | 2009-09-30 | 2010-04-14 | 华南理工大学 | Direct carbon solid oxide fuel cell |
| CN102004225A (en) * | 2010-09-20 | 2011-04-06 | 东南大学 | Test method and device for half cell of fluid bed electrode direct carbon fuel cell |
| CN102170009A (en) * | 2011-03-29 | 2011-08-31 | 中国华能集团清洁能源技术研究院有限公司 | Solid oxide direct carbon fuel cell stack of tablet bubbling bed |
| CN102324539A (en) * | 2011-08-01 | 2012-01-18 | 清华大学 | Fluid bed electrode direct carbon fuel cell device |
| CN203608136U (en) * | 2013-10-14 | 2014-05-21 | 上海新奥能源科技有限公司 | Co-generation system |
| EP2869381A1 (en) * | 2013-11-01 | 2015-05-06 | Danmarks Tekniske Universitet | An integrated catalytic steam reforming fuel cell electrode |
| US20150316328A1 (en) * | 2012-10-10 | 2015-11-05 | Research Triangle Institute | Particulate heat transfer fluid and related system and method |
| CN105206858A (en) * | 2015-09-14 | 2015-12-30 | 山西宇翔信息技术有限公司 | Fluidized bed electrode carbon fuel cell device and control method thereof |
| CN112117476A (en) * | 2020-07-13 | 2020-12-22 | 东南大学 | Distributed biomass gasification and power generation integrated method and device |
| CN212725394U (en) * | 2020-08-03 | 2021-03-16 | 西安建筑科技大学 | Thermoelectric combined supply device for solid oxide fuel cell |
| CN113097544A (en) * | 2021-04-22 | 2021-07-09 | 西安交通大学 | Solid oxide fuel cell and fluidized bed integrated power generation device and method |
| CN113178605A (en) * | 2021-03-17 | 2021-07-27 | 东南大学 | Fluidized bed anode solid oxide fuel cell |
-
2021
- 2021-08-06 CN CN202110899804.XA patent/CN113793963B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060248800A1 (en) * | 2002-09-05 | 2006-11-09 | Miglin Maria T | Apparatus and process for production of high purity hydrogen |
| US20060257702A1 (en) * | 2005-05-16 | 2006-11-16 | Clean Coal Energy, Llc | High temperature direct coal fuel cell |
| CN1741310A (en) * | 2005-07-15 | 2006-03-01 | 东南大学 | Method for fluid-bed electrode directly carbon converting fuel battery and converting device |
| CN1988229A (en) * | 2006-12-22 | 2007-06-27 | 清华大学 | Buried tube type bubbling bed direct carbon fuel cell |
| CN101694883A (en) * | 2009-09-30 | 2010-04-14 | 华南理工大学 | Direct carbon solid oxide fuel cell |
| CN102004225A (en) * | 2010-09-20 | 2011-04-06 | 东南大学 | Test method and device for half cell of fluid bed electrode direct carbon fuel cell |
| CN102170009A (en) * | 2011-03-29 | 2011-08-31 | 中国华能集团清洁能源技术研究院有限公司 | Solid oxide direct carbon fuel cell stack of tablet bubbling bed |
| CN102324539A (en) * | 2011-08-01 | 2012-01-18 | 清华大学 | Fluid bed electrode direct carbon fuel cell device |
| US20150316328A1 (en) * | 2012-10-10 | 2015-11-05 | Research Triangle Institute | Particulate heat transfer fluid and related system and method |
| CN203608136U (en) * | 2013-10-14 | 2014-05-21 | 上海新奥能源科技有限公司 | Co-generation system |
| EP2869381A1 (en) * | 2013-11-01 | 2015-05-06 | Danmarks Tekniske Universitet | An integrated catalytic steam reforming fuel cell electrode |
| CN105206858A (en) * | 2015-09-14 | 2015-12-30 | 山西宇翔信息技术有限公司 | Fluidized bed electrode carbon fuel cell device and control method thereof |
| CN112117476A (en) * | 2020-07-13 | 2020-12-22 | 东南大学 | Distributed biomass gasification and power generation integrated method and device |
| CN212725394U (en) * | 2020-08-03 | 2021-03-16 | 西安建筑科技大学 | Thermoelectric combined supply device for solid oxide fuel cell |
| CN113178605A (en) * | 2021-03-17 | 2021-07-27 | 东南大学 | Fluidized bed anode solid oxide fuel cell |
| CN113097544A (en) * | 2021-04-22 | 2021-07-09 | 西安交通大学 | Solid oxide fuel cell and fluidized bed integrated power generation device and method |
Non-Patent Citations (2)
| Title |
|---|
| 张秀萍 等: "直接碳燃料电池工艺设计研究进展", 《广州化工》 * |
| 张秀萍 等: "直接碳燃料电池工艺设计研究进展", 《广州化工》, vol. 39, no. 2, 31 January 2011 (2011-01-31), pages 29 - 35 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113793963B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kendall et al. | A small solid oxide fuel cell demonstrator for microelectronic applications | |
| CN104577168B (en) | Methanol water hydrogen production power generation system and hydrogen production power generation method | |
| CN109882737B (en) | Gas-electricity-hydrogen comprehensive energy supply system and method | |
| US9343771B2 (en) | Energy storage device and method for the reversible storage of energy | |
| CN109686998A (en) | Association circulating power generation system based on the cooling fuel cell of gas turbine | |
| CN109956450A (en) | A kind of instant hydrogen generating system of methanol-water and its hydrogen production process | |
| CN112117476A (en) | Distributed biomass gasification and power generation integrated method and device | |
| CN114361505B (en) | Three-runner solid oxide fuel cell unit structure and cell stack | |
| CN103490087A (en) | Tubular type SOFC (Solid Oxide Fuel Cell) stack for portable power supply and assembly method thereof | |
| CN102723516A (en) | Direct carbon fuel cell device with liquid metal tin serving as anode | |
| CN107819141A (en) | Integrated fuel cell system | |
| CN114477229A (en) | Device and method for preparing ammonia by combining atmospheric pressure plasma jet flow and SOEC (Soec) | |
| CN110875711B (en) | Fuel preparation system and method based on photovoltaic and solid oxide fuel cell | |
| CN110410289B (en) | SOFC-GT combined power generation system utilizing solar energy for heat supply and high-temperature thermochemical heat storage | |
| CN209266502U (en) | Association circulating power generation system based on the cooling fuel cell of gas turbine | |
| CN113793963A (en) | Fluidized bed catalytic electrode ammonia direct fuel cell system | |
| CN108155402B (en) | Power generation system and power generation method of solid oxide fuel cell | |
| CN109193007A (en) | Portable direct carbon solid oxide fuel cell power generator | |
| CN205580027U (en) | Heat pump air conditioner based on methanol -water reformation hydrogen manufacturing power generation system | |
| CN109650336B (en) | Hydrogen purification system in on-site hydrogen production fuel cell device | |
| CN114243067A (en) | Direct carbon fuel cell | |
| CN105716326A (en) | Heat pump air conditioning based on power generation system for producing hydrogen by methanol water reforming and heating and refrigerating method | |
| CN113346092B (en) | Fluidized bed electrode solid oxide fuel cell device | |
| Forbes et al. | The solid fuel-cell future | |
| CN111908423A (en) | Thermoelectric power generation coupling methanol-water reforming hydrogen production power generation system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |